Co-reporter:Chun-Yu Liu, Lin-Yan Xu, Zhi-Gang Ren, Hui-Fang Wang, and Jian-Ping Lang
Crystal Growth & Design September 6, 2017 Volume 17(Issue 9) pp:4826-4826
Publication Date(Web):July 24, 2017
DOI:10.1021/acs.cgd.7b00766
Treatment of N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy) with AgX (X = Br, I, CN, SCN, dicyanamide (dca)) under different reaction conditions afforded seven mononuclear, dinuclear, and polymeric coordination complexes including [Ag4I4(3-bdppmapy)2]n (1), [Ag2I2(3-bdppmapy)3]·CH3OH (2·CH3OH), [Ag2Br(3-bdppmapy)3]Br·4CH3OH (3·4CH3OH), [Ag4(CN)4(3-bdppmapy)3]·2CH3OH (4·2CH3OH), [Ag(3-bdppmapy)2]SCN (5), [Ag(3-bdppmapy)2](dca) (6), and {[Ag4(dca)4(3-bdppmapy)2]·4DMF}n (7). Compound 1 contains a unique two-dimensional (2D) network in which chairlike [Ag4I4] units are interconnected by μ3-3-bdppmapy bridges. Compounds 2 and 4 hold a similar centrosymmetric framework in which two [(3-bdppmapy)AgI] (2) or [(3-bdppmapy)Ag2(CN)2] (4) units are linked by a μ-3-bdppmapy. Compound 3 has a batlike cationic structure in which two Ag/3-bdppmapy units are joined by a pair of μ-Br and μ-3-bdppmapy bridges. Compounds 5 and 6 have a similar cationic mononuclear structure in which the Ag(I) center is chelated by two 3-bdppmapy ligands. Compound 7 possesses a 2D layer structure in which each one-dimensional (1D) chain [Ag4(dca)4(3-bdppmapy)2]n is connected to its equivalent ones by μ3-dca bridges. Compound 1 as a representative example exhibited excellent catalytic activity toward the photodecomposition of a spectrum of 11 organic dyes in water under UV light irradiation and can be reused five times without noticeable decay of its catalytic efficiency.
Co-reporter:Qingyun Hu, Congcong Zhuo, Yong Wang, Chuanjiang Hu, and Jianping Lang
Inorganic Chemistry September 5, 2017 Volume 56(Issue 17) pp:10204-10204
Publication Date(Web):August 14, 2017
DOI:10.1021/acs.inorgchem.7b00815
An m-phthalic diamide-linked bisporphyrin with a benzylamide substituent has been designed and synthesized. It has two types of carbonyl groups. In the solution of this zinc bisporphyrinate, these carbonyl groups are involved in the formation of two different Zn–O coordination interactions: one is formed between neighboring zinc bisporphyrinates; another is formed within zinc bisporphyrinate. The chirality sensing abilities of this zinc porphyrinate to a number of chiral monoamines have been examined. When zinc bisporphyrinate was mixed with a series of chiral monoamines, the signs of the circular dichroism spectra for the chiral monoamines of the same handedness with an aryl group as the substituent are just opposite to those with an alkyl group as the substituent. NMR studies reveal that stepwise coordinations lead to 1:1 and 1:2 host–guest complexes. The structure of the 1:1 host–guest complex was confirmed by crystallography, it is the first time that a 1:1 host–guest complex formed between zinc bisporphyrinate and a chiral monoamine has been crystallographically characterized. The structure reveals that there is an intramolecular hydrogen bond between the amide oxygen and the coordinated NH2. We further investigated the chirality transfer mechanism by density functional theory calculations. Our studies suggest that the interactions between the linker and guests in this bisporphyrin system are crucial in the chirality transfer process, and the nature of the bulkiest substituent of chiral monoamines makes a difference. For R-type guests, with an alkyl group, the steric repulsion makes the conformer A more energetically favorable, which leads to the anticlockwise twist and negative Cotton effect. However, with an aryl group, the π–π interaction makes the conformer B more energetically favorable, which leads to the clockwise twist and positive Cotton effect.
Co-reporter:Li-Ming Zhang, Hai-Yan Li, Hong-Xi Li, David James Young, Yong Wang, and Jian-Ping Lang
Inorganic Chemistry September 18, 2017 Volume 56(Issue 18) pp:11230-11230
Publication Date(Web):August 25, 2017
DOI:10.1021/acs.inorgchem.7b01616
Reactions of PdCl2 with 2 equiv of N,N′-disubstituted-imidazole-2-thiones R1R2C3N2S (R1 = R2 = Me (1a), iPr (1b), Cy (1c), C6Me3H2 (1d); R1 = Me, R2 = Ph (1e)) under the different conditions afford five mononuclear complexes trans-[(R1R2C3N2S)2PdCl2] (R1 = R2 = Me (2a), iPr (2b), Cy (2c), C6Me3H2 (2d); R1 = Me, R2 = Ph (2e)) and five binuclear Pd(II) complexes [(PdCl2){μ-(R1R2C3N2S)}]2 (R1 = R2 = Me (3a), iPr (3b), Cy (3c), C6Me3H2 (3d); R1 = Me, R2 = Ph (3e)), respectively. Complexes 2a–2e are easily converted into the corresponding 3a–3e by adding equimolar PdCl2 in refluxing MeOH, while the reverse reaction is achieved at room temperature by addition of 2 equiv of 1a–1e. In 2b, 2d, and 2e, each Pd(II) holds a distorted square planar geometry completed by two trans Cl atoms and two trans S atoms. Complexes 3a–3e have a dimeric [Pd2S2] structure in which two {PdCl2} units are interlinked by two N,N′-disubstituted-imidazole-2-thiones. Each Pd(II) adopts a distorted square planar geometry accomplished by two cis Cl atoms and two cis bridging S atoms. Among them, complex 3d has the two largest C6Me3H2 groups on the 2 and 5 positions of imidazole-2-thione, the longest Pd−μ-S bond, the largest S–Pd–S angle, and displays the highest catalytic activity toward Suzuki–Miyaura and copper-free Sonogashira cross-coupling reactions, which are confirmed by density functional theory calculations. The results provide an interesting insight into the introduction of various substituent groups into the periphery ligands of coordination complex-based catalysts, which could tune their geometric structures to acquire the best catalytic activity toward organic reactions.
Co-reporter:Dan Liu, Fei-Fan Lang, Xuan Zhou, Zhi-Gang Ren, David James Young, and Jian-Ping Lang
Inorganic Chemistry October 16, 2017 Volume 56(Issue 20) pp:12542-12542
Publication Date(Web):October 2, 2017
DOI:10.1021/acs.inorgchem.7b02034
Solvothermal reactions of AgNO3 with N1,N4-bis(5-fluoropyridin-3-yl)succinamide (bfps) in MeCN afforded the one-dimensional cationic coordination polymer {[Ag(bfps)]NO3}n (1). Upon treatment of 1 with the anionic azo dye orange II (NaOII) in aqueous solution, the NO3– anions of 1 could be gradually exchanged by the OII– anions via an anion-exchange process. The resulting OII anion-exchanged products {[Ag(bfps)](NO3)0.85(OII)0.15}n (2) and {[Ag(bfps)](NO3)0.1(OII)0.9}n (3) were formed by different molar ratios of 1 and the newly formed phase “{[Ag(bfps)](OII)}n” (4), confirmed by PXRD patterns. Relative to those of the precursors 1 and NaOII, complexes 2 and 3 demonstrated enlarged photocurrent responses and reduced dielectric constants and dielectric losses, which could be correlated with the OII– contents in their structures. Complex 3 acquired a stable anodic photocurrent of 12.06 μA, which was 4.9 times higher than that of 1. The dielectric constant (εr = 4.2) and dielectric loss (0.002) of 3 were nearly frequency independent in the range from 1 to 106 Hz. The results provide an interesting insight into the rational assembly of CP-dye complexes and their tunable optoelectronic applications.
Co-reporter:Qiu-Fang Chen, Xin Zhao, Quan Liu, Ji-Dong Jia, Xiao-Ting Qiu, Ying-Lin Song, David James Young, Wen-Hua Zhang, and Jian-Ping Lang
Inorganic Chemistry May 15, 2017 Volume 56(Issue 10) pp:5669-5669
Publication Date(Web):April 26, 2017
DOI:10.1021/acs.inorgchem.7b00261
Six analogous two-dimensional (2D) [Tp*WS3Cu3]-based (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) networks, namely, {[(Tp*WS3Cu3)2L3](μ3-N3)}n (2: L = 5-methyltetrazolate (Mtta); 3a: L = 5-ethyltetrazolate (Etta)) and {[(Tp*WS3Cu3)2L3]BF4}n (3b: L = Etta; 4: L = 5-propyltetrazolate (Ptta); 5: L = 5-butyltetrazolate (Btta); 6: L = 5-pentyltetrazolate (Petta)) were synthesized by reactions of [Et4N][Tp*WS3] (1), [Cu(CH3CN)4]BF4, NaN3, and NH4BF4 in different nitrile solvents (CH3(CH2)nCN, n = 0, 1, 2, 3, and 4) under solvothermal conditions. In the structures of 2–6, each alkyl tetrazolate L as a bridging ligand was generated in situ from the “click” reaction between azide and nitrile. These 2D (6,3) networks support two types of voids wherein the pendant alkyl groups are accommodated. A tetrahedron cage-like cluster [Tp*W(μ3-S)3(μ3-S′)Cu3]4 (7) was also formed in some of the above reactions and can be readily separated by solvent extraction. The proportion of 7 increased with the elongation of the alkyl chains and finally became the exclusive product when heptylnitrile was employed. Further use of CuCN as a surrogate for [Cu(CH3CN)4]BF4 with the aim of introducing additional CN bridges into the network led us to isolate a tetrazolate-free compound, {[Et4N]{(Tp*WS3Cu3)[Cu2(CN)4.5]}2·2PhCH2CN}n (8·2PhCH2CN), a unique 2D network that features {(Tp*WS3Cu3)[Cu2(CN)5]}22–, {(Tp*WS3Cu3)3[Cu3(CN)7]2[Cu(CN)3]}4–, and {(Tp*WS3Cu3)[Cu4(CN)9]}26– ring subunits. Compounds 5–8 are soluble in DMF and exhibit a reverse saturable absorption and self-focusing third-order nonlinear optical (NLO) effect at 532 nm with hyperpolarizability γ values in the range of 4.43 × 10–30 to 5.40 × 10–30 esu, which are 400–500 times larger than that of their precursor 1. The results provide an interesting insight into the synergetic synthetic strategy related to the assembly of the [Tp*WS3Cu3]2+ cluster core, the “click” formation of the tetrazolate ligands, and the construction of the [Tp*WS3Cu3]2+ cluster-based 2D networks.
Co-reporter:Feng-Ling Yuan, Yan-Qiu Yuan, Meng-Yao Chao, David J. Young, Wen-Hua Zhang, and Jian-Ping Lang
Inorganic Chemistry June 5, 2017 Volume 56(Issue 11) pp:6522-6522
Publication Date(Web):May 11, 2017
DOI:10.1021/acs.inorgchem.7b00592
The one-pot reaction of Cd(NO3)2·4H2O and 5-(6-(hydroxymethyl)pyridin-3-yl)isophthalic acid (H2L) in DMF/H2O (DMF = N,N-dimethylformamide) produced a two-dimensional (2D) metal–organic framework (MOF) of [Cd(L)(H2O)2] (A) bearing aqua-bridged Cd centers, accompanied by two three-dimensional (3D) MOFs [Cd(L)(DMF)0.5] (B) and [Cd(L)] (C). Removing the bridging aqua molecules of A by heating led to the formation of an additional 3D MOF of [Cd(L)] (D) in a single-crystal to single-crystal (SCSC) manner. The search for the preceding compound that could convert to A resulted in the isolation of a 2D MOF [Cd(L)(DMF)] (E) that readily converted to A in water, but with the loss of single crystallinity. Upon excitation at 350 nm, A, D, E, and the ligand H2L fluoresced at 460 nm, 468 nm, 475 nm, and 411 nm, respectively. The fluorescence of A could be used for the selective detection of Fe3+ in water down to 0.58 ppm. This quenching was not affected by the presence of other common metal ions.
Co-reporter:Wu-Xiang Li, Hong-Xi Li, Hai-Yan Li, Min-Min Chen, Yi-Xiang Shi, and Jian-Ping Lang
Crystal Growth & Design July 5, 2017 Volume 17(Issue 7) pp:3948-3948
Publication Date(Web):May 19, 2017
DOI:10.1021/acs.cgd.7b00575
Solvothermal reactions of Zn(NO3)2·6H2O with 1,4-bis(2-(pyridin-4-yl)vinyl)naphthalene (1,4-bpyvna) and 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC) (molar ratio = 1:1:1) at 120 °C in CH3CN/H2O (v/v = 1:2) afforded one three-dimensional (3D) coordination polymer [Zn2(1,4-bpyvna)(1,3,5-HBTC)2(H2O)]n (1). Similar reactions with the same three components at 140 °C in dimethylformamide (DMF)/CH3CN/H2O produced another 3D coordination polymer {[Zn2(1,4-bpyvna)(1,3,5-BTC)(OH)]·H2O}n (2) in 72% yield. When the molar ratio of Zn(NO3)2·6H2O, 1,4-bpyvna, and 1,3,5-H3BTC was changed to 1:1:2, the analogous treatment at 140 °C yielded one one-dimensional coordination polymer {[Zn(1,3,5-HBTC)2(H2O)][1,4-bpyvna-H2]·CH3CN}n (3, 1,4-bpyvna-H2 = 4,4′-((1,1′)-naphthalene-1,4-diylbis(ethene-2,1-diyl))bis(pyridin-1-ium)). Solvothermal reactions of Zn(NO3)2·6H2O with equimolar 1,4-bpyvna and 1 or 2 equiv of 4,4′-oxidibenzoic acid (4,4′-H2OBA) at 120 °C in DMF/CH3CN/hexane resulted in the formation of {[Zn2(1,4-bpyvna)(4,4′-OBA)2]·0.5DMF·2.25H2O}n (4) and {[Zn2(1,4-bpyvna)(4,4′-OBA)2]·3DMF}n (5), respectively. Compounds 1–5 were characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and thermogravimetric analysis. Upon addition of Hg2+ ions to the DMF solution of 1,4-bpyvna, remarkable changes in the absorbance and emissive spectra were observed, associated with color changes, which were easily identified by the naked eye. This ligand could serve as a chemoprobe with the detection limit of Hg2+ being 0.060 ppm. When solid 2 was added in the DMF solution containing Hg(NO3)2, the emission color of 2 was also changed from blue to yellow, and its detection limit of Hg2+ was as low as 0.057 ppm. This compound can be reused for several cycles without evident efficiency decay. Compound 2 would be a promising sensitive naked-eye indicator for low-concentration Hg2+ with high sensitivity and selectivity.
Co-reporter:Tong-Yu Feng, Hong-Xi Li, David James Young, and Jian-Ping Lang
The Journal of Organic Chemistry April 21, 2017 Volume 82(Issue 8) pp:4113-4113
Publication Date(Web):March 3, 2017
DOI:10.1021/acs.joc.6b03095
RuCl3 efficiently catalyzes the alkylation of methylquinolines, methylpyridines, 2-methyl-benzooxazoles, and 2-methyl-quinoxalines with alkyl- or aryl-alcohols as alkylating agents. This synthetically useful and atom economical transformation does not require additional ligands. The mechanistic study indicated the alkylation reaction underwent a stepwise transfer hydrogenation, aldol condensation, and hydrogenation reaction pathway.
Co-reporter:Shi-Yuan Liu, Lin-Yan Xu, Chun-Yu Liu, Zhi-Gang Ren, David James Young, Jian-Ping Lang
Tetrahedron 2017 Volume 73, Issue 17(Issue 17) pp:
Publication Date(Web):27 April 2017
DOI:10.1016/j.tet.2017.03.022
An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.Download high-res image (162KB)Download full-size image
Co-reporter:Yi-Xiang Shi;Wu-Xiang Li;Huan-Huan Chen;David James Young;Wen-Hua Zhang
Chemical Communications 2017 vol. 53(Issue 40) pp:5515-5518
Publication Date(Web):2017/05/17
DOI:10.1039/C7CC02704D
A protonated mononuclear complex [Zn(Hbpvp)Cl3] (1) is assembled by solvothermal reaction of Zn(NO3)2·6H2O with 3,5-bis-(2-(pyridin-4-yl)vinyl)pyridine (bpvp) in DMF/H2O with a few drops of concentrated HCl added. Hydrogen-bonded zigzag chains of 1 crystallize over time to form large-size hollow hexagonal tubular crystals whose evolution from irregular crystal seeds is monitored by SEM and PXRD. Upon UV light irradiation, single crystals of 1 undergo a stereoselective [2+2] photocycloaddition while its Methyl Blue-coated crystals keep intact.
Co-reporter:Yan-Qiu Yuan;Feng-Ling Yuan;Fei-Long Li;Zhi-Min Hao;Jun Guo;David J. Young;Wen-Hua Zhang
Dalton Transactions 2017 vol. 46(Issue 22) pp:7154-7158
Publication Date(Web):2017/06/06
DOI:10.1039/C7DT01579H
Cuboidal [Ni4O4] clusters supported by a pyridine alkoxide ligand have been developed. One of these clusters was selected as a precursor for carbon-hosted Ni nanoparticles (NiNPs/C) which were efficient catalysts for the conversion of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) at room temperature.
Co-reporter:Wei-Jie Gong;Rui Yao;Hong-Xi Li;Zhi-Gang Ren;Jian-Guo Zhang
Dalton Transactions 2017 vol. 46(Issue 48) pp:16861-16871
Publication Date(Web):2017/12/12
DOI:10.1039/C7DT03876C
Reactions of Cd(NO3)2·4H2O with 1,2,4,5-tetrakis(4-pyridylvinyl)benzene (4-tkpvb) and 5-tert-butylisophthalic acid (5-tert-H2BIPA), 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC) or 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) under solvothermal conditions afforded three two-dimensional (2D) Cd(II) coordination polymers [Cd(4-tkpvb)(5-tert-BIPA)]n (1), [{Cd(4-tkpvb)(1,3,5-HBTC)}·0.5DMF]n (2) and [Cd(4-tkpvb)(1,4-NDC)]n (3). Compounds 1–3 were structurally characterized by IR, elemental analysis, powder X-ray diffraction, and single crystal X-ray diffraction. Compounds 1–3 possess unique 2D networks in which 1D double chains [Cd2L2]n (L = 5-tert-BIPA or 1,3,5-HBTC) (1–2) or 1D linear chains [Cd(1,4-NDC)]n (3) are linked by 4-tkpvb ligands. Upon UV light excitation, a 4-tkpvb solution in DMF showed an emission band centered at 446 nm with a shoulder at 475 nm. The addition of Hg2+ ions into the 4-tkpvb solution in DMF remarkably changed its colour from colourless to yellow under natural light, or from blue to grey yellow under UV light, which were clearly visible to the naked eye. Compounds 1–3 suspended in water could emit yellow-green light under UV light irradiation. The representative compound 1 was confirmed to be an uncommon multi-responsive luminescent sensor for Hg2+, CrO42− and Cr2O72− ions in water by the luminescence quenching method. The detection limits for these species were 0.15 μM (Hg2+), 0.08 μM (CrO42−) and 0.12 μM (Cr2O72−), respectively. The luminescence quenching mechanism studies revealed that these quenching processes were involved in either the interaction of Hg2+ with free pyridyl groups in 1 or the overlap between the absorption band of CrO42− or Cr2O72− and the excitation and/or emission bands of 1.
Co-reporter:Xiao-Yan Tang;Hong Yu;Bin-Bin Gao
Dalton Transactions 2017 vol. 46(Issue 43) pp:14724-14727
Publication Date(Web):2017/11/07
DOI:10.1039/C7DT02679J
Complexation of a preformed complex [Hg(Tab)2](PF6)2 (1) with nicotinic acid in the presence of Et3N afforded a mononuclear complex [Hg(Tab)2(nico)]2(PF6)2 (2) (nico = nicotinate, Tab = 4-(trimethylammonio)benzenethiolate) which, upon subsequent treatment with one or three equiv. of CdCl2·2.5H2O, gave rise to an unprecedented heterometallic cage complex [Cd(H2O)6]@{Cd6Cl4(nico)12[Hg(Tab)2(μ-Cl)]2} (3) or a simple salt of [Hg(Tab)2][CdCl4] (4).
Co-reporter:Xiao-Yan Tang;Hong Yu;Bin-Bin Gao
Dalton Transactions 2017 vol. 46(Issue 43) pp:14724-14727
Publication Date(Web):2017/11/07
DOI:10.1039/C7DT02679J
Complexation of a preformed complex [Hg(Tab)2](PF6)2 (1) with nicotinic acid in the presence of Et3N afforded a mononuclear complex [Hg(Tab)2(nico)]2(PF6)2 (2) (nico = nicotinate, Tab = 4-(trimethylammonio)benzenethiolate) which, upon subsequent treatment with one or three equiv. of CdCl2·2.5H2O, gave rise to an unprecedented heterometallic cage complex [Cd(H2O)6]@{Cd6Cl4(nico)12[Hg(Tab)2(μ-Cl)]2} (3) or a simple salt of [Hg(Tab)2][CdCl4] (4).
Co-reporter:Yu-Ting Wang;Bin-Bin Gao;Fan Wang;Shi-Yuan Liu;Hong Yu;Wen-Hua Zhang
Dalton Transactions 2017 vol. 46(Issue 6) pp:1832-1839
Publication Date(Web):2017/02/14
DOI:10.1039/C6DT04599E
The integration of a geometrically rigid Pd(II), a coordinatively monotonous N-heterocyclic carbene 1,3-dimethylimidazoline-2-ylidene (IMe), and a flexible zwitterionic thiolate 4-(trimethylammonio)benzenethiolate (Tab) affords a class of Pd–IMe–Tab complexes with various nuclearities, namely, trans-[Pd(IMe)2(Tab)2](OTf)2 (2, mononuclear), cis-[Pd(IMe)2(Tab)2](OTf)(Cl) (3a, mononuclear), cis-[Pd(IMe)2(Tab)2](PF6)2·MeCN (3b·MeCN, mononuclear), [Pd2(IMe)4(Tab)2](PF6)4·2MeCN (4·2MeCN, dinuclear) and [Pd4(IMe)4(Tab)6](OTf)6(Cl)2 (5, tetranuclear). Further presence of Ag(I) in the assembly provides a heterometallic octanuclear cluster of [Pd4Ag4(IMe)8(Tab)10](PF6)12 (6). Compounds 2–6 are formed by the reaction of trans-Pd(IMe)2Cl2 (1) with various additional reagents via different reaction pathways. These compounds are characterized by means of FT-IR, 1H and 13C NMR, ESI-MS, elemental analysis and X-ray crystallography. Notably, the skeleton of compound 5 features a [Pd4S4] parallelogram wherein each of the four Pd(II) centers bisects the edge defined by the S atoms. The main skeleton of compound 6 is an oval-shaped Pd4Ag4S10 unit, featuring an edge-fused norbornane-like (Pd2Ag4S6) framework appended by two additional PdS2 motifs at the polar positions. Compounds 5 and 6 also feature Pd⋯Pd (5), Pd⋯Ag and Ag⋯Ag (6) interactions. Compound 5 as a representative example is highly effective at catalyzing Suzuki–Miyaura couplings in water, highlighting the potential of applying these types of homo- and heterometallic clusters as catalysts for organic transformations in environmentally benign media.
Co-reporter:Sze-Ling Lee;Fei-Long Hu;Xiu-Juan Shang;Yi-Xiang Shi;Ai Ling Tan;Jens Mizera;Jack K. Clegg;Wen-Hua Zhang;David J. Young
New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 23) pp:14457-14465
Publication Date(Web):2017/11/20
DOI:10.1039/C7NJ03571C
A series of Fe(III) complexes of β-diketonate ligands, 1-(2-pyridyl)-3-(3-pyridyl)-1,3-propanedione (L1), 1-(2-pyridyl)-3-(2-pyridyl)-1,3-propanedione (L2), 1-(2-pyridyl)-3-(4-pyridyl)-1,3-propanedione (L3), 1-(3-pyridyl)-3-(4-pyridyl)-1,3-propanedione (L4), 1-(3-pyridyl)-3-(3-pyridyl)-1,3-propanedione (L5) and 1-(4-pyridyl)-3-(4-pyridyl)-1,3-propanedione (L6), viz. [Fe(L1)3] (1), [Fe(L2)3] (2), [Fe(L3)3] (3), [Fe(L4)3] (4), [Fe(L5)3] (5) and [Fe(L6)3] (6) have been structurally characterized. All but one complex (1) catalyzed the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) in near quantitative yield at 110 °C to give polymers with relatively narrow polydispersities (PDI). The comparison of in situ reaction and a reaction with preformed 1 indicated that the latter was a better catalyst, giving a higher molecular weight. Complex 2 catalyzed this reaction in a more modest yield reflecting its greater thermal stability, shorter Fe–O bonds and minimal distortion in fold angle among the isomeric complexes, suggesting that ligand dissociation is important for catalytic activity.
Co-reporter:Quan Liu, Wen-Hua Zhang, Jian-Ping Lang
Coordination Chemistry Reviews 2017 Volume 350(Volume 350) pp:
Publication Date(Web):1 November 2017
DOI:10.1016/j.ccr.2017.06.027
•More than 50 cyanide-ligated Mo(W)–Cu–S compounds are summarized.•CuCN can be worked as a good metalloligand for Mo(W)–Cu–S–CN assemblies.•CN and Cu+ coordination flexibility lead to structural variety and unpredictability.•The cluster assemblies with CN ligands exhibit excellent NLO performances.Cyanide (CN) assumes a unique role in the development of coordination chemistry, with the first CN-based coordination polymer dye Prussian blue as a milestone example. In this review, we discuss the structures of a rich class of Mo(W)–Cu–S clusters, cluster-based oligomers, 1D, 2D and 3D coordination polymers bearing CN ligands. The stable Mo(W)–Cu–S cluster skeletons in conjugation with the strong Cu–CN linkages offer enhanced stability of these cluster species, making them good nonlinear optical materials.The structures of cyanide-ligated discrete Mo(W)–Cu–S clusters, cluster-based oligomers, one-dimensional, two-dimensional and three-dimensional coordination polymers are summarized and their third-order nonlinear optical properties are discussed.Download high-res image (153KB)Download full-size image
Co-reporter:Lin-Yan Xu, Chun-Yu Liu, Shi-Yuan Liu, Zhi-Gang Ren, David James Young, Jian-Ping Lang
Tetrahedron 2017 Volume 73, Issue 22(Issue 22) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.tet.2017.04.034
•Compound 1 is a PdCl2 adduct of N-diphenylphosphanyl-2-aminopyridine.•Compound 1 can catalyze the reactions of aryl chlorides with aryl boronic acids.•This catalytic system is suitable for a wide scope of substrates.One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-aminopyridine (L1) [(L1)PdCl2] (1) has been prepared and structurally characterized. Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded to give desired products in good to excellent yields.Download high-res image (91KB)Download full-size image
Co-reporter:Wei-Jie Gong, Zhi-Gang Ren, Hong-Xi Li, Jian-Guo Zhang, and Jian-Ping Lang
Crystal Growth & Design 2017 Volume 17(Issue 2) pp:
Publication Date(Web):December 20, 2016
DOI:10.1021/acs.cgd.6b01728
Solvothermal reactions of Cd(NO3)2·4H2O with 4-pyr-poly-2-ene (ppene) in the presence of benzene-1,2-dicarboxylic acid (1,2-H2BDC), benzene-1,3-dicarboxylic acid (1,3-H2BDC), benzene-1,4-dicarboxylic acid (1,4-H2BDC), benzene-1,3,5-tricarboxylic acid (1,3,5-H3BTC), or 4,4′-oxidibenzoic acid (4,4′-H2OBA) afforded five Cd(II) coordination polymers [Cd(ppene)(1,2-BDC)]n (1), [Cd(ppene)(1,3-BDC)]n (2), [{Cd(ppene)(1,4-BDC)}·MeCN]n (3) (Liu et al. Inorg. Chem. Commun. 2015, 58, 1−4), [{Cd(ppene)(1,3,5-HBTC)}·0.5(ppene)]n (4), and [Cd(ppene)(4,4′-OBA)]n (5), respectively. Upon UV light irradiation, 1, 3, and 4 can undergo a double [2 + 2] cycloaddition reaction to yield their corresponding photoproducts including [Cd2(4-tp-3-lad)(1,2-BDC)2]n (1a, 4-tp-3-lad = 2,3,5,6-tetra(pyridin-4-yl)bicyclo[2.2.0]hexane), [{Cd2(4-tp-3-lad)(1,4-BDC)2}·2MeCN]n (3a), and [{Cd2(4-tp-3-lad)(1,3,5-HBTC)2}·(ppene)]n (4a) in a single-crystal-to-single-crystal manner. Compounds 1, 2, 4, 5, 1a, 3a, and 4a have been structurally characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1, 1a, 4 and 4a consist of two-dimensional (2D) (4,4) networks, in which one-dimensional (1D) [Cd2(1,2-BDC)2]n or [Cd2(1,3,5-HBTC)2]n chains are linked by ppene or 4-tp-3-lad bridges. 2 has a three-dimensional (3D) 3-fold interpenetrated framework formed from bridging 1D [Cd2(1,3-BDC)2]n double chains by ppene ligands. Compounds 3a and 5 contain 3D frameworks assembled by linking 2D [Cd2(1,4-BDC)2]n or [Cd2(4,4′-OBA)2]n networks by 4-tp-3-lad or ppene bridges. In the three photoreactions, each ppene ligand had its two conjugated C═C bonds parallel to those of the neighboring ppene. The resulting ppene pair was transformed into the only product, 4-tp-3-lad, through a unique double [2 + 2] cycloaddition. Photoluminescence properties of these compounds in water were also investigated. Compound 3a as a representative example was proven to be an efficient probe for dual detections of nitroaromatics and Hg2+ in aqueous solutions.
Co-reporter:Jun Gao, Zhi-Gang Ren, Jian-Ping Lang
Chinese Chemical Letters 2017 Volume 28, Issue 5(Volume 28, Issue 5) pp:
Publication Date(Web):1 May 2017
DOI:10.1016/j.cclet.2016.12.035
A green protocol for the synthesis of quinoxalines has been developed from catalytic oxidative cyclization of deoxybenzoins with 1,2-phenylenediamines in water. The optimal conditions are involved in the use of a water-soluble mononuclear copper(II) complex of a zwitterionic calix[4]arene [Cu(II)L(H2O)]I2 (1, H4L = [5,11,17,23–tetrakis (trimethylammonium)–25,26,27,28–tetrahydroxycalix[4]arene]) as a catalyst in alkali solution after refluxing for 15 h in O2. The target quinoxaline and its derivatives were obtained in good yields (up to 88%). The procedure described in this paper is simple, practical and environmentally benign.Download high-res image (71KB)Download full-size imageThe oxidative cyclization of deoxybenzoins with 1,2-phenylenediamines to form quinoxalines is catalyzed by a mononuclear copper(II) complex of zwitterionic calix[4]arene.
Co-reporter:Fei-Long Hu, Hui-Fang Wang, Dong Guo, Hui Zhang, Jian-Ping Lang and Jonathon E. Beves
Chemical Communications 2016 vol. 52(Issue 51) pp:7990-7993
Publication Date(Web):03 May 2016
DOI:10.1039/C6CC03256G
A 3D coordination polymer {[Cd(L1)(L2)]2}n (1) spontaneously resolves into enantiomorphic crystals of 1P and 1M without any chiral source. Bulk quantities of 1P and 1M can be predictably and reliably obtained by using chiral cyclohexane-1,2-diamine. 1 can be transformed into {[Cd(L1)(L3)0.5]2}n (2) by highly selective [2+2] photodimerization of L2 ligands. The reverse process can be achieved by microwave irradiation. The cycloreversion/cycloaddition cycles result in chiroptical switching behavior.
Co-reporter:Fan Wang, Yu-Ting Wang, Hong Yu, Jin-Xiang Chen, Bin-Bin Gao, and Jian-Ping Lang
Inorganic Chemistry 2016 Volume 55(Issue 18) pp:9417-9423
Publication Date(Web):August 31, 2016
DOI:10.1021/acs.inorgchem.6b01688
Reaction of AgBr with TabHPF6 (TabH = 4-(trimethylammonio)benzenethiol) readily produces a unique one-dimensional coordination polymer [(TabH)(AgBr2)]n (1), consisting of anionic chains [AgBr2]nn– with hydrogen bonds to TabH+ cations. By examining its electrical resistance and stability upon exposure to ammonia and seven common organic amines in water under ambient conditions, compound 1 is found to exhibit good stability and reproducibly high sensitivity toward these analytes at low concentrations. Especially, it can selectively detect NH3 in water with the detection limit as low as 0.05 ppm. This chemiresistive sensing system has the potential for highly efficient monitoring of ammonia and amines responsible for water pollution, eutrophication, food contamination, and industrial hazards.
Co-reporter:Xin Zhao, Feng Zhou, Quan Liu, Qiu-Fang Chen, Jun-Yi Yang, Wen-Hua Zhang, Ying-Lin Song, and Jian-Ping Lang
Inorganic Chemistry 2016 Volume 55(Issue 4) pp:1861-1871
Publication Date(Web):January 26, 2016
DOI:10.1021/acs.inorgchem.5b02765
In the absence/presence of S8, the one-pot assembly of [Et4N][Tp*WS3] [1; Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis- or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N′,N′-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W–Cu–S clusters, namely, [(Tp*WS3Cu2Cl)2(dppe)] (2), [Tp*WS3Cu4(dppp)2(μ4-Cl)(μ-Cl)]PF6·MeCN (3·MeCN), [(Tp*WS3Cu3)2(μ4-Cl)(μ-Cl)2(dpppS2)] (4), [(Tp*WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp*WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp*WS3Cu3)2(Ph2PS2)3(μ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2–7 are characterized by elemental analysis, IR, UV–vis, 1H and 31P{1H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp*WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2]− anions. Three [Ph2PS2]− anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ6-Cl–. The third-order nonlinear-optical (NLO) properties of 2–7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2–6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2–7 exhibit a self-focusing effect with hyperpolarizability γ values in the range of 4.71 × 10–30–1.02 × 10–29 esu, which are 440–1000 times higher than that of 1. The formation of 4–7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W–Cu–S clusters with interesting structural arrays and better NLO properties.
Co-reporter:Jun-Chi Li, Hong-Xi Li, Hai-Yan Li, Wei-Jie Gong, and Jian-Ping Lang
Crystal Growth & Design 2016 Volume 16(Issue 3) pp:1617
Publication Date(Web):January 14, 2016
DOI:10.1021/acs.cgd.5b01721
A series of ((pyridinyl)-1H-pyrazolyl)pyridine (pypzpy) ligands in which the pyrazolyl ring at 1- and 3-positions is modified by two 2-, 3-, or 4-pyridyl groups were prepared. Reaction of CuI with 2-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (2,2′-pypzpy) in MeCN at room temperature or solvothermal reaction of the same components at 120 °C afforded one binuclear complex [{(2,2′-pypzpy)Cu}(μ-I)]2 (1). Treatment of CuI with 3-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (3,2′-pypzpy) at room temperature or at 120 °C produced one-dimensional (1D) polymer [{Cu3(μ3-I)3}(μ-3,2′-pypzpy)]n (2) and one two-dimensional (2D) polymer [{Cu2(μ-I)(μ3-I)}2(3,2′-pypzpy)2]n (3), respectively. Similar reactions of CuI with 4-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (4,2′-pypzpy) at room temperature or at 150 °C yielded one 1D polymeric complex [{Cu(μ3-I)}2(4,2′-pypzpy)2{Cu(μ-I)}2]n (4). Complexes [{Cu3(μ3-I)3}(μ-2,3′-pypzpy)]n (5), [(CuI)(μ-2,3′-pypzpy)]2 (6), [(Cu2I2)(3,3′-pypzpy)] (7), [(CuI)(4,3′-pypzpy)] (8), [{Cu(μ3-I)}2(μ-2,4′-pypzpy)2{Cu(μ-I)}2]n (9), [(CuI)(3,4′-pypzpy)] (10), and [(CuI)(μ-4,4′-pypzpy)]n (11) could be isolated by solution reactions or solvothermal reactions of CuI with 2-, 3-, 4-(1-(pyridin-3-yl)-1H-pyrazolyl)pyridine (2,3′-, 3,3′-, 4,3′-pypzpy), or 2-, 3-, 4-(1-(pyridin-4-yl)-1H-pyrazolyl)pyridine (2,4′-, 3,4′-, 4,4′-pypzpy). Compounds 1–11 were characterized by IR, elemental analysis, powder X-ray diffraction, and single-crystal X-ray crystallography. Complex 1 contains a normal [Cu(μ-I)]2 dimeric structure. Complexes 2 and 5 consist of a unique displaced staircase chain [Cu2(μ3-I)2]n. Complex 3 has a 2D network formed by linking chairlike [Cu2(μ-I)(μ3-I)]2 units with two pairs of 3,2′-pypzpy bridges. Complexes 4 and 9 have a rare 1D triple chain, in which one internal 1D ladder-like chain [Cu2(μ3-I)2]n is connected with two zigzag chains [Cu(μ-I)]n via 4,2′-pypzpy or 2,4′-pypzpy ligands. Compound 6 consists of two [CuI] units interconnected by two 2,3′-pypzpy ligands. Compound 11 contains a 1D chain assembled by monomeric [CuI] units and 4,4′-pypzpy ligands. The luminescence properties of 1–11 in solid state were also investigated at room temperature. These results offer an interesting insight into how the coordination sites of the pypzpy ligands do exert great impact on their coordination modes, the coordination spheres of the Cu(I) centers, the formation of the [CunIn] motifs and the topological structures of the final complexes.
Co-reporter:Jian-Feng Wang, Shi-Yuan Liu, Chun-Yu Liu, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2016 vol. 45(Issue 22) pp:9294-9306
Publication Date(Web):04 May 2016
DOI:10.1039/C6DT01211F
Reactions of a P–N hybrid ligand, N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy), with silver oxysalts including AgNO3, AgOAc, AgBz (Bz = benzoate) and AgSal (Sal = salicylate) under different reaction conditions give rise to seven coordination compounds {[Ag4(μ–η,η-NO3)2(μ–η,η2-NO3)2](3-bdppmapy)2}n (1), {[Ag4(μ–η,η2-NO3)4](3-bdppmapy)2}n (2), {[Ag2(μ–η2-OAc)(μ–η,η2-OAc)]2(3-bdppmapy)2}n (3), [Ag2(Bz)(μ–η,η2-Bz)(H2O)]2(3-bdppmapy)2 (4), {[Ag4(μ–η2-Bz)2(μ–η,η2-Bz)2](3-bdppmapy)2}n (5), {Ag(Sal)(3-bdppmapy)}n (6) and {[Ag4(Sal)2(μ–η,η2-Sal)2](3-bdppmapy)2}n (7). Single crystal X-ray analyses reveal that 1, 5 and 7 have similar 1D chain structures constructed by [Ag4(μ–η2-Ox)2(μ–η,η2-Ox)2] units (1: Ox− = NO3−; 5: Ox− = Bz−) or [Ag4(Sal)2(μ–η,η2-Sal)2] units (7) and double 3-bdppmapy bridges. Compound 2 has a 2D layer structure derived from [Ag4(μ–η,η2-NO3)4] units and single 3-bdppmapy bridges. 3 displays another 2D layer structure formed by [Ag2(μ–η2-OAc)(μ–η,η2-OAc)] units and double 3-bdppmapy bridges. 4 shows a discrete tetranuclear structure formed by two [Ag2(Bz)(η,η2,μ-Bz)(H2O)] units and a pair of 3-bdppmapy bridges, while 6 adopts a 1D chain composed by [AgSal] units and single 3-bdppmapy bridges. 6 and 7 as representative samples display high catalytic activity toward the photodegradation of rhodamine B (RhB) in water. Compound 7 shows a better photocatalytic performance than that of 6, which correlates well with the differences in their anodic photocurrent responses and their HOMO–LUMO energy gaps derived from the density function theory (DFT) calculations. The formation of 6 and 7 from AgSal and 3-bdppmapy provides a new approach to the design and assembly of Ag(I)-supported CPs with interesting structural architectures and higher photocatalytic activity.
Co-reporter:Hong-Jian Cheng, Xiao-Yan Tang, Rong-Xin Yuan and Jian-Ping Lang
CrystEngComm 2016 vol. 18(Issue 25) pp:4851-4862
Publication Date(Web):09 May 2016
DOI:10.1039/C6CE00768F
Eight Zn(II) coordination polymers with 5-R-1,3-benzenedicarboxylate (R = H, Br) ligands and bis-imidazolyl ligands, {[Zn(1,3-BDC)(abimb)]·H2O}n (1), {[Zn(5-Br-1,3-BDC)(abimb)]2·0.5H2O}n (2), [Zn(1,3-BDC)(nbimb)]n (3), [Zn(5-Br-1,3-BDC)(nbimb)]n (4), {[Zn(1,3-BDC)(bimpa)]·2H2O}n (5), {[Zn(5-Br-1,3-BDC)(bimpa)]·2H2O}n (6), [Zn(1,3-BDC)(bimcz)]n (7) and [Zn(5-Br-1,3-BDC)(bimcz)]n (8) (1,3-H2BDC = 1,3-benzenedicarboxylate; 5-Br-1,3-H2BDC = 5-bromo-1,3-benzenedicarboxylate; abimb = 2-amine-4,4′-bis(1-imidazolyl)-bibenzene; nbimb = 2-nitro-4,4′-bis(1-imidazolyl)-bibenzene; bimpa = bis-(4-imidazol-1-yl-phenyl)-amine; bimcz = 3,6-bis(1-imidazolyl)-carbazole), have been synthesized and structurally characterized by elemental analysis, IR and X-ray single crystal diffraction. 1 and 6 exhibit 4-connected 3D frameworks with the Schläfli symbol (65·8). 2, 7 and 8 display 3D polythreaded networks based on 2D wrinkled layers. 3 and 4 show 3D polycatenated arrays based on 2D puckered layers. 5 has a 3D supramolecular structure consisting of two-fold parallel interwoven layers through hydrogen bonding and π⋯π stacking interactions. The solid state photoluminescence and photocatalytic properties of 1–8 were also investigated.
Co-reporter:Bing Wu, Wen-Hua Zhang and Jian-Ping Lang
CrystEngComm 2016 vol. 18(Issue 17) pp:3048-3054
Publication Date(Web):21 Mar 2016
DOI:10.1039/C6CE00187D
By utilizing the coordination unsaturation of 1,2,3-benzenetricarboxylate (1,2,3-BTA) and protonated N,N′-di(3-pyridyl)succinamide (L) in the as-synthesized 1D coordination polymer (CP) of [(H2L)0.5][Zn(1,2,3-BTA)(H2O)]·2H2O (1), we successfully doped an additional half equivalent of Zn2+ and Co2+ ions to yield [Zn3L(1,2,3-BTA)2(H2O)6]·4H2O (2) and [Zn2CoL(1,2,3-BTA)2(H2O)6]·4H2O (2c). Compounds 2 and 2c are also possible through direct one-pot metal–ligand assembly. With the one-pot method, [Zn2.76Co0.24L(1,2,3-BTA)2(H2O)6]·4H2O (2a) and [Zn2.40Co0.60L(1,2,3-BTA)2(H2O)6]·4H2O (2b) are accordingly prepared to demonstrate the universality of hetero-metallic doping and for probing the doping effect on photocurrent responses. Compounds 2, 2a–2c are 2D CPs formed by linking 1,2,3-BTA-based 1D chains through L ligands. Their photocurrent responses were found to be positively related to the Co2+ percentage of the doped materials.
Co-reporter:Fei-Long Li, Hong-Xi Li and Jian-Ping Lang
CrystEngComm 2016 vol. 18(Issue 10) pp:1760-1767
Publication Date(Web):01 Feb 2016
DOI:10.1039/C5CE02219C
In this work, we fabricate new yolk–shell Pd@ZIF-8 (ZIF = zeolitic imidazolate framework) nanoparticles (NPs) through reactions of the preformed core–shell Pd@ZnO NPs with 2-methylimidazole under mild conditions. In this method, ZnO is used as the self-template and the Zn2+ source for the formation of the ZIF-8 shell. The morphology, composition and structure of the as-prepared yolk–shell nanomaterial are characterized by scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, powder X-ray diffraction, energy dispersive X-ray spectroscopy, and inductively coupled plasma atomic emission spectroscopy. The formation of this well-defined yolk–shell nanostructure is highly dependent on the solvent system and reaction time. This nanomaterial can be employed as an excellent heterogeneous catalyst for the liquid-phase hydrogenation of olefins with high size-selectivity at room temperature, which is mainly due to the inherent porous structure of the outer ZIF-8 shell along with the enclosed Pd NPs. The nanocatalyst system can be recycled at least three times without any evident loss of the catalytic efficiency.
Co-reporter:Quan Liu, Xin Zhao, Feng Zhou, Ying-Lin Song, Wen-Hua Zhang, and Jian-Ping Lang
Crystal Growth & Design 2016 Volume 16(Issue 6) pp:3206-3214
Publication Date(Web):May 6, 2016
DOI:10.1021/acs.cgd.6b00115
We have prepared a family of [WS3Cu2]-based coordination polymers with a rare μ-N type coordination by a simple one-pot assembly of [Et4N][Tp*WS3] (1) with CuCN in the presence of pyridine (py), 4,4′-bipyridine (bipy), 1,2-bis(4-pyridyl)ethane (bpea), and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) at room temperature. The resulting coordination polymers [Tp*WS3Cu2(CN)(μ-py)]2·py (2·py), [Tp*WS3Cu2(CN)2Cu(μ-py)2]2·3py (3·3py), [Et4N][{Tp*WS3(CuCN)2Cu}2(CN)(μ4-bipy)] (4), [Tp*WS3Cu2(CN)(μ4-bpea)0.5]2·CH2Cl2 (5·CH2Cl2), and [Tp*WS3Cu2(CN)(μ6-tpt)1/3]2 (6) share a butterfly-shaped [Tp*WS3Cu2] motif with sizable concave to accommodate pyridyl ligands. The approximate mirror symmetry of the motif also induces the orthogonal coalignment of the pyridyl ligands, reinforcing a unique μ-type association with the Cu centers of the cluster skeleton. Such a coordination mode, though scarce in general coordination chemistry, is universal in our series with good ligand tolerance including ligand size and symmetry. In addition, each butterfly-shaped [Tp*WS3Cu2] motif is linked by CN (2), Cu(CN)2 (3), Cu2(CN)5/μ4-bipy (4), CN/μ4-bpea (5), and CN/μ6-tpt (6) to yield diverse polydimensional structures showing one-dimensional zigzag chains (2 and 3), two-dimensional networks (4 and 5), and a three-dimensional net (6). The third-order nonlinear optical (NLO) property of 2–6 in DMF measured using a Z-scan technique at 532 nm demonstrated that 2–6 have a reverse saturable absorption and self-focusing effects with the hyperpolarizability γ values in the range of 6.32 × 10–30 esu to 9.82 × 10–30 esu. Such values are remarkably larger than that of their precursor complex 1 (1.07 × 10–32 esu). The results provide an interesting insight into how the μ-type coordination mode of N-donor ligands affects the self-assembly of the [Tp*WS3Cu2]-supported coordination polymers and their structural topologies, as well as their third-order NLO performances.
Co-reporter:Bin Guo, Jiang-Yan Xue, Hong-Xi Li, Da-Wei Tan and Jian-Ping Lang
RSC Advances 2016 vol. 6(Issue 57) pp:51687-51693
Publication Date(Web):20 May 2016
DOI:10.1039/C6RA10373A
Four different types of TEMPO derivatives incorporated with an ionic liquid moiety and N,N-bidentate coordination group (IL–TEMPO-N,N) were prepared. The CuBr/IL–TEMPO-N,N system showed high catalytic activity toward the synthesis of aldehydes and imines via the aerobic oxidation of alcohols in 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4). Both the Cu catalyst and IL–TEMPO-N,N co-catalyst in homogeneous catalytic systems could simultaneously be recovered from the products by extraction using Et2O. The remaining catalyst system in the ionic liquid phase could be reused for several cycles without obvious loss of catalytic activity. Protocols for highly efficient and recyclable aerobic oxidation of alcohols to aldehydes and imines were established.
Co-reporter:Xiu-Juan Shang, Wen-Hua Zhang and Jian-Ping Lang
RSC Advances 2016 vol. 6(Issue 14) pp:11400-11406
Publication Date(Web):20 Jan 2016
DOI:10.1039/C5RA22279F
We herein report an interesting cooperative catalytic system containing iron powder and 2-hydroxyethyl 2-bromoisobutyrate (HEBiB), which can efficiently catalyze the ring-opening polymerization of ε-caprolactone (CL) under facile conditions, forming poly(ε-caprolactone) (PCL) with appreciably high molecular weight (Mn), narrow molecular weight distribution and high yield. The 1H NMR and GPC (gel permeation chromatography) measurements of the resulting PCL clearly indicate the presence of the initiator residue at the chain end. Optimization reactions, wherein iron powder or HEBiB alone, the combinative use of iron powder and benzyl alcohol (BnOH), iron powder and alkyl bromides in the absence/presence of benzyl alcohol (BnOH) are introduced, reveal that iron and alkyl bromides collectively initiate the reaction and define the molecular weight of PCL, while the presence of the hydroxyl group leads to higher product yields. The effects of metal contaminants, hydroxyl initiators, solvents, reaction temperatures and reaction times are also investigated. The kinetic and chain extension experiments support the controlled/living nature of the HEBiB/Fe-catalyzed ROP of CL.
Co-reporter:Zhong-Lin Xu, Hong-Xi Li, Zhi-Gang Ren, Wei-Yuan Du, Wei-Chang Xu, Jian-Ping Lang
Tetrahedron 2016 Volume 72(Issue 52) pp:8637
Publication Date(Web):29 December 2016
DOI:10.1016/j.tet.2016.11.048
Co-reporter:Jiang-Yan Xue, Jun-Chi Li, Hong-Xi Li, Hai-Yan Li, Jian-Ping Lang
Tetrahedron 2016 Volume 72(Issue 44) pp:7014-7020
Publication Date(Web):3 November 2016
DOI:10.1016/j.tet.2016.09.032
Four anionic ligands including 1-methyl-3(or 4)-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide ([3,2′-pypzpym]I, [4,2′-pypzpym]I) and 1-methyl-3(or 4)-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide ([2,3′-pypzpym]I, [2,4′-pypzpym]I) are prepared. Reaction of CuI with [3,2′-pypzpym]I affords a mononuclear complex [CuI2(3,2′-pypzpym)] (1) and a one-dimensional coordination polymer [(Cu4I6)(3,2′-pypzpym)2]n (2). Analogous reactions of CuI with [4,2′-pypzpym]I, [2,3′-pypzpym]I or [2,4′-pypzpym]I yield [Cu4I6(4,2′-pypzpym)2] (3), [CuI2(2,3′-pypzpym)] (4) and [CuI2(2,4′-pypzpym)] (5), respectively. Relative to that of CuI, complexes 1–5 exhibit enhanced catalytic activities towards the Chan–Lam cross-coupling reactions of imidazole and arylboronic acids in a H2OMeCN (v/v=2:1). This catalytic system is involved in the CN cross-coupling reaction and works for a variety of imidazole derivatives as well as arylboronic acids with different electronic properties.
Co-reporter:Da-Wei Tan, Hong-Xi Li, David James Young, Jian-Ping Lang
Tetrahedron 2016 Volume 72(Issue 29) pp:4169-4176
Publication Date(Web):21 July 2016
DOI:10.1016/j.tet.2016.05.036
Without using any additional ligands, RuCl3 efficiently catalyses the reductive N-alkylation of aryl nitro compounds with alcohols using bio-based glycerol as the hydrogen source and without the need for any added solvents. The reaction can be easily manipulated to produce either imines or secondary amines in high yields. RuCl3-catalyzed reductive N-alkylation of nitroarenes with alcohols affords the corresponding imine products in good to excellent yields. Under the same reaction conditions, the one-pot sequential reaction of nitroarenes with alcohols and glycerol also gives amines in higher yields.
Co-reporter:Wen-Hua Zhang, Quan Liu, Jian-Ping Lang
Coordination Chemistry Reviews 2015 Volumes 293–294() pp:187-210
Publication Date(Web):15 June 2015
DOI:10.1016/j.ccr.2014.12.010
•The C3 symmetry of Tp and Tp* is essential in forming clusters.•Mo(W)-Cu-S version of biologically relevant PN-type clusters are discussed.•Some clusters are promising building blocks for cluster-based coordination polymers.•Cluster-based coordination polymers show enhanced NLO performances upon assembly.This review summarizes the uses of Tp- and Tp*-based Mo(W) sulfido precursor compounds, namely, [Et4N][Tp*WS3] (P1), [Et4N][Tp*MoS(S4)] (P2), [Et4N][TpMoS(S4)] (P3) and [(Tp*WS2)2(μ-S2)] (P4) for the assembly of a diverse class of heterometallic clusters, predominantly Mo(W)-Cu-S clusters. Some of these clusters also feature as building blocks for cluster-supported coordination polymers to achieve enhanced third-order nonlinear optical performances.In this review, the synthesis of a family of heterometallic Mo(W)-Cu-S clusters from four Tp- and Tp*-based Mo(W) sulfido precursor compounds is described. The assembly of Mo(W)-Cu-S cluster-supported coordination polymers using some of these discrete clusters as building blocks is also summarized. Their specific structures are briefly illustrated. In addition, the third-order nonlinear optical properties of some of these clusters and cluster-supported coordination polymers are discussed.
Co-reporter:Fan Wang, Fu-Ling Li, Miao-Miao Xu, Hong Yu, Jian-Guo Zhang, Hai-Tao Xia and Jian-Ping Lang
Journal of Materials Chemistry A 2015 vol. 3(Issue 11) pp:5908-5916
Publication Date(Web):03 Feb 2015
DOI:10.1039/C5TA00302D
Ambient temperature solid state reaction of a preformed compound {[Pb(Tab)2]2(PF6)4}n (1) (TabH = 4-(trimethylammonio)benzenethiol) with two equiv. of 1,2-bis(4-pyridyl)ethylene (bpe) quantitatively produces a unique two-dimensional coordination polymer {[Pb(Tab)2(bpe)]2(PF6)4}n (2). The Ag(I)-doped coordination polymer {[Pb(Tab)2(bpe)]2(PF6)4·1.64AgNO3}n (2a) is readily prepared by immersing 2 into AgNO3 aqueous solution. Compared with its two precursors 1 and 2, 2a exhibits greatly enhanced catalytic activity towards the photodegradation of a family of 12 azo dyes within a short period of time under UV light irradiation and excellent adaptability on the elimination of azo dyes in water. It is anticipated that the ‘Ag(I)-doping’ synthetic strategy reported in this work may be applicable to other coordination polymer systems containing thiolate ligands for the preparation of various metal ion-doped multidimensional coordination polymers with new topological structures and better catalytic performances in the photodecomposition of azo dyes in industrial wastewater.
Co-reporter:Wang Yao, Fei-Long Li, Hong-Xi Li and Jian-Ping Lang
Journal of Materials Chemistry A 2015 vol. 3(Issue 8) pp:4578-4585
Publication Date(Web):08 Jan 2015
DOI:10.1039/C4TA06378C
We report the synthesis of unique Au–Pd bimetallic alloy nanoparticles (NPs) supported on a hollow Cu2O–CuO core–shell heterostructure via the galvanic replacement method, which represents the first example of Au–Pd alloy nanoparticles immobilized on hollow Cu2O@CuO nanocubes. The morphological evolution can be controlled by the reaction time. The morphology, composition, and structure of the as-prepared Cu2O@CuO/(Au–Pd) material are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), elemental analysis (EDS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The size of the Au–Pd bimetallic NPs deposited onto the Cu2O@CuO nanocubes is ca. 15 nm. These bimetallic NPs showed a high catalytic activity towards the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in water at room temperature. Significantly, the strong synergistic effect between Au and Pd, and the high specific surface area of Cu2O@CuO enhance the catalytic efficiency. The catalytic system can be reused for several cycles without any obvious decay of the catalytic efficiency.
Co-reporter:Bing Wu, Wen-Hua Zhang, Zhi-Gang Ren and Jian-Ping Lang
Chemical Communications 2015 vol. 51(Issue 80) pp:14893-14896
Publication Date(Web):18 Aug 2015
DOI:10.1039/C5CC05990A
Instant adsorption of Congo Red (CR) by a 1D coordination polymer, [(H2L)0.5][Zn(1,2,3-BTA)(H2O)]·2H2O (1·2H2O), leads to the formation of a unique dye composite 1·0.75CR·6H2O, which demonstrates a remarkably enhanced photocurrent response compared to that of its precursor.
Co-reporter:Min-Min Chen, Xuan Zhou, Hong-Xi Li, Xiao-Xi Yang, and Jian-Ping Lang
Crystal Growth & Design 2015 Volume 15(Issue 6) pp:2753
Publication Date(Web):April 21, 2015
DOI:10.1021/acs.cgd.5b00095
A stable two-dimensional (2D) coordination Cd(II) polymer [Cd(ppvppa)(1,4-NDC)]n (1) (ppvppa = N-(pyridin-2-yl)-N-(4-(2-(pyridin-4-yl)vinyl)phenyl)pyridin-2-amine; 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid) was prepared by the solvothermal reactions of Cd(NO3)2·4H2O with ppvppa and 1,4-H2NDC in H2O and MeCN at 150 °C. Compound 1 was characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction and thermogravimetric analysis (TGA). Compound 1 consists of dimeric [Cd2(μ-ppvppa)2] fragments linked by 1,4-NDC bridges to generate a 2D honeycomb network. Complex 1 strongly emits blue light in the solid state when excited at 419 nm at ambient temperature. This emission is selectively quenched by nitro aromatic compounds in water with good sensitivity. Compound 1 also displays recyclable detection of nitro aromatic compounds.
Co-reporter:Ming Dai, Hong-Xi Li and Jian-Ping Lang
CrystEngComm 2015 vol. 17(Issue 26) pp:4741-4753
Publication Date(Web):24 Apr 2015
DOI:10.1039/C5CE00619H
Industrial wastewater with organic pollutants has become one of the most serious problems related to our human environment. One possible treatment is to develop environmentally friendly and efficient photocatalysts. Coordination polymers (CPs) with a structural regularity and synthetic stability provide an important possibility to perform photodegradation. Doping CPs with metal ions or loading CPs on carbon nanomaterials can extend their photoresponse region and thus enhance their catalytic activity toward the photodegradation of organic dyes. In this article, we briefly highlight some of the latest progress in the photodegradation of organic dyes using modified CP-based catalysts. The decomposition of nitro- and chloroaromatics using CPs as photocatalysts is also described.
Co-reporter:Yi-Xiang Shi, Fei-Long Hu, Wen-Hua Zhang and Jian-Ping Lang
CrystEngComm 2015 vol. 17(Issue 48) pp:9404-9412
Publication Date(Web):09 Nov 2015
DOI:10.1039/C5CE02000J
We herein report a fluorescent Zn(II)-supported metal–organic framework (MOF) [Zn4(Hbpvp)2(BTC)3(HCOO)(H2O)2]·4H2O (1) (bpvp = 3,5-bis-(2-(pyridin-4-yl)vinyl)pyridine; H3BTC = 1,3,5-benzenetricarboxylic acid) assembled from solvothermal reactions of ZnSO4·7H2O with bpvp and H3BTC ligands. Compound 1 has a unique two-dimensional (2D) layer structure and exhibits a high sensitivity and a low limit of detection of 1.0 × 10−6 mol L−1 for both 2,4-dinitrophenol (2,4-DNP) and p-benzoquinone (p-BQ) in aqueous solutions, inferred from fluorescence quenching studies. The fluorescent intensity of 1 recovers upon removal of analytes, making it a promising recyclable dual-targeted luminescent probe for 2,4-DNP and p-BQ in water.
Co-reporter:Ming Dai, Tian-Yi Gu, Xin Zhao, Hong-Xi Li and Jian-Ping Lang
CrystEngComm 2015 vol. 17(Issue 43) pp:8345-8352
Publication Date(Web):28 Sep 2015
DOI:10.1039/C5CE01473E
Reactions of Zn(NO3)2·6H2O with tetrakis(4-pyridyl)cyclobutane (tpcb) in MeOH followed by addition of benzene or toluene gave rise to two two-dimensional (2D) coordination polymers {[Zn(tpcb)(NO3)2]·2S}n (1: S = benzene; 2: S = toluene). The analogue reactions of Pb(NO3)2 with tpcb in similar solvent systems resulted in the formation of {[Pb(tpcb)0.5(NO3)2(MeOH)]·benzene}n (3) and [Pb(tpcb)(NO3)2(MeOH)]n (4), respectively. Slow evaporation of the MeOH solution containing Pb(NO3)2 and tpcb generated [Pb(tpcb)(NO3)2(H2O)]n (5). Compounds 1 and 2 show similar 2D networks but differ in their packing modes, namely “overlapping” and “crisscross” modes. Compound 3 exhibits a 3D porous framework in which its 1D channels are occupied by benzene molecules. Compound 4 consists of 1D [Pb(tpcb)(NO3)2(MeOH)]n chains which are linked by weak Pb⋯N secondary interactions to form a 2D gridlike network. Compound 5 has a 3D structure constructed by dinuclear [Pb2(tpcb)6(NO3)4(H2O)2] units and tpcb bridges with a Schläfli symbol of (4·62)·(42·610·82). The solvent effects may be ascribed to the formation of the five 2D and 3D coordination polymers 1–5. The inclusion of benzene and toluene molecules in the frameworks of 1 and 2 along with the time lengths of their crystal growth may provide an interesting approach to the selective separation of benzene and toluene.
Co-reporter:Chun-Ning Lü, Min-Min Chen, Wen-Hua Zhang, Duan-Xiu Li, Ming Dai and Jian-Ping Lang
CrystEngComm 2015 vol. 17(Issue 9) pp:1935-1943
Publication Date(Web):24 Nov 2014
DOI:10.1039/C4CE02074J
A set of four metal–organic frameworks, namely, [Zn(1,3-BDC)(bmimb)]n (1), [Zn(1,4-BDC)(bmimb)]n (2), [Cd(1,3-BDC)(bmimb)]n (3), and [Cd(1,4-BDC)(bmimb)]n (4), have been prepared under solvothermal conditions (1,3-BDC = 1,3-benzenedicarboxylate; 1,4-BDC = 1,4-benzenedicarboxylate; bmimb = 4,4′-bis(4-methyl-1-imidazolyl)biphenyl). The long bmimb ligand (N⋯N separation of ca. 14.1 Å) induces interpenetration of 1, 2 and 4 to increase both the framework stability and the density of effective catalytic metal centers. Compounds 1, 2 and 4 are interpenetrated 3D structures while 3 features a 2D structure. Compound 1 exhibits a parallel 2D → 3D polycatenation while 2 and 4 are isomorphous and feature 3D → 3D interpenetration. Compounds 1–4 fluoresce in the range of 350–372 nm in the solid state, whereas compounds 2 and 3 catalyze the almost complete photodegradation of rhodamine B (RhB) in water within ca. 4 h and can be recycled at least five times without loss in their crystallinity.
Co-reporter:Fei-Long Hu, Shu-Long Wang, Brendan F. Abrahams and Jian-Ping Lang
CrystEngComm 2015 vol. 17(Issue 26) pp:4903-4911
Publication Date(Web):20 May 2015
DOI:10.1039/C5CE00594A
Five coordination polymers [Zn(oba)(4-spy)]2·(4-spy)0.25·(H2O) (1), [Zn2(oba)2(HT-ppcb)]2·(4-spy)0.25 (1a), [Zn(oba)(4-(2-npy))]2·(4-(2-npy))0.25·(H2O)1.25 (2), [Zn(oba)(4-npy)]2·(4-npy)0.25 (3) and [Zn2(oba)2(HT-pncb)]· (4-npy)0.25 (3a) (H2oba = 4,4′-oxydibenzoic acid; 4-spy = (E)-4-styrylpyridine; HT-ppcb = 1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane; 4-(2-npy) = (E)-4-(2-(naphthalen-2-yl)vinyl)pyridine; 4-npy = (E)-4-(2-(naphthalen-1-yl)vinyl)pyridine; HT-pncb = rctt-1,3-bis(4-pyridyl)-2,4-bis(1-naphthyl)cyclobutane) were structurally determined. In each case, pairs of Zn(II) centres are linked by oba2− anions to form a 2D network. Olefinic pyridyl ligands bound to Zn(II) extend above and below the mean plane of the network and are located within the windows of adjacent parallel networks. Each window contains a pair of vinyl-pyridyl ligands that are tethered to networks that lie above and below and arranged in a head-to-tail manner. 1–3 show different alignments of the CC bond pair achieved by introducing olefinic ligands with different sizes of their terminal groups. In 1, the CC bonds are parallel and close enough for a [2 + 2] cycloaddition reaction to occur upon exposure to UV light. The CC bonds in 2 are too far apart to combine and no reaction occurs upon UV irradiation. In 3, the CC bonds are less than 4.0 Å apart and has a criss-cross arrangement. Exposure of 3 to UV light leads to a [2 + 2] cycloaddition reaction. Analysis of the “before” and “after” structures shows a large conformational change associated with the rotation of the olefinic bonds and/or the naphthyl groups when the photodimerization of criss-cross CC bonds is undergone.
Co-reporter:Quan Liu, Zhi-Gang Ren, Li Deng, Wen-Hua Zhang, Xin Zhao, Zhen-Rong Sun and Jian-Ping Lang
Dalton Transactions 2015 vol. 44(Issue 1) pp:130-137
Publication Date(Web):09 Oct 2014
DOI:10.1039/C4DT02725F
We herein describe a coordination polymer system built upon the reactions of a W/Cu/S cluster precursor [Et4N][Tp*WS3(CuBr)3] (1, Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with three equivalents of CuCN through solvent modulation. Four coordination polymers, namely, [Tp*WS3Cu3(μ3-DMF)(CN)3Cu(Py)] (2), [Tp*WS3Cu3(μ3-DMF)(CN)3Cu] (3), [Tp*WS3Cu3(μ3-DMF)(CN)3Cu]·4aniline (4·4aniline) and [Tp*WS3Cu3(μ3-DMF)(CN)3Cu]·2(DMF)0.5 (5·2(DMF)0.5), are isolated in different solvent systems and characterized by means of elemental analysis, FT-IR, UV-Vis, ESI-MS and single-crystal X-ray diffraction. Compounds 2–5 feature μ3-DMF association with the nest-shaped [WS3Cu3] cluster cores, yielding cubane-type [WS3Cu3O] clusters which are further linked to single Cu(I) ions through CN bridges to provide 1D or 2D structures. Compounds 3–5 have identical chemical compositions in their main fragments but with distinctively different structural features, and are therefore topological isomers. Compound 2 has a ladder-type structure in which the side rails contain alternately linked cluster cores and Cu(I) ions. Compound 3 has a 2D (6,3) network with alternately arranged cluster cores and Cu(I) ions. Both 4 and 5 have 2D structures with 4·82 topology. In 4, a pair of cluster cores and Cu(I) ions form a 4-membered ring which is further linked to four equivalent rings through four CN ligands via a cluster core-to-Cu arrangement; while in the structure of 5, the same 4-membered rings as those in 4 are extended to equivalent rings via a cluster core-to-cluster and Cu-to-Cu arrangement. The hyperpolarizabilities (γ) of the polymeric networks exhibit an enhancement of more than 10 times compared to their parent cluster, 1.
Co-reporter:Hai-Xiao Qi, Jian-Feng Wang, Zhi-Gang Ren, Jin-Jiao Ning and Jian-Ping Lang
Dalton Transactions 2015 vol. 44(Issue 12) pp:5662-5671
Publication Date(Web):10 Feb 2015
DOI:10.1039/C5DT00167F
Solvothermal reactions of HAuCl4·4H2O with a P–S hybrid ligand N,N-bis(diphenylphosphanylmethyl)-amino-thiocarbamide (dppatc) at 80 °C and 115 °C produced two Au–P–S complexes, [Au2(dppatc)2]Cl2 (1) and [Au2(dppmt)2]n (2) (dppmtH = (diphenylphosphino)methanethiol). 1 and 2 were characterized by elemental analyses, IR and UV-vis spectra, thermal-gravity analyses, powder X-ray diffraction and single crystal X-ray diffraction analyses. Compound 1 contains a dinuclear [Au2(dppatc)2]2+ dication, while 2 has a one-dimensional chain formed by Au⋯Au aurophilic interactions. Compounds 1 and 2 exhibited excellent catalytic activity toward the photodegradation of nitrobenzene, p-nitrophenol and 2,4-dinitrophenol in aqueous solutions. The degradation reactions followed the zero-order kinetic model, in which the three nitroaromatics could be converted into CO2 and H2O in 92–96% yields.
Co-reporter:Shu-Long Wang, Fei-Long Hu, Ju-Ying Zhou, Yan Zhou, Qin Huang, and Jian-Ping Lang
Crystal Growth & Design 2015 Volume 15(Issue 8) pp:4087
Publication Date(Web):June 22, 2015
DOI:10.1021/acs.cgd.5b00642
Seven Zn(II) coordination polymers including [Zn(pbda)(p-bimb)]·H2O (1), [Zn(pbda)(bpa)0.5] (2), [Zn(pbda)(bpp)] (3), [Zn(Hpbda)2(bibm)2] (4), [Zn(pbta)0.5(m-bimb)]·H2O (5), [Zn(pbta)0.5(bpp)(H2O)] (6), and [Zn(H2pbta)(bibm)]·H2O (7) (H2pbda = 4,4′-{[1,4-phenylenebis(methylene)]bis(oxy)}dibenzoic acid; p-bimb = 1,4-bis(1H-imidazol-l-yl)methyl)benzene; bpa = 1,2-bis(4-pyridyl)ethane; bpp = 1,3-bis(4-pyridyl)-propane; bibm = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl; m-bimb = 1,3-bis(1H-imidazol-l-yl)methyl)-benzene; H4pbta = 5,5′-phenylenebis(methylene)-1,1′-3,3′-(benzene-tetracarboxylic acid) were prepared under solvothermal conditions and structurally characterized. Compound 1 shows a three-dimensional (3D) channel-like architecture constructed by helical chain subunits. Compound 2 shows a rare 2D + 2D + 2D → 2D network with both polyrotaxane and polycatenane features. 3 holds a 2D layer structure constituted of metal-sharing right- and left-handed helical chains. Compound 4 presents a one-dimensional (1D) chain which is decorated by long side arms around the chain. Compound 5 possesses a 2D wave-like layer formed by [Zn2(m-bimb)]n chains by linear pbta ligands. Compound 6 displays a 3D framework that is stabilized by hydrogen bonding interactions between the coordinated H2O molecules and the neighboring carboxylate oxygen atoms. Compound 7 possesses a 1D + 1D → 2D polycatenation motif. The results demonstrated that the rigidity versus flexibility of the ligands along with the number of carboxyl groups make an impact on the structural diversities of the entangled coordination polymers. Moreover, compounds 3 and 6 as representative examples possessed high catalytic efficiency for the photodecomposition of methyl blue in water using natural sunlight irradiation.
Co-reporter:Fei-long Hu, Yi-Xiang Shi, Huan-Huan Chen and Jian-Ping Lang
Dalton Transactions 2015 vol. 44(Issue 43) pp:18795-18803
Publication Date(Web):24 Sep 2015
DOI:10.1039/C5DT03094C
One coordination polymer [Zn2(L)2(bpe)2(H2O)2] (1) (L = 4,4′-((1,2-phenylenebis(methylene))bis(oxy))dibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethene) was prepared and structurally determined. Compound 1 has a chain structure in which its pair of bpe ligands is arranged in a head-to-tail manner with their CC bonds being close enough for a [2 + 2] cycloaddition reaction. Upon exposure to UV light, compound 1 undergoes a single-crystal-to-single-crystal (SCSC) [2 + 2] photodimerization to generate one 2D coordination polymer [Zn(L)(rctt-tpcb)0.5(H2O)] (1a) (rctt (regio cis, trans, trans)-tpcb = tetrakis(4-pyridyl)cyclobutane). The tpcb ligands in the crystals of 1a show an intriguing in situ thermal isomerisation. The nanospheres of 1 can be obtained by recrystallization in DMSO/alcohol. The nanospheres of 1a can also be readily produced from the corresponding nanospheres of 1 by the photocyclodimerization method. Compared with those of 1a, the nanospheres of 1 display highly selective sensing of Fe3+ ions over mixed metal ions through fluorescence quenching. Moreover, the nanospheres of 1a can rapidly adsorb CR (congo red), MB (methylene blue) or RhB (rhodamine B) over MO (methyl orange) from aqueous solutions. This work offers a new photoinduced post-synthetic method for the synthesis of multifunctional MOFs, which show luminescence sensing of Fe3+ ions and dye adsorption properties.
Co-reporter:Duan-Xiu Li;Zhi-Gang Ren;David J. Young
European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 11) pp:1981-1988
Publication Date(Web):
DOI:10.1002/ejic.201500069
Abstract
The coordination polymers (CPs) [Zn2(tipm)(1,3-BDC)2] (1) and [Co2(tipm)(1,3-BDC)2]·0.5CH3CN (2·0.5CH3CN) were synthesized by the reactions of Zn(NO3)2 or Co(NO3)2 with tetrakis[4-(1-imidazolyl)phenyl]methane (tipm) and benzene-1,3-dicarboxylic acid (1,3-H2BDC) under solvothermal conditions. Compounds 1 and 2 are isostructural and possess complicated three-dimensional frameworks with the Schläfli symbol (4·72)(62·73·12)(4·62·73). Cobalt ions were incorporated into the Zn-based CP framework 1 during solvothermal crystallization to yield [Zn(2–2x)Co2x(tipm)(1,3-BDC)2]·bH2O (x = 2.4 %, b = 0 for 1a, x = 23 %, b = 1 for 2a·H2O). Doped CPs 1a and 2a·H2O exhibited greater catalytic photodegradation of the dye rhodamine B (RhB) than the undoped complexes 1 and 2 and many literature examples.
Co-reporter:Jin-Jiao Ning, Jian-Feng Wang, Zhi-Gang Ren, David James Young, Jian-Ping Lang
Tetrahedron 2015 Volume 71(Issue 23) pp:4000-4006
Publication Date(Web):10 June 2015
DOI:10.1016/j.tet.2015.04.052
Suzuki–Miyaura coupling reactions of arylboronic acids with aryl bromides were mediated by PdCl2 and bdppmapy (N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine) that both stabilizes and solubilizes the catalyst in predominantly ethanol as a solvent. Excellent yields for a wide variety of substrates were obtained under relatively mild conditions in this ‘green’ solvent.
Co-reporter:Wei-Jie Gong, De-Xian Liu, Fei-Long Li, Jun Gao, Hong-Xi Li, Jian-Ping Lang
Tetrahedron 2015 Volume 71(Issue 8) pp:1269-1275
Publication Date(Web):25 February 2015
DOI:10.1016/j.tet.2014.12.095
An efficient approach to decarboxylative C3-acylation of benzothiophenes or benzofurans with α-oxocarboxylic acids via palladium-catalyzed C–H bond activation was developed. This method was compatible with a variety of functional groups and provided an attractive route to 3-acylbenzothiophenes and 3-acylbenzofurans in good to high yields.
Co-reporter:Dong Liu, Hui-Fang Wang, Brendan F. Abrahams and Jian-Ping Lang
Chemical Communications 2014 vol. 50(Issue 24) pp:3173-3175
Publication Date(Web):03 Feb 2014
DOI:10.1039/C3CC49749F
A 2D network [Zn4(OH)2(5-NO2-1,3-BDC)2(5-NO2-1,3-HBDC)2(ppene)2]n underwent a highly selective [2+2] photodimerization reaction upon UV irradiation. The coordination polymer retains its single crystallinity after photoreaction.
Co-reporter:Duan-Xiu Li, Chun-Yan Ni, Min-Min Chen, Ming Dai, Wen-Hua Zhang, Wen-Yan Yan, Hai-Xiao Qi, Zhi-Gang Ren and Jian-Ping Lang
CrystEngComm 2014 vol. 16(Issue 11) pp:2158-2167
Publication Date(Web):02 Jan 2014
DOI:10.1039/C3CE42360C
Four Cd(II) coordination polymers formulated as {[Cd3(tpcb)2)(η,η-μ-SO4)2(H2O)6]SO4·16H2O}n (1), {[Cd(tpcb)0.75(OH)(H2O)2](NO3)}n (2), {[Cd2(tpcb)(SO4)2(H2O)6]·2MeOH·3H2O}n (3), and {[Cd(tpcb)(NO3)(H2O)2](NO3)}n (4) were synthesized by reactions of CdSO4 or Cd(NO3)2 with tetrakis(4-pyridyl)cyclobutane (tpcb) under solvothermal conditions or at ambient temperature. Compounds 1–4 were characterized by elemental analysis, IR spectroscopy, thermal analysis, powder X-ray diffraction analysis and single crystal X-ray diffraction. Compounds 1, 2, and 4 possess three different complicated 3D frameworks with the Schläfli symbols of (46)(412·54·64·88), (63)4(62·84)3 and (83)(86), respectively, while 3 presents a 1D chain structure. Compounds 1–4 exhibited relatively good photocatalytic activity towards the degradation of methyl orange (MO), methyl blue (MB) and rhodamine B (RhB) in aqueous solution. These results offered a good insight into the temperature effects on the assembly of Cd(II) coordination polymers and their photocatalytic applications.
Co-reporter:Fei-Long Hu, Shu-Long Wang, Bing Wu, Hong Yu, Fan Wang and Jian-Ping Lang
CrystEngComm 2014 vol. 16(Issue 28) pp:6354-6363
Publication Date(Web):13 Feb 2014
DOI:10.1039/C3CE42545B
Seven new complexes [Cd(oba)(2,2′-bipy)]2 (1), [Co(oba)(bbm)]·1.5H2O (2), [Mn3(oba)3(bbm)(H2O)2]·DMF·2H2O (3), [Mn2(bibm)2(oba)2] (4), [Co(oba)(bibm)]2·H2O (5), [Co5(bpb)3(oba)4(Hoba)2(H2O)2] (6) and [Ni2(bpb)2(oba)2(DMF)(H2O)]2·5H2O (7) (H2oba = 4,4′-oxydibenzoic acid, bbm = 1,4-di(1H-imidazol-1-yl)benzene, bibm = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl, bpb = 1,4-di(pyridin-4-yl)benzene, 2,2′-bipy = 2,2′-bipyridine) have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, X-ray powder diffraction and X-ray single crystal diffraction. Compound 1 displays a 3-fold polythreaded 2D network, while 2 has sql layers and these layers are further stacked in a 2D → 3D polycatenation model. Compound 3 shows a 3D porous net with {421·54·63} topology with 1D channels that are filled by DMF and water molecules while 4 possesses a 2D (4,4) layer structure composed of [Mn2(bibm)2(oba)2] units. Compound 5 exhibits a five-fold interpenetrating 3D framework while 6 displays a 2D → 3D polycatenation motif. Compound 7 has a three-fold interpenetrating 3D framework. These results provide some insight into the ligand geometry-driven assembly of entangled coordination polymers. Thermal stability and photoluminescence properties of 1–7 were studied. The optical and photocatalytic properties of 3 and 6 were also investigated.
Co-reporter:Dong Liu and Jian-Ping Lang
CrystEngComm 2014 vol. 16(Issue 1) pp:76-81
Publication Date(Web):13 Sep 2013
DOI:10.1039/C3CE41609G
Two coordination complexes [Cd2(CBA)4(4-spy)4] (1) and [Cd2(5-NO2-1,3-BDC)2(5-NO2-1,3-HBDC)2(H2O)4]·(4-spy–H)2 (2) were prepared by the hydrothermal reactions of Cd(NO3)2·4H2O, 4-styrylpyridine (4-spy) and 4-chlorobenzoic acid (HCBA) or 5-nitrobenzene-1,3-dicarboxylic acid (5-NO2-1,3-H2BDC). Each pair of 4-spy molecules in [Cd2(CBA)4(4-spy)4] and [Cd2(5-NO2-1,3-BDC)2(5-NO2-1,3-HBDC)2(H2O)4]·(4-spy–H)2 are arranged in a head-to-head (HH) or head-to-tail (HT) fashion, which, upon UV irradiation, dimerizes into 1,2-bis(4-pyridyl)-3,4-bis(phenyl)cyclobutane (HH-ppcb) or 1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane (HT-ppcb) in 100% yield, respectively. Compared with liquid-phase organic reactions, these solid-state photochemical [2 + 2] cycloadditions of olefin molecules provide good opportunities to synthesize regiospecific cyclobutanes.
Co-reporter:Wang Yao, Wei-Jie Gong, Hong-Xi Li, Fei-Long Li, Jun Gao and Jian-Ping Lang
Dalton Transactions 2014 vol. 43(Issue 42) pp:15752-15759
Publication Date(Web):18 Aug 2014
DOI:10.1039/C4DT01856G
DMF-stabilized Au nanoparticles (NPs) with three different particle sizes were prepared by controlling the reaction temperatures and times. In the absence of any additional ligands, these Au NPs showed high catalytic activity in the Ullmann homocoupling of aryl iodides in DMF. The effects of Au particle size on the coupling reaction were investigated by the use of three Au catalysts with mean particle sizes of ca. 1.0 nm, 2.5 nm, and 5.5 nm, respectively. The catalytic activity of the Au NPs was found to be in the order of Au (2.5 nm) > Au (<1.0 nm) > Au (5.5 nm), indicating that surface Au atoms do not have the same catalytic activity toward such a homocoupling reaction.
Co-reporter:Da-Wei Tan, Jing-Bo Xie, Qi Li, Hong-Xi Li, Jun-Chi Li, Hai-Yan Li and Jian-Ping Lang
Dalton Transactions 2014 vol. 43(Issue 37) pp:14061-14071
Publication Date(Web):30 Jul 2014
DOI:10.1039/C4DT01765J
Reactions of a pincer ligand 2-(1H-pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine (pzpypzH) with Cu(NO3)2, Cu(ClO4)2, CuSO4, CuCl2 or CuI produced three dinuclear Cu(II) complexes [{Cu(NO3)}(μ-pzpypz)]2 (1), [{Cu(ClO4)}(μ-pzpypz)]2 (2), [Cu2(μ-SO4)(μ-pzpypz)2]·2MeOH (3·2MeOH), one mononuclear Cu(II) complex [CuCl2(pzpypzH)] (4) and one trinuclear Cu(I)/Cu(II) complex [(ICu)(μ-I)2Cu2(μ-pzpypz)2] (5), respectively. Treatment of 4 with two equiv. of AgNO3 in DMF also gave rise to 1. Complexes 1–5 were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Complex 1 or 2 has a dimeric structure in which two {Cu(X)} (X = NO3, ClO4) fragments are interconnected by two μ-pzpypz− ligands. 3 also adopts a dimeric structure in which two Cu(II) centers are interconnected by a pair of μ-pzpypz− ligands and one μ-SO42− ion. The Cu(II) center in 4 is five-coordinated by three N atoms of the pzpypzH ligand and two Cl atoms. In 5, two Cu(II) centers are bridged by two μ-pzpypz− ligands and one CuI32− unit, forming a unique trinuclear structure. Complexes 1–5 displayed high catalytic activity toward the ammoxidation of alcohols to nitriles and the aerobic oxidation of alcohols to aldehydes in H2O. The nitrile or aldehyde products could be readily separated from the catalytic system by extraction and the residual aqueous solution containing 1 retained good activity for several cycles.
Co-reporter:Run-Tian He, Jian-Feng Wang, Hui-Fang Wang, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2014 vol. 43(Issue 25) pp:9786-9794
Publication Date(Web):30 Apr 2014
DOI:10.1039/C4DT00815D
Reaction of PdCl2 with N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) afforded a mononuclear complex [(bdppmapy)PdCl2] (1). Compound 1 was characterized by elemental analysis, IR, 1H, 13C and 31P NMR, electrospray ion mass spectra (ESI-MS) and X-ray single crystal crystallography. The Pd(II) center in 1 is chelated by bdppmapy, showing a cis-square planar geometry. With the assistance of additive Cu2O, complex 1 exhibited good catalytic activity toward the decarboxylative cross-coupling reactions between 4-picolinic acid and aryl bromides. In the presence of only 2 mol% catalyst, a family of 4-aryl-pyridines could be isolated in up to 83% yield.
Co-reporter:Yang-Yang Fang, Wei-Jie Gong, Xiu-Juan Shang, Hong-Xi Li, Jun Gao and Jian-Ping Lang
Dalton Transactions 2014 vol. 43(Issue 22) pp:8282-8289
Publication Date(Web):19 Mar 2014
DOI:10.1039/C4DT00475B
The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be utilized as a pre-catalyst to initiate the ring-opening polymerization of ε-caprolactone in the presence of alcohol but 2 did not work. The 1/alcohol system displayed characteristics of a well-controlled polymerization with the resulting poly(ε-caprolactone) having low molecular weight distributions, a linear tendency of molecular weight evolution with conversion, and polymer growth observed for the sequential additions of ε-caprolactone monomer to the polymerization reaction. The polymerization was completely turned off by the in situ reduction of the catalytic Fe center via Cp2Co and then turned back upon the addition of [Cp2Fe]PF6. The rate of polymerization was modified by switching in situ between the Fe(III) and Fe(II) species.
Co-reporter:Li-Kuan Zhou, Quan Liu, Xin Zhao, Fei-Long Hu, Shu-Chen Liu, Zhi-Gang Ren, Zhen-Rong Sun and Jian-Ping Lang
Dalton Transactions 2014 vol. 43(Issue 12) pp:4734-4744
Publication Date(Web):07 Jan 2014
DOI:10.1039/C3DT53320D
Treatment of [Et4N][Tp*WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with CuX (X = Br, SCN) and PPh3 or 1,1-bis(diphenylphosphino)methane (dppm) produced two neutral trinuclear clusters [Tp*W(μ3-S)(μ-S)2Cu2Br(PPh3)] (2) and [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(dppm)]2·MeCN·Et2O (3·MeCN·Et2O). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6 and 1,3-bis(diphenylphosphino)propane (dppp), N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy), N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda), or 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzenediamine (dpppda) afforded four clusters containing butterfly-shaped [Tp*WS3Cu2] cores, [Tp*W(μ3-S)(μ-S)2Cu2(dpppds)](PF6)·1.25MeCN (dpppds = 1,3-bis(diphenylphosphino)propane disulfide) (4·1.25MeCN), [Tp*W(μ3-S)(μ-S)2Cu2(bdppmapy)](PF6)·3MeCN (5·3MeCN) and {[Tp*W(μ3-S)(μ-S)2Cu2]2(L)]}(PF6)2·Sol (6·Et2O: L = dppeda, Sol = Et2O; 7·1.25MeCN: L = dpppda, Sol = 1.25MeCN). Compounds 2–7 were characterized by elemental analysis, IR, UV-Vis, 1H and 31P{1H} NMR spectra, electrospray ion mass spectra (ESI-MS) and single-crystal X-ray diffraction. Compound 2 or 3 has a butterfly-shaped [Tp*WS3Cu2] core in which one [Tp*WS3] unit binds two Cu(I) centers via one μ3-S and two μ-S atoms. In the cationic structure of 4 or 5, one in situ-formed dpppds or bdppmapy combines with the [Tp*WS3Cu2] core via each of its two S atoms or two P atoms coordinated at each Cu(I) center. In the bicationic structure of 6 or 7, two [Tp*WS3Cu2] cores are linked by one dppeda or dpppda bridge to form a bicyclic structure. The isolation of 2–7 with unstable [Tp*WS3Cu2] cores may be ascribed to the coordination of P- or S-donor ligands at Cu(I) centers of these cores. The third-order nonlinear optical (NLO) properties of 2–7 in DMF were also investigated by using the femtosecond degenerate four-wave mixing (DFWM) technique at 800 nm.
Co-reporter:Xin-Yi Wu, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2014 vol. 43(Issue 4) pp:1716-1723
Publication Date(Web):11 Oct 2013
DOI:10.1039/C3DT52412D
Reactions of the tetraphosphine ligand N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine) (dppeda) or 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) with NiCl2, ancillary ligand (C2H5)2NCS2Na (Na(dtc)) and NH4PF6 afforded two binuclear complexes [(dtc)Ni(dppeda)Ni(dtc)](PF6)2 (1) and [(dtc)Ni(dpppda)Ni(dtc)](PF6)2 (2). Compounds 1 and 2 were characterized by elemental analyses, IR spectra, 1H, 13C{1H} NMR and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, thermogravimetric (TGA) experiments and single crystal X-ray diffraction. The Ni(II) atoms in both compounds form a square planar coordination geometry while the ligands hold a similar end-to-end coordination mode. Both products can catalyze the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) while 1 exhibited a higher catalytic activity than 2. Influencing aspects such as solvent, temperature, the ratio of ε-CL to catalyst, the presence of benzyl alcohol, concentration of ε-CL and reaction intervals were investigated.
Co-reporter:Ming Dai, Xin-Ran Su, Xiao Wang, Bing Wu, Zhi-Gang Ren, Xuan Zhou, and Jian-Ping Lang
Crystal Growth & Design 2014 Volume 14(Issue 1) pp:240-248
Publication Date(Web):December 11, 2013
DOI:10.1021/cg4014416
Solvothermal reactions of Zn(NO3)2 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,4-naphthalenedicarboxylic acid (1,4-H2ndc) and 2,3-naphthalenedicarboxylic acid (2,3-H2ndc) in different solvents led to the formation of three polydimensional coordination polymers {[Zn2(H2O)(1,4-ndc)2(tpcb)]}n (1), {[Zn(1,4-ndc)(tpcb)0.5]}n (2), and {[Zn2(H2O)(2,3-ndc)2(tpcb)]}n (3). Compounds 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Compound 1 is a three-dimensional (3D) (3,3)-connected net with a (10·122)·(102·12) Schläfli symbol. Compound 2 holds a 2-fold interpenetrating 3D framework with a (42·62·72)·(4·62·73) Schläfli symbol, which shows hexagonal-prism-like one-dimensional channels. Compound 3 shows a two-dimensional (3,8)-connected network. The solid state luminescent, optical, and thermal stability properties of 1–3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methyl orange and methyl blue in polluted water was explored. The results provided some interesting insights into solvent effects on the structures of zinc(II) coordination polymers and their photocatalytic applications.
Co-reporter:De-Xian Liu;Fei-Long Li;Hong-Xi Li;Wei-Jie Gong;Jun Gao
European Journal of Organic Chemistry 2014 Volume 2014( Issue 22) pp:4817-4822
Publication Date(Web):
DOI:10.1002/ejoc.201402416
Abstract
An efficient method for synthesis of 1,3-diynes through the CuI/1,10-phenanthroline-catalyzed oxidative decarboxylative homocoupling of aryl pioprolic acids in aqueous DMF has been developed. The catalytic system was suitable for a variety of arylpropiolic acids, and the corresponding 1,3-diynes could be prepared in high yields. The catalytic system was recovered from the organic products by filtration and its aqueous DMF filtrate retained good activity even after at least four cycles of use.
Co-reporter:Li Li;Hai-Yan Li;Zhi-Gang Ren
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 5) pp:824-830
Publication Date(Web):
DOI:10.1002/ejic.201301433
Abstract
The reaction of 3-aminopyridine with formaldehyde afforded a clamplike ligand, 3,7-di(3-pyridyl)-1,5-dioxa-3,7-diazacyclooctane (L). The diffusion of a CH2Cl2 solution of L into an MeCN solution of CuX produced one decanuclear cluster [Cu10Cl10(L)4] (1) and two tetranuclear clusters [Cu4X4(L)2(MeCN)2] [X = Br (2), I (3)]. Compound 1 possesses a unique [Cu10Cl10] cluster core consisting of two stairlike [Cu5Cl5] fragments that share two μ6-Cl and two μ-Cl atoms. Compounds 2 and 3 have a stairlike [Cu4X4] cluster core that is anchored by two L ligands. The trans configuration of the two pyridyl groups of the free L ligand was converted into the cis configuration of the two pyridyl groups of each bridging L ligand in 1–3. The photoluminescence properties of 1–3 in the solid state were also investigated.
Co-reporter:Li Li;Hai-Yan Li;Zhi-Gang Ren
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 5) pp:
Publication Date(Web):
DOI:10.1002/ejic.201400071
Abstract
Invited for the cover of this issue is the group of Jian-Ping Lang at Soochow University, P. R. China. The cover image shows the structure containing the decanuclear chlorocuprate(I) cluster in which two stairlike [Cu5Cl5] fragments share two μ6-Cl and two μ-Cl atoms to form a unique [Cu10Cl10] cluster framework. In the background is a gate with the motto of the university “Unto a Full Grown Man”.
Co-reporter:Li Li;Hai-Yan Li;Zhi-Gang Ren
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 5) pp:
Publication Date(Web):
DOI:10.1002/ejic.201490021
Co-reporter:Jing-Bo Xie, Jia-Jing Bao, Hong-Xi Li, Da-Wei Tan, Hai-Yan Li and Jian-Ping Lang
RSC Advances 2014 vol. 4(Issue 96) pp:54007-54017
Publication Date(Web):10 Oct 2014
DOI:10.1039/C4RA11743C
Reactions of 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid (pypzacacH) ligand with Cu(OAc)2, Cu(NO3)2, CuSO4, Cu(ClO4)2 or CuCl2 produced four dinuclear Cu(II) complexes [{(MeOH)Cu(OAc)}(μ-κ2:κ1-pypzacac)]2·0.5H2O (1·0.5H2O), [{Cu(pypzacac)}(μ-κ2:κ1-pypzacac)2{Cu(H2O)2}](NO3)·2(MeOH)0.5·6H2O (2·2(MeOH)0.5·6H2O), [{(MeOH)Cu(mpypzacac)}(μ-SO4)]2·2MeOH (3·2MeOH; mpypzacac = methyl 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetate), [{Cu(mpypzacac)2}(μ-κ2:κ1-pypzacac){Cu(mpypzacac)}](ClO4)3·MeOH (4·MeOH) and one polymeric Cu(II) complex [(CuCl)(μ-κ3:κ1-pypzacac)]n (5), respectively. The mpypzacac ligand in 3 and 4 was in situ generated via the Cu2+-catalyzed dehydrative esterification of acetic acid of the pypzacacH ligand. Complexes 1–5 are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 contains two {(MeOH)Cu(OAc)} fragments that are interconnected by two μ-κ2:κ1-pypzacac− ligands, forming a dimeric structure. In 2, {Cu(pypzacac)} and {Cu(H2O)2} units are bridged by a pair of μ-κ2:κ1-pypzacac− ligands. In 3, two {Cu(mpypzacac)} fragments are linked by two μ-κ1:κ1-SO42− ions to form a dinuclear structure. Complex 4 also adopts a dimeric structure in which {Cu(mpypzacac)2} and {Cu(mpypzacac)} units are interconnected by one μ-κ3:κ1-pypzacac− ligand. Complex 5 contains a 1D chain in which (CuCl) fragments are interlinked by μ-κ3:κ1-pypzacac− ligands. Complexes 1–5 exhibited excellent catalytic performance in the ammoxidation of alcohol to nitrile and the aerobic oxidation of alcohol to aldehyde in water. The catalytic aqueous solution was easily separated and could be reused for several cycles without any obvious decay of catalytic efficiency.
Co-reporter:Fei-Long Hu, Shu-Long Wang, Hong-Xi Li, Bing Wu, Jian-Ping Lang
Inorganic Chemistry Communications 2014 Volume 47() pp:75-79
Publication Date(Web):September 2014
DOI:10.1016/j.inoche.2014.07.023
•1D water chains are encapsulated in the channels formed by 2D layers of 1.•Hemidirected coordination geometry of Pb atom is observed in 3.•Compound 3 exhibits a 2D → 3D polycatenation network.•The results offer an insight into effects of linker and metal ion on the structures.Three new coordination polymers, [Mn(L)(H2O)2]2·5H2O (1), [Cu(L)(4,4′-bipy)]2·H2O (2) and [Pb(L)(4,4′-bipy)0.5] (3) (H2L = 5-(pyridin-4-yl)isophthalic acid; 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by IR, thermogravimetric analysis, X-ray powder diffraction and X-ray single crystal diffraction. Complex 1 shows a 2D layer structure which stacks with the other ones to form 1D channels to hold 1D water chains. Complex 2 displays a 3D + 3D → 3D polycatenation network. 3 shows a unique 2D + 2D → 3D polycatenation net in which each Pb center has a hemidirected coordination geometry due to the existence of “inert pair effect”. The thermal and luminescent properties of 1–3 were also examined.Solvothermal reactions of MnSO4·7H2O with 5-(pyridin-4-yl)isophthalic acid (H2L) afforded one 2D layer polymer [Mn(L)(H2O)2]2·5H2O while treatment of CuSO4·5H2O or Pb(NO3)2 with H2L and 4,4′-bipy under solvothermal conditions produced two 3D pillared-layer polymers [Cu(L)(4,4′-bipy)]2·H2O and [Pb(L)(4,4′-bipy)0.5]. These complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were investigated.
Co-reporter:Bing Wu, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2014 Volume 48() pp:81-85
Publication Date(Web):October 2014
DOI:10.1016/j.inoche.2014.08.025
•The [Ag(L)] chains are connected via weak interactions to form a 3D net of 1.•The [Ag(L)] helical chains are linked by weak interactions to afford a 3D net of 2.•Two [Ag(L)] chains are linked by the Ag⋯O interactions to yield a 3D net of 3.•The results offer an insight into effects of weak interactions on the structures.Reactions of N,N′-di(3-pyridyl)succinamide (L) with AgOTf, AgTFA and AgNO3 (OTf = triflate, TFA = trifluoroacetate) produced three coordination polymers {Ag(L)(OTf)·DMF·MeCN}n (1·DMF·MeCN), {Ag(L)(TFA)·2H2O}n (2·2H2O) and {[Ag(L)]2(NO3)2}n (3), respectively. In 1, two one-dimensional (1D) [Ag(L)] chains are joined by the Ag⋯Ag, π⋯π and hydrogen-bonding interactions to form a 1D double chain, which is further linked to other equivalent ones via the hydrogen bonding interactions to yield a three-dimensional (3D) structure. In 2, the 1D [Ag(L)] helical chains are connected by the Ag⋯O, π⋯π, CH⋯π and hydrogen-bonding interactions to afford a 3D framework. In 3, two kinds of 1D [Ag(L)] chains are linked by the Ag⋯O and hydrogen-bonding interactions to form a 3D structure. The luminescent properties of 1–3 along with L were also investigated.Three coordination polymers derived from N,N′-di(3-pyridyl)succinamide (L) and AgOTf, AgTFA and AgNO3 were synthesized. The 1D [Ag(L)]n chains in these complexes are connected by the Ag⋯O, π⋯π, CH⋯π and hydrogen-bonding interactions to form three different 3D supramolecular frameworks.
Co-reporter:Jing Shi, Fu-Ling Li, Hong-Xi Li, Fan Wang, Hong Yu, Zhi-Gang Ren, Wen-Hua Zhang, Jian-Ping Lang
Inorganic Chemistry Communications 2014 Volume 46() pp:159-162
Publication Date(Web):August 2014
DOI:10.1016/j.inoche.2014.05.035
•[Zn(Tab)4](PF6)2 reacts with Ni(II) ions and donor ligands gave three complexes.•Complex 2 has a linear trinuclear cationic structure.•Complex 3 is one mononuclear cationic complex.•Complex 4 has a dimeric cationic structure.•Complexes 2–4 can catalyze the N-arylation reaction.Reactions of NiCl2·6H2O or Ni(ClO4)2·6H2O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)ethane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab)4](PF6)2 (1) resulted in the formation of one trinuclear cationic complex [(2,2′-bipy)4Ni3(μ-Tab)4]Cl0.5(PF6)5.5 (2), one mononuclear cationic complex [Ni(Tab)2(dppe)](PF6)2 (3), and one dinuclear cationic complex [Ni2(dppb)(μ-Tab)2(Tab)2](PF6)2(ClO4)2 (4). Complexes 2–4 were characterized by elemental analysis, IR, UV–vis, 1H and 31P NMR, and single-crystal X-ray diffraction. In the [(2,2′-bipy)4Ni3(μ-Tab)4]6 + hexacation of 2, the central Ni(II) atom is connected to two [Ni(2,2′-bipy)2]2 + fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni]2 + species are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 2–4 displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines.Reactions of [Zn(Tab)4](PF6)2 with Ni(II) ions and 2,2′-bipy, dppe or dppb produced one trinuclear cationic complex, one mononuclear cationic complex and one dinuclear cationic complex. These three complexes displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids with amines to produce N-arylated amines.
Co-reporter:Quan Liu;Wenhua Zhang;Zhenrong Sun;Jianping Lang
Chinese Journal of Chemistry 2014 Volume 32( Issue 10) pp:1065-1071
Publication Date(Web):
DOI:10.1002/cjoc.201400412
Abstract
Treatment of a W/Cu/S precursor [Et4N][Tp*WS3(CuBr)3] (1) with three equiv. of CuCN in DMF/MeCN/benzonitrile (or α-tolunitrile) yielded two [Tp*WS3Cu3(µ3-DMF)]-based coordination polymers, [Tp*WS3Cu3(µ3-DMF)(CN)3Cu]2·2DMF (2·2DMF) and [Tp*WS3Cu3(µ3-DMF)(CN)3Cu(α-tolunitrile)]2·3MeCN (3·3MeCN), respectively. Structural analysis revealed that 2 adopts a 2D network with a 4.82 topology while 3 has a 1D ladder-type chain. The third-order nonlinear optical responses of 2 and 3 in DMF were 10 times enhanced compared to those of the precursor cluster 1.
Co-reporter:Qi Li;Li-Ming Zhang;Jia-Jing Bao;Hong-Xi Li;Jing-Bo Xie
Applied Organometallic Chemistry 2014 Volume 28( Issue 12) pp:861-867
Publication Date(Web):
DOI:10.1002/aoc.3227
This work reports Suzuki–Miyaura cross-coupling reactions of arylboronic acid with aryl halide or aryl dibromide mediated by PdCl2 (0.05 mol%) and sodium 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-1-yl)butane-1-sulfonate (0.05 mol%) at 100 °C in water. The corresponding cross-coupling products were obtained in good to excellent yields. The catalytic system was recovered from the organic products by extraction with ether and the residual aqueous catalyst phase showed high activity after reuse of at least four cycles. Copyright © 2014 John Wiley & Sons, Ltd.
Co-reporter:Hong-Jian Cheng, Rong-Xin Yuan, Chun-Ning Lü, Jian-Ping Lang
Inorganic Chemistry Communications 2014 40() pp: 138-142
Publication Date(Web):
DOI:10.1016/j.inoche.2013.11.045
Co-reporter:Ming Dai, Zhou Yang, Chun-Yan Ni, Hong Yu, Yang Chen, Hong-Xi Li, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2014 40() pp: 205-210
Publication Date(Web):
DOI:10.1016/j.inoche.2013.12.010
Co-reporter:Li-Kuan Zhou, Quan Liu, Bing Wu, Hong Yu, Fei-Long Hu, Xin Zhao, Shu-Chen Liu, Jian-Ping Lang
Polyhedron 2014 Volume 83() pp:60-67
Publication Date(Web):24 November 2014
DOI:10.1016/j.poly.2014.04.010
Treatment of [Et4N][Tp∗MoS(S4)] (Tp∗ = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1a) with [Ag(MeCN)4]PF6 and PPh3 or Agdca (dca = dicyanamide) afforded two new neutral compounds [Tp∗MoO(μ–O)2MoO(μ–O)2MoO(μ–O)2OMoTp∗]·8(MeCN)0.5 (2·8(MeCN)0.5) and [Tp∗Mo(μ–S)(μ–S2)(μ–S3)MoTp∗]·DMF (3·DMF). Reactions of [Et4N][Tp∗WS3] (1b) with AgX (X = SCN, NO3, CN) in the presence of N- or P-donor ligands formed one binuclear cluster [Et4N][Tp∗WS(μ–S)2EW(NCS)2] (E = 0.5O + 0.5S) (4) and two W/Ag/S clusters [Tp∗WO(μ–S)2Ag(dppe)]·MeCN (5·MeCN) and [{Tp∗WS(μ–S)(μ3–S)Ag2(py)2}2(μ–CN)2] (6). These compounds were characterized by elemental analysis, IR, UV–Vis, 1H NMR and single-crystal X-ray crystallography. Compound 2 possesses a centrosymmetric tetranuclear structure in which two dinuclear [Tp∗MoO(μ–O)2MoO] units are linked by a pair of μ–O bridges. Compound 3 contains a dimeric structure in which two [Tp∗Mo] units are linked by one μ–S, one μ–S2 and one μ–S3 bridge. Compound 4 has another dimeric anionic structure in which one [Tp∗WS] unit and one [(SCN)2WE] unit are linked via a pair of μ–S bridges. Compound 5 has a dimeric structure in which one [Ag(dppe)]+ unit is linked by two μ–S atoms of [Tp∗WO(μ–S)2]− moiety. Compound 6 adopts a centrosymmetric hexanuclear structure in which two unique trinuclear [Tp∗WS(μ–S)(μ3–S)Ag2(py)2] units are interconnected by a couple of μ–CN bridges. The isolation of 2–6 provided an insight into not only the complexity arising from reactions of 1a and 1b with Ag(I) salts in the presence or absence of N- or P-donor ligands but also the interesting assembly chemistry of the Mo(W)/Ag/S clusters.Reactions of [Et4N][Tp∗MoS(S4)] or [Et4N][Tp∗WS3] with [Ag(MeCN)4]ClO4, Agdca, AgSCN, AgNO3 or AgCN in the presence or absence of N-, or P-donor ligands afforded one tetranuclear Mo/O cluster [Tp∗MoO(μ–O)2MoO(μ–O)2MoO(μ–O)2OMoTp∗], one binuclear Mo/S cluster [Tp∗Mo(μ–S)(μ–S2)(μ–S3)MoTp∗], one binuclear W/S cluster [Et4N][Tp∗WS(μ–S)2EW(NCS)2] (E = 0.5O + 0.5S), one binuclear W/Ag/S cluster [Tp∗WO(μ–S)2Ag(dppe)], and one hexanuclear cluster [Tp∗WS(μ–S)(μ3–S)Ag2(py)2(μ–CN)]2. These compounds were characterized by elemental analysis, IR spectra UV–Vis, 1H NMR and X-ray crystallography.
Co-reporter:De-Xian Liu, Fei-Long Li, Hong-Xi Li, Jun Gao, Jian-Ping Lang
Tetrahedron 2014 70(14) pp: 2416-2421
Publication Date(Web):
DOI:10.1016/j.tet.2014.02.022
Co-reporter:De-Xian Liu, Wei-Jie Gong, Hong-Xi Li, Jun Gao, Fei-Long Li, Jian-Ping Lang
Tetrahedron 2014 70(21) pp: 3385-3389
Publication Date(Web):
DOI:10.1016/j.tet.2014.03.098
Co-reporter:Fan Wang, Chun-Yan Ni, Quan Liu, Fu-Ling Li, Jing Shi, Hong-Xi Li and Jian-Ping Lang
Chemical Communications 2013 vol. 49(Issue 81) pp:9248-9250
Publication Date(Web):30 Jul 2013
DOI:10.1039/C3CC45066J
Ambient temperature solid-state reaction of Pb(OAc)2 with TabHPF6 afforded an intermediate product [Pb(Tab)2]2(PF6)4, which further reacted with 4,4′-bipy in the solid state to generate a unique 2D cationic coordination polymer [Pb(Tab)2(4,4′-bipy)](PF6)2 in quantitative yield. Both complexes possess a low dielectric constant and low dielectric loss in the high electric field frequency range.
Co-reporter:Hong-Xi Li, Wei Zhao, Hai-Yan Li, Zhong-Lin Xu, Wen-Xia Wang and Jian-Ping Lang
Chemical Communications 2013 vol. 49(Issue 39) pp:4259-4261
Publication Date(Web):19 Oct 2012
DOI:10.1039/C2CC36736J
The Cu(I)-mediated C–S bond cleavage of 5-methyl-4-(p-tolyl)pyrimidine-2-thiol (mtpmtH) gave one 30-nuclear cluster [Cu30I16(mtpmt)12(μ10-S4)], one polymeric complex [(bmtpms)Cu-(μ-I)]n and one tetranuclear complex [(bmptmds){Cu(μ-I)}2]2; the 30-nuclear cluster displayed excellent catalytic performances in the coupling reactions of N-heterocycles and arylboronic acids and could be recycled and reused.
Co-reporter:Dong Liu, Jian-Ping Lang and Brendan F. Abrahams
Chemical Communications 2013 vol. 49(Issue 26) pp:2682-2684
Publication Date(Web):14 Feb 2013
DOI:10.1039/C3CC39286D
The SCSC transformation of a 1D polymer [Cd(1,3-bdc)(4-spy)2]n produced a 2D polymer [Cd(1,3-bdc)(4-spy)(HT-ppcb)0.5]n through the [2+2] photodimerization reaction. Hydrothermal reactions of HT-ppcb with CdCl2, 1,3-H2bdc and H2O2 afforded another 2D polymer {[Cd(H2O)(1,3-bdc)(bpbpf)]·H2O}n in which HT-ppcb underwent in situ oxidation to form a unique furan-based ligand bpbpf.
Co-reporter:Zhen-Hong Wei, Chun-Yan Ni, Hong-Xi Li, Zhi-Gang Ren, Zhen-Rong Sun and Jian-Ping Lang
Chemical Communications 2013 vol. 49(Issue 42) pp:4836-4838
Publication Date(Web):08 Apr 2013
DOI:10.1039/C3CC41280F
Reactions of [Et4N][TpMoS(S4)] with three equiv. of CuI in MeCN or in pyridine gave rise to one dicubane and one tetracubane anionic clusters, [Et4N]2[{TpMo(μ3-S)3Cu3I}2(μ-I){Cu(μ-I)2(μ4-I)2}] and [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)], and their third-order nonlinear optical (NLO) responses were greatly enhanced relative to that of the precursor.
Co-reporter:Fei-Long Hu, Yan Mi, Yun-Qiong Gu, Li-Gang Zhu, Sheng-Lan Yang, Han Wei and Jian-Ping Lang
CrystEngComm 2013 vol. 15(Issue 45) pp:9553-9561
Publication Date(Web):05 Aug 2013
DOI:10.1039/C3CE41059E
The self-assembly of transition metal salts with 5-(pyridin-4-yl)isophthalate ligand and N-donor ligands affords a series of entangled coordination frameworks based on different metal cluster cores, namely, [Co(L)(H2O)2]·H2O (1), [Ni(L)(H2O)]·H2O (2), [Co4(L)2(SO4)(H2O)5(OH)2]·15.5H2O (3), [Co2(L)2(2,2′-bpy)2]2·H2O (4), [Co2(L)2(phen)2] (5), [Ni(L)(en)(H2O)2]2·2H2O (6), [Ni(L)(dap)]·3H2O (7), [Co(L)(bph)(H2O)2]·H2O (8), [Co(L)(bbm)0.5]·4H2O (9), [Co(L)(bimb)0.5]4·13H2O (10) [L = 5-(pyridin-4-yl)isophthalic acid; 2,2′-bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline; en = ethane-1,2-diamine; dap = propane-1,2-diamine; bph = (1E,2E)-1,2-bis(pyridin-4-ylmethylene)hydrazine; bbm = 1,4-di(1H-imidazol-1-yl)benzene; bimb = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl]. Their structures were characterized by elemental analysis, IR spectra and TG analyses and further determined by single-crystal X-ray diffraction analysis. The auxiliary ligands play important roles in the formation of various entangled networks. 1–2 show a 2D layer network and its layers are held together by π–π stacking interactions and other unconventional interactions. Complex 3 displays an unusual Co4 cluster core which is linked by η1,η1,η1,μ3-SO42− and μ3-OH ions. Upon adding chelating ligands, 4–5 show 2D → 2D entangled polymers with polycatenated and polyrotaxane features based on 4,4-sql layers. 6–7 still exhibit layer strutures, although they have chelating ligands, which may be due to the absence of π–π stacking interactions. 8–10 present pillar-layer structures which are supported by different lengths of pillars. Three-fold interpenetration with polycatenated features are observed in 8–9. 10 exhibits a 4-fold interpenetrating 3D structure with large channel running through its net.
Co-reporter:Fei-Long Hu, Wei Wu, Peng Liang, Yun-Qiong Gu, Li-Gang Zhu, Han Wei, and Jian-Ping Lang
Crystal Growth & Design 2013 Volume 13(Issue 11) pp:5050-5061
Publication Date(Web):September 24, 2013
DOI:10.1021/cg401212s
Reactions of several transition metal [M = Mn(II), Cu(II), Zn(II), Co(II)] salts with 4,4′-{[1,2-phenylenebis(methylene)]bis(oxy)}dibenzoic acid (H2L) and auxiliary N-donor ligands afforded a series of entangled coordination frameworks, [Mn2L2(4,4′-bpy)2][Mn2L2(H2O)2]·2H2O (1), [CuL(bbm)]·0.5H2O (2), [CuL(4,4′-bpy)0.5] (3), [Zn3L2(4,4′-bpy)2(HCOO)2] (4), [ZnL(4,4′-bpy)]2·H2O (5), [Co4L4(bpp)2]·DMF (6), [Co2L2(bbm)]2·2H2O (7), and [CoL(2,2′-bpy)] (8) [2,2′-bpy = 2,2′-bipyridine; 4,4′-bpy = 4,4′-bipyridine; bbm =1,4-di(1H-imidazol-1-yl)benzene; bpp = 1,3-bis(4-pyridyl)propane]. Their structures were characterized by elemental analysis, IR spectra, and TG analysis and further determined by single-crystal X-ray diffraction analysis. Compound 1 has an uncommon 2Dlayer + 1Dchain → 3D framework, while 2 displays a 2-fold interpenetrated 3D framework. Compounds 3–5 show different entangled networks though they adopt the same 4,4′-bpy as the auxiliary ligand. Compounds 3 and 5 show 2-fold interpenetrated 2D networks, showing both polycatenane and polyrotaxane characters. Compound 4 possesses a 2D → 3D polythreaded architecture. Compound 6 has a 3-fold interpenetrated 3D framework by using bpp as the second ligand. Compound 7 presents a 3D framework with a (44·62·88·12)(44·62)(8) topology. Compound 8 presents a 1D helical chain constructed by linking [Co(2,2′-bpy)]2+ units via L ligands. The results provided an interesting insight into how metal ions, auxiliary N-donor ligands, and molar ratios of the components exert great impact on the formation of these entangled networks. The thermal and luminescent properties of 1–8 in solid state at ambient temperature were also investigated.
Co-reporter:Jü-Hua Yang, Xin-Yi Wu, Run-Tian He, Zhi-Gang Ren, Hong-Xi Li, Hui-Fang Wang, and Jian-Ping Lang
Crystal Growth & Design 2013 Volume 13(Issue 5) pp:2124-2134
Publication Date(Web):March 20, 2013
DOI:10.1021/cg4002048
Reactions of N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1–8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1–3 and 5 hold a one-dimensional (1D) chain in which [Ag(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag10(μ-CN)12]n2n– net are plugged with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains. The degradation versus expansion of the bulk AgX frameworks do affect the formation of [AgaXb]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent properties of 1–8 in the solid state were also investigated.
Co-reporter:Cheng Xu, Zhi-Yuan Zhang, Zhi-Gang Ren, Li-Kuan Zhou, Hong-Xi Li, Hui-Fang Wang, Zhen-Rong Sun, and Jian-Ping Lang
Crystal Growth & Design 2013 Volume 13(Issue 6) pp:2530-2539
Publication Date(Web):May 8, 2013
DOI:10.1021/cg400239d
Treatment of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with [Cu(MeCN)4]PF6 and NH4PF6 (molar ratio = 1:2:1) in excess pyridine (py) produced one discrete trinuclear cluster [Et4N][Tp*WS3Cu2(py)3](PF6)2 (2). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6, and 4,4′-bipyridine (4,4′-bipy) (or 1,2-bis(4-pyridyl)ethane (bpea)) (molar ratio = 1:2:1:2) afforded a two-dimensional (2D) [Tp*WS3Cu2]-based cationic polymer {[Tp*WS3Cu2(4,4′-bipy)1.5](PF6)·2MeCN}n (3·2MeCN) and a one-dimensional (1D) [Tp*WS3Cu2]-based cationic polymer {[(Tp*WS3Cu2)2(bpea)3](PF6)2·2DMF}n (4·2DMF), respectively. Analogous reactions of 1 with CuCN, NH4PF6, and 4,4′-bipy (or 1,2-bis(4-pyridyl)ethylene (bpee)) (molar ratio = 1:2:1:2) gave rise to a 2D [Tp*WS3Cu2]-based polymer {[Tp*WS3Cu2(μ-CN)(4,4′-bipy)0.5]·MeCN}n (5·MeCN) and a three-dimensional (3D) [Tp*WS3Cu2]-based anionic polymer {[Et4N][(Tp*WS3Cu2)2{Cu(μ-CN)2.5}2(bpee)]·3MeCN}n (6·3MeCN), respectively. Compounds 2–6 were characterized by elemental analysis, IR, UV–vis, 1H NMR, and single-crystal X-ray diffraction. The cluster cation of 2 has a butterfly-shaped [Tp*WS3Cu2] core structure in which one [Tp*WS3] unit binds two Cu atoms via one μ3-S and two μ-S atoms. 3 consists of one 2D (6,3) network in which butterfly-shaped [Tp*WS3Cu2] units are interlinked by the 4,4′-bipy ligands. 4 contains butterfly-shaped [Tp*WS3Cu2] units that are interconnected by bpea bridges to form one 1D zigzag chain. 5 holds another 2D (6,3) network in which the 1D [{Tp*WS3Cu2}2(μ-CN)2]n chains are bridged by 4,4′-bipy ligands. 6 possesses a 3-connected 3D (103) anionic net in which each 2D [{(Tp*WS3Cu2)2Cu2(μ-CN)4}4(μ-CN)4(bpee)2]n4n– network is interlinked to its neighboring ones via pairs of bpee ligands. The isolation of 2–6 with unstable [Tp*WS3Cu2] cores may be ascribed to the coordination of N-donor ligands or linkers at Cu(I) centers of these cores and the formation of polydimensional [Tp*WS3Cu2]-based frameworks (in the case of 3–5). The third-order nonlinear optical (NLO) properties of 2–6 in DMF were also investigated by using a femtosecond degenerate four-wave mixing (DFWM) technique at 800 nm.
Co-reporter:Ling Wang, Bin Guo, Hong-Xi Li, Qi Li, Hai-Yan Li and Jian-Ping Lang
Dalton Transactions 2013 vol. 42(Issue 44) pp:15570-15580
Publication Date(Web):10 Sep 2013
DOI:10.1039/C3DT51970H
Reaction of Cu(OAc)2·H2O and 1H-pyrazole-3,5-dicarboxylic acid dimethyl ester (Hdcmpz) in MeOH at room temperature afforded one tetranuclear Cu(II)/pyrazolate complex [{Cu2(μ-OAc)2}2(μ-dcmpz)2(μ-OAc)2] (1) in 89% yield. The similar reaction in refluxing MeOH produced a hexanuclear metallamacrocyclic Cu(II)/pyrazolate complex [{Cu(μ-dcmpz)}2(μ-OMe)2]3 (2) in 85% yield. Treatment of the same components under solvothermal conditions resulted in the formation of another tetranuclear Cu(II)/pyrazolate/carboxylate complex [{Cu(MeOH)}4(μ-mcccpz)4] (3, Hmcccpz = 5(3)-(methoxycarbonyl)-1H-pyrazole-3(5)-carboxylic acid) in 30% yield. The mcccpz2− ion in 3 was in situ generated via the hydrolysis of one of two esters on dcmpz ligand. Complexes 1–3 were characterized by elemental analysis, IR and single-crystal X-ray diffraction. An X-ray analysis revealed that 1 contains two {Cu(μ-OAc)}2 fragments that are interconnected by two μ-η2,η2-dcmpz− ligands and two μ-η1,η1-OAc− ions, forming a unique tetrameric structure. Complex 2 is composed of three {Cu(μ-dcmpz)}2 fragments linked by three pairs of μ-OMe− anions, forming a metallamacrocyclic crown structure. 3 consists of four {Cu(MeOH)} fragments linked by two pairs of μ-η1,η2-mcccpz2− ligands, forming a tetrameric [2 × 2] grid-like structure. Complexes 1–3 displayed high catalytic activity toward the condensation of nitriles with 2-aminoalcohol under solvent-free conditions to produce various 2-oxazolines.
Co-reporter:Zhi-Yuan Zhang, Wei-Jie Gong, Fan Wang, Min-Min Chen, Li-Kuan Zhou, Zhi-Gang Ren, Zhen-Rong Sun and Jian-Ping Lang
Dalton Transactions 2013 vol. 42(Issue 26) pp:9495-9504
Publication Date(Web):10 Apr 2013
DOI:10.1039/C3DT50759A
Reactions of [Et4N][Tp*MoS(S)4] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with 3 equiv. of CuX (X = Cl, Br, I, CN) or [Cu(MeCN)4]ClO4 in CH2Cl2–MeCN or CH2Cl2–DMF afforded [Et4N]2[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] (2), [Et4N][Tp*Mo(μ3-S)3(CuX)3] (3: X = Br; 4: X = I), [Et4N][Tp*MoO(μ-S)2(CuX)] (5: X = I; 6: X = CN) and [Tp*Mo(μ3-S)3Cu3(μ3-S′)]4 (7). Compounds 2–7 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, electrospray ion mass spectra (ESI-MS) and X-ray crystallography. The cluster dianion of 2 has a complete cubane-like [Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] structure while the anion of 3 or 4 consists of an incomplete cubane-like [Tp*Mo(μ3-S)3(CuX)3] structure. The anion of 5 or 6 has a binuclear structure, in which one [Tp*MoO(μ-S)2] moiety and one CuX unit are linked by a pair of μ-S atoms. The structure of 7 may be considered as a supercube whose eight corners are occupied by four incomplete cubane-like [Tp*Mo(μ3-S)3Cu3] fragments and four μ3-S′ atoms. The third-order nonlinear optical (NLO) properties of 2–6 in DMF were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Compounds 2–6 exhibited good NLO performances and their NLO responses were enhanced relative to that of 1.
Co-reporter:Lian-Wen Zhu, Hong-Xi Li, Zhi-Gang Ren, Hui-Fang Wang, Wang Yao and Jian-Ping Lang
RSC Advances 2013 vol. 3(Issue 35) pp:15421-15426
Publication Date(Web):23 Jul 2013
DOI:10.1039/C3RA40634B
Through the precoating of TiO2 on Ni foam and the subsequent hydrothermal reaction of the coated species with NaOH and tetrabutyl titanate, we successfully demonstrated the engineered growth of TiO2 nanofibers on the NiO–Ni foam. The adsorption and photodecomposition of Rhodamine B in water showed that the resulting foam is very convenient for the purification of contaminated water. Selective permeability of Au nanoparticles of different sizes revealed that the modified foam possesses size-dependent separation functionality.
Co-reporter:Ming Dai, Lian-Wen Zhu, Ju-Hua Yang, Hong-Xi Li, Min-Min Chen, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2013 Volume 29() pp:70-75
Publication Date(Web):March 2013
DOI:10.1016/j.inoche.2012.11.038
The solvothermal reactions of Zn(NO3)2∙6H2O with 1,4-benzenedicarboxylic acid (1,4-H2bdc) and 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)butane (dmpzb) or 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)hexane (dmpzh) afforded two three-dimensional coordination polymers [Zn3(1,4-bdc)3(dmpzb)]n(1) and [Zn2(1,4-bdc)2(dmpzh)]n(2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compound 1 has an 8-connected 3D net (a 364185262 Schläfli symbol) assembled from trinuclear [Zn3(1,4-bdc)3] units and 1,4-bdc and dmpzb bridges. Compound 2 has a 6-connected 3D net (with a 485463 Schläfli symbol) constructed from binuclear [Zn2(1,4-bdc)2] units and 1,4-bdc and dmpzh linkers. The solid state luminescent and thermal stability properties of 1 and 2 at ambient temperature were also investigated. The results showed that the spacer lengths of bipyrazol-based ligands did affect the topological structures of zinc(II) coordination polymers.Two 3D coordination polymers [Zn3(1,4-bdc)3(dmpzb)]n and [Zn2(1,4-bdc)2(dmpzh)]n were generated from solvothermal reactions of Zn(NO3)2∙6H2O with 1,4-benzenedicarboxylic acid (1,4-H2bdc) and 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)butane (dmpzb) or 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)hexane (dmpzh). Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Highlights► Solvothermal reactions of Zn2 +, 1,4-H2bdc and dmpzb or dmpzh gave two polymers. ► Compound 1 has a 3D net assembled from [Zn3(1,4-bdc)6] units and dmpzb linkers. ► Compound 2 has a 3D net assembled from [Zn2(1,4-bdc)4] units and dmpzh linkers. ► Spacer length effect exerts an impact on the structures of the coordination polymers.
Co-reporter:Hong-Jian Cheng, Bing Wu, Lian-Wen Zhu, Chun-Yan Ni, Ming Dai, Hong-Xi Li, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2013 Volume 31() pp:13-17
Publication Date(Web):May 2013
DOI:10.1016/j.inoche.2013.02.013
Co-reporter:Zhen-Jun Huang, Hong-Jian Cheng, Ming Dai, Chun-Yan Ni, Hong-Xi Li, Kai-Peng Hou, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2013 Volume 31() pp:33-36
Publication Date(Web):May 2013
DOI:10.1016/j.inoche.2013.02.016
•Solvothermal reactions of PbI2 with KI, I2 and dppe gave one 1D and two 3D polymers.•Compound 1 has the EP2 + dications embedded in-between 1D [Pb2I6]n2n − chains.•2 and 3 have 3D nets formed from [Pb3I6] units or [Pb2I4]n chains and dppeo bridges.Reactions of PbI2 with KI, I2 and 1,2-bis(diphenylphosphino)ethane (dppe) (molar ratio = 1:5:3:4) in MeCN/EtOH under solvothermal conditions afforded a one-dimensional (1D) coordination polymer [(EP)(Pb2I6)]n (EP2 + = ethane-1,2-diylbis(ethyldiphenylphosphonium)) (1) and a three-dimensional (3D) coordination polymer [{(Pb3(μ-I)6)(dppeo)3}·EtOH]n (2) (by-product). Treatment of the same components with H2O2 under similar conditions produced another 3D coordination polymer [{Pb2(μ-I)2(μ3-I)2}(dppeo)]n (dppeo = ethane-1,2-diylbis(diphenylphosphine oxide)) (3). Compound 2 could also be prepared in a medium yield from solvothermal reactions of PbI2 with KI, I2 and dppeo (molar ratio = 1:5:3:4). Compounds 1–3 were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 contains one 1D anionic [PbI3]nn − chain with EP2 + dications being embedded between chains. The EP2 + dication was in situ generated via the cleavage of CO bond of EtOH followed by alkylation of dppe. Compound 2 consists of trinuclear [Pb3(μ-I)6] fragments that are interlinked via dppeo bridges to form a 3D 6-connected net (a 41263 Schläfli symbol). Compound 3 has a 3D net (with a 66 Schläfli symbol) constructed from 1D [Pb2(μ-I)2(μ3-I)2]n chains linked by dppeo ligands. The dppeo ligand in 3 was formed in situ from the oxidation of dppe by H2O2. The optoelectronic properties of 1–3 were also investigated.Reactions of 1,2-bis(diphenylphosphino)ethane (dppe) with PbI2, KI and I2 under solvothermal conditions afforded one 1D anionic polymer [(EP)(Pb2I6)]n and one 3D polymer [{(Pb3(μ-I)6)(dppeo)3} · EtOH]n. Analogous reactions of PbI2 with KI, I2 and dppeo generated another 3D polymer [{Pb2(μ-I)2(μ3-I)2}(dppeo)]n. The three complexes were structurally characterized and their optoelectronic properties were studied.
Co-reporter:Lian-Wen Zhu, Li-Kuan Zhou, Hong-Xi Li, Hui-Fang Wang, Jian-Ping Lang
Materials Letters 2013 Volume 95() pp:13-16
Publication Date(Web):15 March 2013
DOI:10.1016/j.matlet.2013.01.004
We report a one-pot route to the formation of free-standing, large-area CNTs/TiO2 nanofiber membrane with enhanced photocatalytic activity. Tetra-n-butyl titanate was reacted with NaOH to form high-quality titanate nanofibers with diameters below 200 nm and longitudinal dimensions of several tens of micrometers. CNTs were condensed with the as-prepared nanofibers and enabled the nanofibers to assemble into a free-standing membrane. It is proposed that the CNTs act as linkers between the nanofibers, and it is crucial for the formation of the membrane under the hydrothermal conditions. Benefiting from the introduction of CNTs, the as-prepared nanofiber membrane exhibited higher photocatalytic activity than pure TiO2 nanofibers.Graphical abstractHighlights► A free-standing CNTs/TiO2 nanofiber membrane was prepared via a one-pot route. ► CNTs are condensed with the nanofibers and enabled them to grow into a membrane. ► Benefiting from CNTs, the membrane exhibited enhanced photocatalytic activity.
Co-reporter:Wen-Yan Yan, Run-Tian He, Min Dai, Zhi-Gang Ren, Hong-Xi Li, Jian-Ping Lang
Inorganic Chemistry Communications 2013 Volume 36() pp:51-55
Publication Date(Web):October 2013
DOI:10.1016/j.inoche.2013.08.002
•Hydrothermal reaction of Zn(NO3)2 with titmb or bitmb and H2BDC gave three complexes.•Compound 1 has a 1D chain formed from [Zn2(titmb)2] and [Zn(1,4-BDC)(H2O)2] units.•Compound 2 has a 2D network formed from [Zn(1,3-BDC)]n chains and titmb linkers.•Compound 3 has a 2D network formed from [Zn2(bitmb)2] cycles and 1,3-BDC bridges.•It offers insight into how the resulting arrays are affected by ligand geometry.Reactions of Zn(NO3)2∙ 6H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) in the presence of 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,3-benzenedicarboxylic acid (1,3-H2BDC) under hydrothermal conditions afforded one 1D and one 2D coordination polymers [Zn3(titmb)2(1,4-BDC)3(H2O)6] (1) and [Zn2(titmb)(1,3-BDC)2(H2O)] (2), respectively. Similar reactions of Zn(NO3)2∙ 6H2O with 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and 1,4-H2BDC gave rise to one 2D coordination polymer [Zn2(bitmb)2(1,4-BDC)2] (3). Compound 1 has a 1D linear chain formed from linking 24-membered [Zn2(titmb)2] metallamacrocycles and [Zn(1,4-BDC)(H2O)2] units via imidazolyl groups of titmb ligands. Compound 2 has a 2D network assembled from connecting spiral [Znn(1,3-BDC)n] chains with titmb linkers, while compound 3 also has a 2D network formed by linking 24-membered [Zn2(bitmb)2] metallamacrocycles via 1,3-BDC bridges. The ligands titmb and bitmb in compounds 1–3 adopt less-common cis–trans–trans and cis–trans conformations, respectively. Their thermal and photoluminescent properties were also investigated.Three Zn(II) coordination polymers [Zn3(titmb)2(1,4-BDC)3(H2O)6] and [Zn2(titmb)(1,3-BDC)2(H2O)], [Zn2(bitmb)2(1,4-BDC)2] were generated from hydrothermal reactions of Zn(NO3)2∙ 6H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) or 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,3-benzenedicarboxylic acid (1,3-H2BDC). These complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.
Co-reporter:Duan-Xiu Li, Min-Min Chen, Fei-Long Li, Zhi-Gang Ren, Bing Wu, Jian-Ping Lang
Inorganic Chemistry Communications 2013 Volume 35() pp:302-306
Publication Date(Web):September 2013
DOI:10.1016/j.inoche.2013.07.014
•Reaction of CdSO4 with tpcb and 5-R-1,3-H2BDC (R = H, NO2) gave two complexes.•1 has a 3D (4,4)-connected net with a (66)2(64 · 82) Schläfli symbol.•2 has a 3D (3,4,5)-connected net with a (52 · 8)(54 · 6 · 8)(4 · 53 · 62 · 7 · 82 · 10) topology.•It offers insight into how the MOF arrays are affected by substituent groups.Hydrothermal reactions of CdSO4 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,3-benzenedicarboxylic acid (1,3-H2BDC) or 5-nitro-1,3-benzenedicarboxylic acid (5-NO2-1,3-H2BDC) resulted in the formation of two coordination polymers [Cd(tpcb)0.5(1,3-BDC)]n (1) and {[Cd2(tpcb)(5-NO2-1,3-BDC)2(OH2)2] · 4H2O}n (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 and 2 exhibit two different types of two-fold interpenetrating 3D architectures with (66)2(64 · 82) and (52 · 8)(54 · 6∙8)(4 · 53 · 62 · 7 · 82 · 10) Schläfli symbols, respectively. Their thermal and photoluminescent properties were also investigated.Two Cd(II) 3D coordination polymers [Cd(tpcb)0.5(1,3-BDC)]n and {[Cd2(tpcb)(5-NO2-1,3-BDC)2(OH2)2] · 4H2O}n were generated from hydrothermal reactions of CdSO4 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,3-benzenedicarboxylic acid (1,3-H2BDC) or 5-nitro-1,3-benzenedicarboxylic acid (5-NO2-1,3-H2BDC). These complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.
Co-reporter:Hong-Ye Ding, Hong-Jian Cheng, Fan Wang, De-Xian Liu, Hong-Xi Li, Yang-Yang Fang, Wei Zhao, Jian-Ping Lang
Journal of Organometallic Chemistry 2013 s 741–742() pp: 1-6
Publication Date(Web):
DOI:10.1016/j.jorganchem.2013.05.012
Co-reporter:Xi Chen, Hong-Xi Li, Zhi-Yuan Zhang, Wei Zhao, Jian-Ping Lang and Brendan F. Abrahams
Chemical Communications 2012 vol. 48(Issue 37) pp:4480-4482
Publication Date(Web):14 Mar 2012
DOI:10.1039/C2CC30581J
Solvothermal reactions of [Et4N][Tp*WS3(CuCl)3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with CuCN and KCu(CN)2 afforded two [Tp*WS3Cu3]-based coordination polymers [Tp*WS3Cu3(μ3-DMF){Cu(CN)3}]2 (2) and K[Tp*WS3Cu3(μ3-DMF){Cu2(CN)4.5}]2 (3). The third-order NLO and PL responses of 1 were activated and greatly amplified through its assembly via the [Cu(CN)3]2− and [Cu4(CN)9]5− species in 2 and 3.
Co-reporter:Ai-Xia Zheng ; Jing Si ; Xiao-Yan Tang ; Li-Li Miao ; Miao Yu ; Kai-Peng Hou ; Fan Wang ; Hong-Xi Li
Inorganic Chemistry 2012 Volume 51(Issue 19) pp:10262-10273
Publication Date(Web):September 17, 2012
DOI:10.1021/ic301191n
Reactions of [Zn(Tab)4](PF6)2 (Tab = 4-(trimethylammonio)benzenethiolate) (1) with 2,2′-bipyridine (2,2′-bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), N-methylimidazole (N-Meim), and 2,6-bis(pyrazol-3-yl)pyridine (bppy) or with CoCl2·6H2O at the presence of N-donor ligands (2,2′-bipy, phen, 4,4′-dimethyl-2,2′-bipyridine (4,4′-dmbpy), 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy))gave rise to a family of zinc or cobalt thiolate complexes, [Zn(Tab)2(L)](PF6)2 (2: L = 2,2′-bipy, 3: L = phen, 4: L = 2,9-dmphen), [Zn(Tab)2(N-Meim)2](PF6)2 (5), [Zn(Tab)2(bppy)](PF6)2 (6), [Co(Tab)2(L)2](PF6)3 (7: L = 2,2′-bipy, 8: L = phen, 9: L = 4,4′-dmbpy), and [Co(Tab)(bdmppy)Cl](PF6) (10). These compounds were characterized by elemental analysis, IR spectra, UV–vis spectra,1H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray diffraction. The Zn(II) in [Zn(Tab)2Ln]2+dications of 2-5 is tetrahedrally coordinated by two Tab ligands and one L or two N-Meim ligands. In 6, the Zn(II) has a distorted trigonal-bipyramidal geometry, coordinated by two Tab ligands and one tridentate bppy ligand. The Co(III) in the [Co(Tab)2(L)2]3+ trications of 7-9 is octahedraly chelated by two bidentate L ligands and two Tab ligands. In 10, the Co(II) adopts a distorted trigonal-bipyramidal geometry, coordinated by one Cl–, one Tab ligand, and one tridentate bdmppy. In the formation of 2-6, two Tab ligands are removed from the [Zn(Tab)4]2+ dication when it is attacked by L ligands, while in the cases of 7-9, the Zn(II) of the [Zn(Tab)4]2+ dication was replaced by Co(III) (derived from oxidation of Co(II) by O2) followed by the removal of two Tab ligands via L ligands. In the case of 10, the central Zn(II) of the [Zn(Tab)4]2+ dication was displaced by Co(II) followed by the removal of three Tab ligands via one Cl– and one tridentate bdmppy. These ligand and metal replacement reactions may provide some interesting information on the interactions of the [Zn(S-Cys)4]2- unit of Zn-MTs with N-heterocyclic ligands and toxic metal ions encountered in a natural environment.
Co-reporter:Xi Chen, Hong-Xi Li, Zhi-Yuan Zhang, Cheng Xu, Kai-Peng Hou, Li-Kuan Zhou, Jian-Ping Lang and Zhen-Rong Sun
CrystEngComm 2012 vol. 14(Issue 11) pp:4027-4033
Publication Date(Web):22 Mar 2012
DOI:10.1039/C2CE25143D
Reactions of the precursor cluster [Et4N][Tp*W(μ3–S)3(CuCl)3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with 2 equiv of AgSCN produced one 1D [Tp*W(μ3–S)3Cu3]-based coordination polymer [Tp*W(μ3–S)3Cu2Cu(μ–SCN)(μ3–SCN)]2·Et2O (2·Et2O) while analogous reactions of 1 with Nadca (dca = dicyanamide) formed one 2D [Tp*W(μ3–S)3Cu3]-based coordination polymer [Tp*W(μ3–S)3Cu3(μ1,5–dca)(μ1(3),5–dca)]2·CH2Cl2 (3·CH2Cl2). Compounds 2–3 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR spectra, and the crystal structures of 2·Et2O and 3·CH2Cl2 were determined by single-crystal X-ray crystallography. The structure of 2 consists of the incomplete cubanelike [Tp*W(μ3–S)3Cu3] cores which are interlinked by SCN bridges. Compound 3 contains repeating dimeric [Tp*W(μ3–S)3Cu3(μ1(3),5–dca)]2 units, which are further interconnected by four Cu–μ–dca–Cu bridges to form a 2D layer with a 63 topology. The third-order nonlinear optical (NLO) properties of 1–3 in DMF were also investigated using femtosecond a degenerate four-wave mixing DFWM technique. The two assemblies 2 and 3 exhibited good third-order NLO performances through connecting the cluster [Tp*W(μ3–S)3Cu3] cores of 1 bearing no NLO properties via thiocyanate or dicyanamide bridges.
Co-reporter:Xiao-Juan Yang, Hong-Xi Li, Zhong-Lin Xu, Hai-Yan Li, Zhi-Gang Ren and Jian-Ping Lang
CrystEngComm 2012 vol. 14(Issue 5) pp:1641-1652
Publication Date(Web):19 Dec 2011
DOI:10.1039/C2CE06312C
Reactions of CuI with bis(4-phenylpyrimidine-2-thio)alkane ligands with different spacer lengths, [(phpy)(CH2)n(phpy)] (phpyH = 4-phenylpyrimidine-2-thiol; n = 1, bphpym; n = 2, bphpye; n = 3, bphpypr; n = 4, bphpyb; n = 5, bphpyp; n = 6, bphpyh), afforded a set of six [CunIn]-based coordination polymers, [{Cu(μ3-I)}2(phpym)]n (1), [{Cu(μ3-I)}4(bphpye)]n (2), [{(MeCN)Cu3(μ-I)2(μ4-I)}2(bphpypr)2]n (3), [{((MeCN)Cu)(μ-I)}2(bphpyb)]n (4), [{Cu2(μ-I)(μ3-I)}2(bphpyp)2]n (5) and [{((MeCN)Cu)(μ3-I)}2{Cu(μ-I)}2(bphpyh)2]n (6), respectively. Compounds 1–6 were characterized by elemental analysis, IR and single-crystal X-ray crystallography. 1 and 2 consist of an unique 2D network in which the 1D staircase [Cu2I2]n chains are linked by phpym or phpye ligands via the μ-η1(N)-η1(N) or μ-η1(N),η1(S)-η1(N),η1(S) coordination modes, respectively. Complexes 3 and 5 consist of double butterfly-shaped {(MeCN)Cu3(μ-I)2(μ4-I)}2 units or chair-like [Cu2(μ-I)(μ3-I)]2 units that are linked to their neighboring ones by pairs of bphpypr or bphpyp bridges to form a 1D double chain. 4 contains a 1D zigzag chain assembled by dimeric [{(MeCN)Cu}(μ-I)]2 cores and bphpyb ligands. In 6, unique 1D tandem-rhomboid [Cu2I2]n chains are connected by dphpyh ligands to form a 2D staircase network. In addition, the photoluminescent properties of 1–6 in the solid state at ambient temperature were investigated.
Co-reporter:Henry Chan, Yang Chen, Ming Dai, Chun-Ning Lü, Hui-Fang Wang, Zhi-Gang Ren, Zheng-Jun Huang, Chun-Yan Ni and Jian-Ping Lang
CrystEngComm 2012 vol. 14(Issue 2) pp:466-473
Publication Date(Web):26 Oct 2011
DOI:10.1039/C1CE05770G
Solvothermal reactions of CuI with 4-cyanopyridine (4-cypy) or 4,4′-bipyridine (4,4′-bipy) and alcohols (methanol, ethanol, propanol, isopropanol) in the presence of I2 and a trace amount of water in acetonitrile gave rise to a family of multi-dimensional iodocuprate complexes of 4-cyanopyridinium and N,N′-dialkyl-4,4′-bipyridinium including {[MC]2[Cu4(μ3-I)4(μ-I)2]}n (MC+ = N-methyl-4-cyanopyridium) (1), {[PC][(Cu2I4)1/4(Cu2I4)1/4]}n (PC+ = N-propyl-4-cyanopyridinium) (2), {[iPC][(Cu2I4)1/4((Cu1/2)4I4)1/4]}n (iPC+ = N-isopropyl-4-cyanopyridium) (3), {[EV]1/4[((Cu1/2)4I4)1/4]}n (EV2+ = N,N′-diethyl-4,4′-bipyridinium) (4) and {[PV]1/2[(Cu2I4)1/4((Cu1/2)4I4)1/4]}n (PV2+ = N,N′-dipropyl-4,4′-bipyridinium) (5). The resulting 4-cyanopyridinium and viologen cations were generated in situ via the cleavage of the C–O bond of alcohols followed by alkylation of 4-cypy or 4,4′-bipy. X-ray analysis revealed that compound 1 consists of a unique three-dimensional anionic [Cu4I6]n2n− framework while compounds 2–5 contain one-dimensional anionic [Cu2I4]n2n− chains that are enclosed into different cationic channels formed by either 4-cyanopyridinium or N,N′-dialkyl-4,4′-bipyridinium. The dielectric properties of 1–5 were investigated.
Co-reporter:Ming Dai, Wen-Yan Yan, Zhi-Gang Ren, Hui-Fang Wang, Wei-Jie Gong, Fu-Ling Li, Xin Zhao, Hong-Xi Li and Jian-Ping Lang
CrystEngComm 2012 vol. 14(Issue 19) pp:6230-6240
Publication Date(Web):19 Jun 2012
DOI:10.1039/C2CE25482D
Reactions of Zn(NO3)2 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,4-benzenedicarboxylic acid (1,4-H2BDC), 4,4′-biphenyldicarboxylic acid (4,4′-H2BPDB), 5-methyl-1,3-benzenedicarboxylic acid (5-CH3-1,3-H2BDC), 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC), 5-amino-1,3-benzenedicarboxylic acid (5-NH2-1,3-H2BDC), 4,4′-benzophenonedicarboxylic acid (4,4′-H2BPNDB) under solvothermal conditions led to the formation of six polydimensional coordination polymers {[Zn5(1,4-BDC)5(tpcb)2.5]·5H2O}n (1), {[Zn2(4,4′-BPDB)2(tpcb)]·0.5MeCN}n (2), [Zn2(OH2)2(5-CH3-1,3-BDC)2(tpcb)]n (3), {[Zn2(1,3,5-HBTC)2(tpcb)]·H2O}n (4), {[Zn2(5-NH2-1,3-BDC)2(tpcb)·H2O]}n (5), and [Zn2(4,4′-BPNDB)2(tpcb)]n (6). Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compounds 1 and 6 have different 3D (4,4) connected structures. Compounds 2–4 have different two-fold interpenetrating 3D (4,4)-connected structures. Compound 5 holds a 2D (3,4)-connected structure. The solid state luminescent properties of compounds 1–6 at ambient temperature were also investigated. The results provided some interesting insights into ligand effects on the structures and luminescent properties of zinc(II) coordination polymers.
Co-reporter:Hong-Jian Cheng, Hong-Xi Li, Zhi-Gang Ren, Chun-Ning Lü, Jing Shi and Jian-Ping Lang
CrystEngComm 2012 vol. 14(Issue 18) pp:6064-6071
Publication Date(Web):13 Jun 2012
DOI:10.1039/C2CE25677K
Hydrothermal reactions of CdCl2·2.5H2O with 4,4'-bis(1-imidazolyl)bibenzene (bimb) and 1,3-benzenedicarboxylate (1,3-H2BDC), 5-methyl-1,3-benzenedicarboxylate (5-Me-1,3-H2BDC), 5-amino-1,3-benzenedicarboxylate (5-NH2-1,3-H2BDC), 5-hydroxy-1,3-benzenedicarboxylate (5-HO-1,3-H2BDC), 5-nitro-1,3-benzenedicarboxylate (5-NO2-H21,3-BDC), or 5-sulfo-1,3-benzenedicarboxylate (5-HSO3-1,3-H2BDC) resulted in the formation of six Cd(II) coordination polymers, [Cd(5-R-1,3-BDC)(bimb)]n (R = H (1), R = Me (2), R = NH2 (3), R = OH (4)), {[Cd2(H2O)(5-NO2-1,3-BDC)2(bimb)]·2H2O}n (5) and [Cd(5-SO3-1,3-HBDC)(bimb)]n (6). Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. 1–4 exhibit similar 3D frameworks in which 2D [Cd4(5-R-1,3-BDC)4]n (R = H, Me, NH2 and OH) layers are interlinked by bimb ligands. 5 has a two-fold interpenetrating 3D framework in which 1D [Cd2(5-NO2-1,3-BDC)2]n chains are interconnected by bimb ligands. 6 shows a 3D (3,5)-connected framework in which 2D [Cd2(5-SO3-1,3-HBDC)2]n networks are bridged by bimb ligands. The Schläfli symbols for these six 3D nets are (4·62)(4·66·83) (1–4), (42·6)(42·6·102·12) (5) and (4·6·8)(4·65·83·10) (6). The solid state photoluminescent properties of 1–6 were also investigated.
Co-reporter:Sha Sun, Zhi-Gang Ren, Ju-Hua Yang, Run-Tian He, Fan Wang, Xin-Yi Wu, Wei-Jie Gong, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2012 vol. 41(Issue 27) pp:8447-8454
Publication Date(Web):23 May 2012
DOI:10.1039/C2DT30860F
The reaction of [Ag(MeCN)4]ClO4 with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in CH2Cl2/MeOH afforded an unexpected cationic binuclear complex [Ag2(L1)2(η,η-μ-ClO4)2](ClO4)2 (L1 = N,N′-bis(diphenylphosphanylmethyl)-3H-4,5-dihydroimidazole-1-ium) (1). Compound 1 was also prepared in high yield from reactions of [Ag(MeCN)4]ClO4 with N,N′-bis(diphenylphosphanylmethyl)ethylenediamine (bdppeda) in the presence of formaldehyde (HCHO) or formic acid (HCOOH). Analogous reactions of AgCl with bdppeda and HCHO resulted in the formation a neutral binuclear complex [Ag2(L2)2(μ-Cl)2] (L2 = N,N-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) (2). Treatment of 1 with concentrated HCl gave rise to a partially anion-exchanged product [Ag2(L1)2(μ-Cl)2](ClO4)2 (3). Compounds 1 and 3 have a similar cationic binuclear structure, in which a [Ag2(η,η-μ-ClO4)2] or [Ag2(μ-Cl)2] ring is sandwiched by two in situ-formed cationic L1 ligands. The L1 ligand may be generated by the Ag(I)-assisted condensation reaction between bdppeda and HCHO or HCOOH. Compound 2 holds a neutral binuclear structure, in which a [Ag2(μ-Cl)2] ring is connected by two in situ-formed L2 ligands from its top and bottom sites. The neutral ligand L2 may be produced from another Ag(I)-assisted condensation reaction between bdppeda and HCHO. The in situ formation of the L1 and L2 ligands provides a new route to the N-heterocyclic diphosphine ligands, and an interesting insight into the coordination chemistry of their metal complexes.
Co-reporter:Xiao-Yan Tang, Rong-Xin Yuan, Jin-Xiang Chen, Wei Zhao, Ai-Xia Zheng, Miao Yu, Hong-Xi Li, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2012 vol. 41(Issue 20) pp:6162-6172
Publication Date(Web):09 Mar 2012
DOI:10.1039/C2DT30313B
Reactions of TabHPF6 (Tab = 4-(trimethylammonio)benzenethiolate) with three equiv. of M(OAc)2·2H2O (M = Zn, Cd) gave rise to two tetranuclear adamantane-like compounds, [M4(μ-Tab)6(Tab)4](PF6)8·S (1·S: M = Zn, S = DMF·4H2O; 2·S: M = Cd, S = DMF·5H2O). The similar reactions of MCl2 (M = Zn, Cd, Hg) with four equiv. of TabHPF6 in the presence of Et3N afforded three mononuclear compounds [M(Tab)4](PF6)2·S (3·S: M = Zn, S = 2(H2O)0.5; 4·S: M = Cd, S = 2(H2O)0.5; 5·S: M = Hg, S = 2DMF). Treatment of the precursor complex 3 or 5 with equimolar MCl2 and two equiv. of TabHPF6 and Et3N produced one dinuclear compounds [M(μ-Tab)(Tab)2]2(PF6)4·2DMF·2H2O (6·2DMF·2H2O: M = Zn; 8·2DMF·2H2O: M = Hg) while analogous reactions of 4 with CdCl2·2H2O gave rise to [Cd(μ-Tab)2(Tab)]2(PF6)4·2DMF (7·2DMF). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR and single-crystal X-ray crystallography. In 1 or 2, four M2+ ions and six S atoms of Tab ligands constitute an adamantane-like [M4(μ-S)6] cage in which each M2+ ion is tetrahedrally coordinated by one terminal S and three bridged S atoms from four different Tab ligands. In 3–5, each M2+ center of the [M(Tab)4]2+ dication is tetrahedrally coordinated by four S atoms of Tab ligand. Two [M(Tab)2]2+ dications in 6 or 8 are further bridged by a pair of Tab ligands to form a dimeric [M(μ-Tab)(Tab)2]24+ structure. Each dimeric [(Tab)Cd(μ-Tab)2Cd(Tab)]4+ unit in 7 is linked to its two neighboring units via two couples of bridging Tab ligands, thereby generating a unique 1D cationic chain. These results may provide useful information on interpreting structural data of MTs containing group 12 metals.
Co-reporter:Li-Li Miao, Hong-Xi Li, Miao Yu, Wei Zhao, Wei-Jie Gong, Jun Gao, Zhi-Gang Ren, Hui-Fang Wang and Jian-Ping Lang
Dalton Transactions 2012 vol. 41(Issue 12) pp:3424-3430
Publication Date(Web):03 Feb 2012
DOI:10.1039/C2DT12145J
Treatment of [CuCl2(bppyH2)] (1, bppyH2 = 2,6-di(1H-pyrazol-3-yl)pyridine) with 2 equiv. of AgNO3 in DMF gave rise to a binuclear Cu(II) complex [Cu2(bppyH)2(NO3)2] (bppyH = 2-(pyrazol-3-yl)-6-(pyrazolate)pyridine) (2). Complex 2 was characterized by elemental analysis, IR and single crystal X-ray diffraction. Complex 2 has a dimeric structure in which the two Cu(II) centers are bridged by a couple of the in situ-generated bppyH− anions. Each Cu(II) center is further coordinated by one O atom of a NO3− anion and three N atoms of one bppyH− anion. Complex 2 exhibited a higher catalytic activity in the polymerization of methyl methacrylate (MMA) than the precursor complex 1. Even though the ratio of catalyst to MMA was raised up to 1:1500, the PDI for 2 (reaction time was fixed at 4 h) is 1.63 and the conversion is up to 72%. The effects of solvent, reaction temperature and the ratio of MMA to catalyst were also investigated.
Co-reporter:Ai-Xia Zheng, Hong-Xi Li, Kai-Peng Hou, Jing Shi, Hui-Fang Wang, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2012 vol. 41(Issue 9) pp:2699-2706
Publication Date(Web):20 Jan 2012
DOI:10.1039/C2DT12219G
Reaction of MeHgI with Ag2O in H2O followed by addition of equimolar TabHPF6 in MeCN gave rise to a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF6 (1) (TabH = 4-(trimethylammonio)benzenethiol) in a high yield. Treatment of 1 with KI and KSCN afforded an anion exchange product [MeHg(Tab)]I·0.25H2O (2·0.25H2O) and [MeHg(Tab)]SCN (3), respectively, while that of 1 with equimolar Tab resulted in the formation of another MeHg/Tab compound [MeHg(Tab)2]PF6 (4). The cation of 2 or 3 shows an approximately linear structure in which the central Hg(II) is coordinated by one C atom of one CH3 group and one S atom of a Tab ligand. The Hg(II) center of the cation of 4 is trigonally coordinated by one C atom of the CH3 group and two S atoms of two Tab ligands. The analogous reaction of 1 with NH4SCN led to the cleavage of the Hg–C bond of 1 and the formation of a known four-coordinated Hg(II)/Tab complex [Hg(Tab)2(SCN)2] (5). When 4 was treated with 4,6-Me2pymSH or EtSH, another four-coordinated Hg(II)/Tab complex [Hg(Tab)4]3(PF6)6 (6) was generated in a high yield. The Hg(II) center of each cation of 6 is tetrahedrally coordinated by four S atoms of four Tab ligands. The results suggested that cleavage of the Hg–C bond in the methylmercury complex 1 could be completed by increasing the coordination number of its Hg(II) center by S-donor ligands and protonating the methyl group by weak acids.
Co-reporter:Ai-Xia Zheng, Hui-Fang Wang, Chun-Ning Lü, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2012 vol. 41(Issue 2) pp:558-566
Publication Date(Web):02 Nov 2011
DOI:10.1039/C1DT11663K
Reactions of Cd(NO3)2·4H2O with TabHPF6 (TabH = 4-(trimethylammonio)benzenethiol) and Et3N in the presence of NH4SCN and five other N-donor ligands such as 2,2′-bipyridine (2,2′-bipy), phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), 2,6-bis(pyrazd-3-yl)pyridine (bppy) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy) gave rise to a family of Cd(II)/thiolate complexes of N-donor ligands, {[Cd2(μ-Tab)4(NCS)2](NO3)2·MeOH}n (1), [Cd2(μ-Tab)2(L)4](PF6)4 (2: L = 2,2′-bipy; 3: L = phen), [Cd(Tab)2(L)](PF6)2 (4: L = 2,9-dmphen; 5: L = bppy), and [Cd2(μ-Tab)2(Tab)2(bdmppy)]2(PF6)8·H2O (6·H2O). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. For 1, each [Cd(NCS)]+ fragment is connected to its equivalents via a pair of Tab bridges to a one-dimensional chain. For 2 and 3, two [Cd(2,2′-bipy)2]2+ or [Cd(phen)2]2+ units are linked by a pair of Tab bridges to form a cationic dimeric structure. The Cd atom in [Cd(Tab)2(L)]2+ dication of 4 or 5 is coordinated by two Tab ligands and chelated by two N atoms from 2,9-dmphen (4) or three N atoms from bppy (5), forming a distorted tetrahedral (4) or trigonal bipyramidal (5) coordination geometry. For 6, each of two [Cd(Tab)(bdmppy)] fragments is linked to one [(Tab)Cd(μ-Tab)2Cd(Tab)] fragment via two Tab bridges to generate a unique cationic zigzag tetrameric structure where the Cd centers take a tetrahedral or a trigonal bipyramidal coordination geometry. The results may provide an interesting insight into mimicking the coordination spheres of the Cd(II) sites of metallothioneins and their interactions with various N-donor ligands encountered in nature.
Co-reporter:Lianwen Zhu;Zhigang Ren;Jianping Lang
Chinese Journal of Chemistry 2012 Volume 30( Issue 7) pp:1469-1473
Publication Date(Web):
DOI:10.1002/cjoc.201200178
Abstract
A membrane consisting of TiO2 nanofibers was successfully fabricated through a simple solvothermal water/n-hexane interface reaction of tetra-n-butyl titanate with NaOH followed by post treatments of acid washing and calcination. Tetra-n-butyl titanate reacts with NaOH at the interface to form high-quality nanofibers with lateral dimensions below 200 nm and longitudinal dimensions of several tens of micrometers. The membrane is formed by the interpenetration and overlapping of the flexible nanofibers and distributed by holes with sizes ranging from several tens of nanometers to several hundreds of nanometers. Because of the porous structure, this nanofiber membrane exhibited a high efficiency in the photodecomposition of dyes in water.
Co-reporter:Lianwen Zhu;Zhigang Ren;Jianping Lang
Chinese Journal of Chemistry 2012 Volume 30( Issue 7) pp:
Publication Date(Web):
DOI:10.1002/cjoc.201290018
Co-reporter:Ai-Xia Zheng, Zhi-Gang Ren, Hui-Fang Wang, Hong-Xi Li, Jian-Ping Lang
Inorganica Chimica Acta 2012 Volume 382() pp:43-51
Publication Date(Web):15 March 2012
DOI:10.1016/j.ica.2011.10.008
Reactions of PdCl2·2H2O with 2 equiv. of 4-(trimethylammonio)benzenethiolate (Tab) (prepared in situ from a mixture of TabHPF6 and Et3N in MeOH) and seven phosphine ligands: PPh3, 1,1-bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), and 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda), afforded a family of mononuclear and dinuclear Pd(II)/Tab/phosphine complexes, [Pd2(PPh3)2(Tab)2(μ-Tab)2](PF6)4 (1), [Pd2(dppm)2(Tab)2(μ-Tab)](PF6)4 (2), [Pd2(dppb)(Tab)2(μ-Tab)2]Cl4 (3), [PdL(Tab)2](PF6)2 (4: L = dppe; 5: L = dppp) and {[PdL(Tab)2]2}Cl4 (6: L = dppeda; 7: L = dpppda). These compounds were characterized by elemental analysis, IR spectra, UV–Vis spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. In the structure of 1–7, each Pd(II) adopt an approximate square planar coordination geometry. The results provide an interesting insight into the chemistry of palladium(II)/thiolate/phosphine complexes.Graphical abstractTreatment of PdCl2·2H2O with 2 equiv. of Tab and PPh3, dppm, dppe, dppp, dppb, dppeda, or dpppda, afforded mono- and di-nuclear Pd(II)/Tab/phosphine complexes, [Pd2(PPh3)2(Tab)2(μ-Tab)2](PF6)4, [Pd2(dppm)2(Tab)2(μ-Tab)](PF6)4, [Pd2(dppb)(Tab)2(μ-Tab)2]Cl4, [PdL(Tab)2](PF6)2 (L = dppe; dppp) and {[PdL(Tab)2]2}Cl4 (L = dppeda; dpppda). These complexes were characterized by elemental analysis, IR, UV–Vis, 1H and 31P{1H} NMR, ESI-MS and single-crystal X-ray crystallography.Highlights► Reaction of PdCl2 with Tab and phosphine ligands gave complexes 1–7. ► These complexes formed either mononuclear or binuclear structures. ► Mononuclear (4 and 5) and binuclear compounds (6 and 7) could survive in solution. ► Binuclear compounds (1–3) could not keep their solid state structures. ► The results provide an insight into the chemistry of Pd(II)/Tab/phosphine complexes.
Co-reporter:Li-Min Wan;Hong-Xi Li;Wei Zhao;Hong-Ye Ding;Yang-Yang Fang;Pei-Hong Ni
Journal of Polymer Science Part A: Polymer Chemistry 2012 Volume 50( Issue 23) pp:4864-4870
Publication Date(Web):
DOI:10.1002/pola.26308
Abstract
In the presence of excess NaOH, reaction of Cu(OAc)2·H2O with equimolar ammonium calix[4]arene [H4L]I4 (1, H4L = [5,11,17,23-tetrakis(trimethylammonium)-25,26,27,28-tetrahydroxycalix[4]arene]) resulted in the formation of a mononuclear cationic Cu(II) complex [Cu(II)L(H2O)]I2 (2) in 43% yield. Complex 2 was characterized by elemental analysis, infrared (IR), and single crystal X-ray diffraction. The Cu(II) atom in 2 is coordinated by four oxygen atoms of one L4− ligand and one O atom from one water molecule, forming a square pyramidal geometry. Complex 2 exhibited high catalytic activity in the oxidative polymerization of 2,6-dimethylphenol using O2 as oxidizing agent in water under mild conditions. The selective polymerization produced poly(2,6-dimethyl-1,4-phenylene oxide) in high yields with almost no diphenoquinone. The influence of the polymerization temperature, the time interval, the molar ratio of 2,6-dimethylphenol/2, the concentrations of sodium hydroxide, and sodium n-dodecyl sulfate were examined. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
Co-reporter:Lei-Lei Liu, Hong-Xi Li, Li-Min Wan, Zhi-Gang Ren, Hui-Fang Wang and Jian-Ping Lang
Chemical Communications 2011 vol. 47(Issue 39) pp:11146-11148
Publication Date(Web):02 Sep 2011
DOI:10.1039/C1CC14262C
Reactions of [H4L][PF6]4 with 4 equiv. of Mn(OAc)2·4H2O in the presence of air gave rise to a mononuclear Mn(III)–superoxo complex [Mn(III)L(O2)(H2O)](PF6)2, which contains a bowl-shaped cationic structure with a D4d symmetry. It has an unprecedented linear end-on Mn(III)–O2 unit and exhibited good efficiency and selectivity in the catalytic oxidation of alkenes with O2 plus isobutyraldehyde under mild conditions.
Co-reporter:Xiao-Yan Tang ; Ai-Xia Zheng ; Hai Shang ; Rong-Xin Yuan ; Hong-Xi Li ; Zhi-Gang Ren
Inorganic Chemistry 2011 Volume 50(Issue 2) pp:503-516
Publication Date(Web):December 14, 2010
DOI:10.1021/ic101587h
Reactions of [Hg(Tab)2](PF6)2 (TabH = 4-(trimethylammonio)benzenethiol) (1) with acetic acid (HAc), propanoic acid (HPro), salicylic acid (HSal), benzoic acid (HBez), malonic acid (H2Mal), oxalic acid (H2Oxa), adipic acid (H2Adi), or methylimindiacetic acid (H2Meida) in the presence of Et3N gave rise to a family of mercury(II)-thiolate-carboxylate compounds, [Hg(Tab)2(Ac)](PF6)·0.5H2O (2·0.5H2O), [Hg(Tab)2(Pro)](PF6) (3), [Hg(Tab)2(Sal)](PF6)·MeOH (4·MeOH), [Hg(Tab)2(Sal)](Sal)·MeOH (5·MeOH), [Hg(Tab)2(Bez)](PF6)·H2O (6·H2O), [Hg(Tab)2(HMal)](Mal)0.5 H2O (7·H2O), [{Hg(Tab)2}2(μ-Oxa)](PF6)2 H2O (8·2H2O), [{Hg(Tab)2}2(μ-Adi)](PF6)2 (9), [Hg(μ-Tab)(μ-Adi)]2n (10), and [Hg(Tab)2(Meida)]·2.5H2O (11·2.5H2O). These compounds were characterized by elemental analysis, IR spectra, UV−vis spectra, 1H NMR, and single-crystal X-ray crystallography. Each mercury(II) atom in [Hg(Tab)2]2+ dication of 2−7 is further coordinated by two oxygen atoms from one Ac−, Pro−, Sal−, Bez−, Mal2− or HMal− anion, forming a unique seesaw-shaped coordination geometry. In 8 or 9, two [Hg(Tab)2]2+ dications are connected by one bridging oxalate or adipate dianion to generate a dimeric structure with each mercury(II) center adopting a seesaw-shaped geometry. In 10, a pair of octahedrally coordinated mercury(II) atoms are bridged by two sulfur atoms of two Tab ligands to form a [Hg(μ-Tab)2Hg]4+ fragment, which is further connected to its equivalent ones via four adipate dianions, thereby forming a rare two-dimensional network. In 11, the mercury(II) atom in the [Hg(Tab)2]2+ dication is coordinated by one nitrogen and two oxygen atoms from one Meida2− dianion to have a rare square pyramidal geometry. The formation of 2−11 from 1 may be applicable to mimicking the interactions of the mercury(II) sites of Hg-MerR and Hg-MT with various amino acids encountered in nature.
Co-reporter:Li-Pei Wei ; Zhi-Gang Ren ; Lian-Wen Zhu ; Wen-Yan Yan ; Sha Sun ; Hui-Fang Wang ; Jian-Ping Lang ;Zhen-Rong Sun
Inorganic Chemistry 2011 Volume 50(Issue 10) pp:4493-4502
Publication Date(Web):April 8, 2011
DOI:10.1021/ic200147d
Treatment of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS2)2(μ-S2)] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH2Cl2 or CHCl3 formed three neutral W/Cu/S clusters [{Tp*W(μ3-S)3Cu3(μ-Cl)}2Cu(μ-Cl)2(μ7-Cl)(MeCN)]2 (3), [{Tp*W(μ3-S)3Cu3}2Br(μ-Br)2(μ4-Br)(MeCN)] (4), and [{Tp*W(μ3-S)3Cu3}2{Cu2(μ-I)4(μ3-I)2}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et4NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et4N][{Tp*W(μ3-S)3Cu3X}2(μ-X)2(μ4-X)] (6: X = Cl; 7 X = Br). Compounds 2−7 were characterized by elemental analysis, IR, UV−vis, 1H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS2] fragments in which two W atoms are connected by one S22− dianion. Compounds 3−7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ3-S)3Cu3]2+ dications are linked via a μ7-Cl− bridge, two μ-Cl− bridges, and a [Cu(MeCN)(μ-Cl)2]+ bridge. For 4, one [Tp*W(μ3-S)3Cu3(MeCN)]2+ dication and one [Tp*W(μ3-S)3Cu3Br]+ cation are linked via a μ4-Br− and two μ-Br− bridges. For 5, the two [Tp*W(μ3-S)3Cu3]2+ dications are bridged by a linear [(μ-I)2Cu(μ3-I)2Cu(μ-I)2]4+ species. For 6 and 7, two [Tp*W(μ3-S)3Cu3X]+ cations are linked by a μ4-X− and two μ-X− bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2−7 in MeCN/CH2Cl2 were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.
Co-reporter:Yang Chen, Zhou Yang, Xin-Yi Wu, Chun-Yan Ni, Zhi-Gang Ren and Jian-Ping Lang
Physical Chemistry Chemical Physics 2011 vol. 13(Issue 22) pp:10781-10786
Publication Date(Web):06 May 2011
DOI:10.1039/C1CP20422J
Solvothermal reactions of CuI with isopropanol, 4,4′-bipyridine, I2 and a small amount of water in MeCN produced one coordination compound [isopropylviologen][CuI3] (isopropylviologen = N,N′-diisopropyl-4,4′-bipyridinium) (1). The dielectric constants of the single crystal of 1 along the three crystal axes are different with the largest diversity ratio of ∼3.3, showing dielctric anisotropic behavior. Under low temperature (<273 K) or medium electric field frequency range (1 KHz–1 MHz), the dielectric constant of the title compound is nearly unchanged, exhibiting a temperature/frequency-independent characteristics. The crystalline powder of 1 has a low dielectric constant and low dielectric loss in the medium electric field frequency range, which is comparable to the traditional low-k material SiO2.
Co-reporter:Dong Liu, Yu-Jie Chang and Jian-Ping Lang
CrystEngComm 2011 vol. 13(Issue 6) pp:1851-1857
Publication Date(Web):06 Dec 2010
DOI:10.1039/C0CE00575D
The hydrothermal reactions of Zn(NO3)2·6H2O with 1,4-bis[2-(4-pyridyl)ethenyl]benzene (1,4-bpeb), NaOH, and 1,4-phenylenediacetic acid (1,4-H2PDA), 1,3-phenylenediacetic acid (1,3-H2PDA) or 1,2-phenylenediacetic acid (1,2-H2PDA) afforded three coordination polymers {[Zn(1,4-PDA)(1,4-bpeb)]·2H2O}n (1), [Zn(1,3-PDA)(1,4-bpeb)]n (2) and [Zn4(μ-OH)2(1,2-PDA)3(1,4-bpeb)2]n (3), respectively. All these compounds were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 exhibits a five-fold interpenetrating 3D diamondoid framework constructed by linking Zn atoms with trans-1,4-PDA and trans-trans-trans-1,4-bpeb ligands. 2 has a 2D (4,4) network formed by connecting dinuclear [Zn2(1,3-PDA)2] (1,3-PDA serving as a trans conformation) units with trans-cis-trans-1,4-bpeb ligands. 3 could be considered as a 2D 5-connected network derived from linking tetranuclear [Zn4(μ-OH)2(1,2-PDA)3] (1,2-PDA acting as cis and trans conformations) units via trans-cis-trans-1,4-bpeb bridges. The results provided some insight into the ligand geometry-driven assembly of coordination polymers. Thermal stability and photoluminescent properties of 1–3 were also investigated.
Co-reporter:Liang Zhang, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
CrystEngComm 2011 vol. 13(Issue 5) pp:1400-1405
Publication Date(Web):12 Nov 2010
DOI:10.1039/C0CE00513D
Reactions of CuX (X = Cl, Br, I, SCN, CN) with 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazole)propane (tdmpp) gave rise to five coordination polymers, [{Cu2X2(tdmpp)}·Sol]n (1: X = Cl, Sol = 0.5MeCN; 2: X = Br, Sol = 0.5MeCN; 3: X = I, Sol = MeCN; 4: X = SCN), and [Cu3(CN)3(tdmpp)]n (5). Compounds 1–5 were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compounds 1–4 contain a 1D helical (1–3) or linear (4) chain assembled by [CuX]2 cores and tdmpp ligands. While for 5, the zigzag [CuCN]n chain is linked by tdmpp ligands to form a 2D (4,4) staircase network. The oxidation state of copper in these coordination networks is assumed to be +1. The solid state luminescent properties of compounds 1–5 at ambient temperature were also investigated.
Co-reporter:Yang Chen, Zhou Yang, Cheng-Xin Guo, Chun-Yan Ni, Hong-Xi Li, Zhi-Gang Ren and Jian-Ping Lang
CrystEngComm 2011 vol. 13(Issue 1) pp:243-250
Publication Date(Web):03 Sep 2010
DOI:10.1039/C0CE00309C
Solvothermal reactions of PbI2 with 4-cyanopyridine (4-cypy) or 4,4′-bipyridine (4,4′-bipy) and alcohols (ethanol, propanol, iso-propanol, benzyl alcohol, α,α′-dihydroxy-p-xylene) in the presence of PbI2, I2 and a trace amount of water in acetonitrile gave rise to a family of 1D iodoplumbate complexes of 4-cyanopyridinium and N,N′-dialkyl-4,4′-bipyridinium including {[EC]4[(Pb2I6)2]·2MeCN}n (EC+ = N-ethyl-4-cyanopyridium) (1), {[PC][PbI3]}n (PC+ = N-propyl-4-cyanopyridium) (2), {[iPC]3[(PbI3)(Pb2I6)]}n (iPC+ = N-isopropyl-4-cyanopyridium) (3), {[BzC][PbI3]}n (BzC+ = N-benzyl-4-cyanopyridium) (4), {[Cxy]2[(Pb2I6)2]}n (Cxy2+ = 1,4-bis(4-cyanopyridium)-xylene) (5), {[EV]1.5[Pb3I9]}n (EV2+ = N,N′-diethyl-4,4′-bipyridinium) (6), {[PV]1.5[Pb3I9]}n (PV2+ = N,N′-dipropyl-4,4′-bipyridinium) (7), and {[iPV]2[Pb4I12]}n (iPV2+ = N,N′-diisopropyl-4,4′-bipyridinium) (8). The resulting 4-cyanopyridinium and viologen cations were generated in situ via the cleavage of C–O bond of alcohols followed by alkylation of 4-cypy or 4,4′-bipy. X-Ray analysis revealed that compounds 1–8 contain one-dimensional anionic [PbI3]nn− (1–5, 8) and [Pb3I9]n3n− (6 and 7) chains that are enclosed into the different cationic channels formed from the 4-cyanopyridinium and N,N′-dialkyl-4,4′-bipyridinium. In addition, the optoelectronic and dielectric properties of 1–8 were also investigated.
Co-reporter:Wang Jing, Zhi-Gang Ren, Ming Dai, Yang Chen and Jian-Ping Lang
CrystEngComm 2011 vol. 13(Issue 16) pp:5111-5118
Publication Date(Web):16 Jun 2011
DOI:10.1039/C1CE05156C
Solvothermal reactions of 1,1′-(1,6-hexanediyl)bis-1H-benzimidazole (hbbm) with Zn(II), or Cd(II) salts yielded six coordination polymers, [MX2(hbbm)]n (1: M = Zn, X = Cl; 2: M = Zn, X = Br), {[CdI2(hbbm)]·0.5H2O}n (3), [CdCl2(hbbm)2]n (4), [Cd3(η,μ-OAc)2(μ-OAc)2(OAc)2(hbbm)2]n (5), and [Zn2(μ-OAc)4(hbbm)]n (6). Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compounds 1–3 contain a 1D zigzag chain in which [MX2] units are linked by hbbm bridges. For 4, each [Cd4Cl8(hbbm)4] unit acting as a planar four-connecting node connects other four equivalent ones via eight hbbm molecules to form a 2D (4,4) network. For 5, each linear [Cd3(η,μ-OAc)2(μ-OAc)2(OAc)2] unit is linked by two pairs of hbbm bridges to afford a 1D double chain. For 6, each [Zn2(μ-OAc)4] unit is connected by hbbm bridges to form a 1D U-type chain, which further interweaves with other adjacent chains to form a unique 3D net. The solid state luminescent properties of 1–6 at ambient temperature were also investigated.
Co-reporter:Lei-Lei Liu, Zhi-Gang Ren, Lian-Wen Zhu, Hui-Fang Wang, Wen-Yan Yan, and Jian-Ping Lang
Crystal Growth & Design 2011 Volume 11(Issue 8) pp:3479
Publication Date(Web):June 10, 2011
DOI:10.1021/cg200308k
Solvothermal reactions of LnCl3·6H2O (Ln = Nd, Eu, Yb) with equimolar amounts of 5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene (H4L) at 90 or 140 °C gave rise to a set of six lanthanide(III) coordination polymers {[Nd2ClL(HCOO)(DMF)3(H2O)]·0.5DMF·MeCN·1.5H2O}n (1), {[Ln2ClL(HCOO)(DMF)]·sol}n (2: Ln = Eu, sol =0.5MeCN·1.5H2O; 3: Ln = Yb, sol = 1.5H2O), and {[H3O][LnL(H2O)]·DMF·MeCN·H2O}n (4: Ln = Nd; 5: Ln = Eu; 6: Ln = Yb). Complexes 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1–3 have two-dimensional (2D) networks in which [Nd6Cl4L2(DMF)12(H2O)2] units (1) or [Ln6Cl4L2(DMF)2] (Ln = Eu (2), Yb (3)) are interlinked by the carboxyl groups of formates. Compounds 4–6 exhibit 2-fold interpenetrating 2D networks in which each [Ln4L(H2O)4] “four-flier pinwheel” unit works as a planar eight-connecting node to connect its eight equivalents via four L ligands. The formation of 1–6 provided an interesting insight into the temperature effect on the construction of lanthanide(III)/polycarboxylate coordination polymers under solvothermal conditions.
Co-reporter:Lei-Lei Liu, Zhi-Gang Ren, Li-Min Wan, Hong-Ye Ding and Jian-Ping Lang
CrystEngComm 2011 vol. 13(Issue 19) pp:5718-5723
Publication Date(Web):20 Jul 2011
DOI:10.1039/C1CE05377A
Reaction of 5,11,17,23-tetramino-25,26,27,28-tetrahydroxy-calix[4]arene (1) with MeI and NaOAc·3H2O in DMF produced a tetracationic calix[4]arene [H4L]I4 (2) {H4L = [5,11,17,23-tetrakis(trimethylammonium)-25,26,27,28-tetrahydroxycalix[4]arene]} in 90% yield. Anion exchange of 2 with [Ag(MeCN)4](PF6) in MeCN afforded [H4L](PF6)4 (3). Treatment of 3 with Na2CO3 or NaNO3 in MeCN afforded two mono-deprotonated complexes [H3L](PF6)3·MeCN (4·MeCN) and [(H3L)2{(NO3)6(H2O)6}]·4MeCN (5·4MeCN). Compounds 4·MeCN and 5·4MeCN have been characterized by elemental analysis, IR spectra, 1H NMR, and single-crystal X-ray crystallography. 4·MeCN contains a 3D cationic H–bonded [H3L]n3n+ net in which PF6− anions are embedded into its 1D channels. 5·4MeCN consists of another 3D cationic H–bonded [H3L]n3n+ net in which the unique four-clawed crown-like nitrate–water cluster [(NO3)6(H2O)6]6− anions are included into the inter-spaces between the layers of [H3L]3+ trications. The formation of this nitrate–water cluster anion may demonstrate interesting information about the hydration of nitrate in water-related systems.
Co-reporter:Zhi-Gang Ren, Sha Sun, Min Dai, Hui-Fang Wang, Chun-Ning Lü, Jian-Ping Lang and Zhen-Rong Sun
Dalton Transactions 2011 vol. 40(Issue 33) pp:8391-8398
Publication Date(Web):22 Jul 2011
DOI:10.1039/C1DT10685F
Reactions of the preformed cluster [(η5-C5Me5)2Mo2(μ3-S)4Cu2(MeCN)2](ClO4)2 (1) with two tetraphosphine ligands, 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) and N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), produced two bicyclic clusters {[(η5-C5Me5)2Mo2(μ3-S)4Cu2]2(L)}(ClO4)4 (3: L = dpppda; 4: L = dppeda). Analogous reactions of 1 or [(η5-C5Me5)2Mo2(μ3-S)4Cu2(MeCN)2](PF6)2 (2) with two N,P mixed ligands, N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) and N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy), afforded two monocyclic clusters {[(η5-C5Me5)2Mo2(μ3-S)4Cu2]2(L)2}X4 (5: L = bdppmapy, X = ClO4; 6: L = dppmapy, X = PF6). Compounds 3–6 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, 1H and 31P{1H} NMR spectra, ESI-MS and single-crystal X-ray crystallography. In the tetracations of 3–6, two cubane-like [Mo2(μ3-S)4Cu2] cores are linked either by one dpppda or dppeda bridge to form a bicyclic structure or by a pair of bdppmapy or dppmapy bridges to afford a monocyclic structure. The third-order nonlinear optical (NLO) properties of 1 and 3–6 in MeCN were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 50 fs pulse width at 800 nm. Compounds 3–6 exhibited enhanced third-order NLO performances relative to that of 1.
Co-reporter:Xue Lü, Xi Chen, Zhi-Gang Ren, Jian-Ping Lang, Dong Liu and Zhen-Rong Sun
Dalton Transactions 2011 vol. 40(Issue 31) pp:7983-7992
Publication Date(Web):06 Jul 2011
DOI:10.1039/C1DT10230C
Treatment of [Et4N][Tp*W(μ3-S)3(CuBr)3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with an excess of α-methylpyridine (α-MePy) and NH4PF6 in CH2Cl2 afforded a cationic cluster [Tp*W(μ3-S)3Cu3(α-MePy)3(μ3-Br)](PF6) (2) while the reaction of 1 with an excess of 1,4-pyrazine (1,4-pyz) and NH4PF6 in MeCN–CH2Cl2 at 65 °C produced a polymeric cluster [Tp*W(μ3-S)3Cu3(1,4-pyz)((1,4-pyz)0.5)2(μ3-Br)][Tp*W(μ3-S)3(CuBr)3] (3). Reactions of 1 with melamine (MA) in 1:1 or 1:2 gave rise to another polymeric cluster [{Tp*W(μ3-S)3Cu3Br(μ3-Br)}2(MA)2] (4) and a neutral cluster [Tp*W(μ3-S)3Cu3Br(μ3-Br)(MA)2] (5), respectively. Compounds 2–5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, electrospray ionization (ESI) mass spectra and X-ray crystallography. The cation of 2 has a cubane-like [Tp*W(μ3-S)3Cu3(μ3-Br)] structure with each α-MePy ligand coordinated at one Cu(I) center. For 3, each [Tp*W(μ3-S)3Cu3(μ3-Br)] core is interconnected by 1,4-pyz bridges to form a 1D cationic zigzag chain with the [Tp*W(μ3-S)3(CuBr)3]− anions arranged along its two sides. For 4, each [Tp*W(μ3-S)3Cu3(μ3-Br)] core is interlinked by MA bridges to afford a 1D spiral chain. 5 adopts a cubane-like [Tp*W(μ3-S)3Cu3(μ3-Br)] structure in which one terminal Br and two MA ligands are coordinated at three Cu centers. The third-order nonlinear optical (NLO) properties of 1–5 in DMF were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Compounds 1–5 exhibit good NLO responses, and 3 and 4 possess the largest second-order hyperpolarizability γ values among the known W/Cu/S clusters bearing the [Tp*WS3] unit.
Co-reporter:Dong Liu, Ni-Ya Li and Jian-Ping Lang
Dalton Transactions 2011 vol. 40(Issue 10) pp:2170-2172
Publication Date(Web):09 Nov 2010
DOI:10.1039/C0DT00931H
Photochemical single-crystal to single-crystal transformation of one 1D polymer [Cd(bpe)(CBA)2]n afforded a new 1D polymer [Cd(rctt-tpcb)0.5(CBA)2]n which underwent hydrothermal reaction in strong acidic solution to form a 3D coordination polymer {[Cd(rtct-tpcb)Cl2]·2H2O}n.
Co-reporter:Ai-Xia Zheng, Zhi-Gang Ren, Ling-Ling Li, Hai Shang, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2011 vol. 40(Issue 3) pp:589-596
Publication Date(Web):30 Nov 2010
DOI:10.1039/C0DT00620C
Reactions of a gold(I) thiolate complex [Au(Tab)2]2(PF6)2 (Tab = 4-(trimethylammonio)benzenethiolate) with equimolar 1,2-bis(diphenylphosphine)ethane (dppe), 1,3-bis-(diphenylphosphine)propane (dppp) or 1,4-bis-(diphenylphosphine)butane (dppb) in MeOH–DMF–CH2Cl2 gave rise to three polymeric complexes [Au2(Tab)2(dppe)]2(PF6)4·2MeOH (1·2MeOH), [Au2(Tab)2(dppp)]Cl2·0.5MeOH·4H2O (2·0.5MeOH·4H2O), and [Au4(μ-Tab)2(Tab)2(dppb)](PF6)4·4DMF (3·4DMF), respectively. Analogous reaction of 1 with dppb in DMF/C2H4Cl2 produced one tetranuclear complex [Au2(μ-Tab)(Tab)2]2Cl4·2DMF·4H2O (4·2DMF·4H2O). Complexes 1–4 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H and 31P{1H} NMR and single crystal X-ray analysis. Compounds 1 and 2 consist of [Au(Tab)]2 dimeric fragments that are bridged by dppe or dppp ligands to form a 1D linear chain extending along the a axis. For 3, each [Au4(Tab)2(μ-Tab)2] fragment is linked by a pair of dppb ligands to afford another 1D chain extending along the c axis. For 4, the four [Au(Tab)]+ fragments are linked by two Au–Au bonds and two doubly bridging Tab ligands to form a {[Au(Tab)]4(μ-Tab)2} chair-like cyclohexane structure. Hydrogen-bonding interactions in 2 and 4 lead to the formation of interesting 2D hydrogen-bonded networks. The luminescent properties of 1–4 in solid state were also investigated.
Co-reporter:Yang Chen, Zhou Yang, Xin-Yi Wu, Chun-Yan Ni, Zhi-Gang Ren, Hui-Fang Wang and Jian-Ping Lang
Physical Chemistry Chemical Physics 2011 vol. 13(Issue 13) pp:5659-5667
Publication Date(Web):10 Feb 2011
DOI:10.1039/C0CP02431G
The solvothermal reactions of BiI3, KI, I2, 4,4′-bipyridine (4,4′-bipy), and a small amount of water in alcohol and acetonitrile produced four bipyridinium iodobismuthates {[MQ]3[Bi2I6(μ-I)3][Bi2I6(μ-I)2(MQ)2]3} (1, MQ+ = N-methyl-4,4′-bipyridinium), {[EQ]3[Bi2I6(μ-I)3][Bi2I6(μ-I)2(EQ)2]3} (2, EQ+ = N-ethyl-4,4′-bipyridinium), [MV][BiI5] (Eur. J. Inorg. Chem., 2010, 5326) (3, MV2+ = N,N′-dimethyl-4,4′-bipyridinium), and [EV]2[Bi4I10(μ-I)4(μ3-I)2] (4, EV2+ = N,N′-diethyl-4,4′-bipyridinium). In these reactions, 4,4′-bipy was partly or completely alkylated by alkyl groups generated from the cleavage of C–O bond of alcohols, forming the N-alkyl-4,4′-bipyridinium cation (Q+) and the N,N′-dialkyl-4,4′-bipyridinium dication (V2+), respectively. Compounds 1–4 were characterized by elemental analysis, IR, 1H NMR and single-crystal X-ray diffraction analysis. The optical, electrical conductive and dielectric properties of these compounds were investigated. The dielectric constants of the Q+-based compounds were larger than the values of the V2+-based ones, which showed that the weak electrostatic interactions in the structures may benefit the polarizability of molecules, thereby resulting in a larger dielectric response of the structures under an external electric field, while the strong electrostatic interactions between the positive and negative charge units would lead to a low dielectric constant (low-k) behavior of these compounds.
Co-reporter:Zhou Yang, Yang Chen, Chun-Yan, Ni, Zhi-Gang Ren, Hui-Fang Wang, Hong-Xi Li, Jian-Ping Lang
Inorganic Chemistry Communications 2011 Volume 14(Issue 9) pp:1537-1540
Publication Date(Web):September 2011
DOI:10.1016/j.inoche.2011.06.019
Solvothermal reactions of Cu2(OH)2CO3 with 1,2-bis(4-pyridyl)ethane (bpe) and iodobenzene or 4-iodotoluene in acetonitrile and aqueous ammonia afforded two arylamine-solvated [Cu2I2]-based coordination polymers {[Cu2I2(bpe)2]∙Am}n (1: Am = aniline; 2: Am = p-toluidine). Compounds 1 and 2 were characterized by elemental analysis, IR spectra, and powder X-ray diffraction (PXRD). Compounds 1 and 2 have a two-dimensional (4,4) topological network in which every rhombic [Cu2I2] dimer acts as a planar four-connected node to link other four equivalent ones by four bpe bridges. Each layer is further stacked via π–π interactions to form a 3D structure with 1D rhombic channels occupied by the guest aniline or p-toluidine molecules. These guest molecules were in situ generated through Ullmann coupling reactions of iodobenzene or 4-iodotoluene with ammonia. The thermal and photoluminescent properties of 1 and 2 were also investigated.Two arylamine-solvated [Cu2I2]-based coordination polymers {[Cu2I2(bpe)2]∙Am}n (1: Am = aniline; 2: Am = p-toluidine) were generated from solvothermal reactions of Cu2(OH)2CO3 with 1,2-bis(4-pyridyl)ethane (bpe) and iodobenzene or 4-iodotoluene in MeCN and aqueous ammonia. Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Research Highlights► Reaction of Cu2(OH)2CO3 with bpe and PhI in MeCN and aqueous NH3 gave compound 1. ► Compound 1 has a [Cu2I2]-based 2D (4,4) topological network. ► The aniline molecule was in situ formed through Ullmann reactions of PhI with NH3.
Co-reporter:Yu-Jie Chang, Dong Liu, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2011 Volume 14(Issue 2) pp:403-406
Publication Date(Web):February 2011
DOI:10.1016/j.inoche.2010.12.012
Solvothermal reactions of CdSO4·8/3H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and HCl in H2O, MeOH or EtOH afforded three coordination complexes [Cd5Cl2(μ-Cl)4(μ3-Cl)2(η,η,η-μ3-SO4)2(H2O)2(Htitmb)2]n (1), [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)2(titmb)2]n (2) and [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] (3), respectively. All the compounds were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 has a 1D chain in which each centrosymmetric double butterfly-shaped [Cd5Cl2(μ-Cl)4(μ3-Cl)2(H2O)2] unit interlinks with its equivalent ones via two couples of η,η,η-μ3-SO4 anions and two pairs of the Htitmb ligands. Compound 2 consists of one centrosymmetric [Cd5Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)4(titmb)2] unit that interconnects with equivalent ones via sharing Cd3 and its symmetry-related ones, forming a 1D zigzag chain. Compound 3 consists of a [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] unit linked by a pair of titmb ligands. The results may provide some insight into solvent effects on the formation of different coordination compounds from the same components.Reactions of CdSO4·8/3H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and HCl in 1:1:1 molar ratio in H2O, MeOH or EtOH under solvothermal conditions gave rise to three different coordination complexes [Cd5Cl2(μ-Cl)4(μ3-Cl)2(η,η,η-μ3-SO4)2(H2O)2(Htitmb)2]n, [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)2(titmb)2]n and [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2], respectively. The three complexes were structurally characterized by elemental analysis, IR, thermogravimetric analysis and X-ray crystallography.Research Highlights► Reactions of CdSO4, titmb and HCl in three solvents gave three complexes. ► Compound 1 is a 1D chain polymer. ► Compound 2 is a 1D zigzag chain polymer. ► Compound 3 is a tetranuclear Cd compound. ► Solvent effects on forming different complexes from the same components were found.
Co-reporter:Duan-Xiu Li, Zhi-Gang Ren, Hui-Fang Wang, Jian-Ping Lang
Inorganic Chemistry Communications 2011 Volume 14(Issue 10) pp:1665-1668
Publication Date(Web):October 2011
DOI:10.1016/j.inoche.2011.07.002
Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four AgP bonds. The in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry.Complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1) was generated from the in situ reaction of AgNO3 with N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylenediamine and aminothiocarbamide. The dppatc ligand could be readily formed by reaction of diphenylphosphine with formaldehyde and aminothiocarbamide while reaction of AgNO3 with dppatc produced 1 in high yields.Highlights► Reaction of AgNO3 with dppeda and aminothiocarbamide gave complex 1 in a low yield. ► The dppatc ligand could be readily generated by the reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. ► Reactions of AgNO3 with dppatc produced 1 in a relatively high yield.
Co-reporter:Lei-Lei Liu, Li-Min Wan, Zhi-Gang Ren, Jian-Ping Lang
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:1069-1072
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.03.077
Reactions of 25,26,27,28-tetrahydroxy-calix[4]arene (1) with 4 equiv. of m-carboxybenzenediazonium chloride in the presence of NaOAc∙3H2O in DMF produced a new azo calix[4]arene [H4L] (2) (H4L = 5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene) in 96% yield. Hydrothermal reactions of Cd(NO3)2·4H2O with H4L at 90 °C under pH = 5.0–6.0 gave rise to a coordination polymer {[H3O]2[Cd7L4(DMF)4(EtOH)2(H2O)2]·5DMF·11.5EtOH·H2O}n (3). Compound 3 was characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compound 3 consists of a 3D framework with an unprecedented (3346526371)(364135861) topology. The thermal properties of 2 and 3 were also investigated.A novel 3D coordination polymer {[H3O]2[Cd7L4(DMF)4(EtOH)2(H2O)2]·5DMF·11.5EtOH·H2O}n (3) {H4L = 5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene} was synthesized by reactions of Cd(NO3)2·4H2O and H4L under the solvothermal conditions. The molecular structure of 3 was characterized by elemental analysis, IR, and X-ray crystallography and its thermal property was investigated.Research Highlights► Reaction of Cd(NO3)2, cali[4]arene tetracaboxylic acid in DMF gave compound 3. ► Compound 3 is a 3D coordination polymer. ► Compound 3 has an unprecedented (3346526371)(364135861) topology.
Co-reporter:Hai-Yan Li, Yong Zhang, Yuan-Chen Ding, Mei Wang, Li-Xing Dai, Jian-Ping Lang
Journal of Molecular Structure 2011 Volume 996(1–3) pp:90-94
Publication Date(Web):14 June 2011
DOI:10.1016/j.molstruc.2011.04.022
Solvothermal reactions of CuX (X = Cl, Br, I, CN) with bis(4-bromo-3,5-dimethylpyrazol-1-yl)methane (brdmpzm) in MeCN gave rise to four one-dimensional coordination polymers [Cu(μ-X)(brdmpzm)]n (X = Cl (1), Br (2), I (3), CN (4)). Compounds 1–4 were characterized by elemental analysis, IR spectra and X-ray crystallography. X-ray analysis revealed that 1–3 have a 1D split-stair chain derived from connecting [Cu(brdmpzm)] fragments via μ-X bridges, while 4 consists of a zigzag chain formed by linking [Cu(brdmpzm)] fragments via μ-CN bridges. The luminescence properties of 1–4 along with free brdmpzm ligand at ambient temperature were also investigated.Highlights► Solvothermal reactions of CuX with brdmpzm afforded four 1D polymers 1–4. ► 1–3 have a split-stair chain formed by linking [Cu(brdmpzm)] units via X bridges. ► 4 contains a zigzag chain formed by linking [Cu(brdmpzm)] units via CN bridges.
Co-reporter:Hong-Xi Li, Mei-Ling Cheng, He-Ming Wang, Xiao-Juan Yang, Zhi-Gang Ren, and Jian-Ping Lang
Organometallics 2011 Volume 30(Issue 2) pp:208-214
Publication Date(Web):December 15, 2010
DOI:10.1021/om100671s
Protonolysis reactions of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 (Ln = Pr, Nd, Sm, Eu) with 3 equiv of 4,6-dimethylpyrimidine-2-thiol (dmpymtH) gave rise to the four Ln(III) pyrimidine-2-thionate complexes Li[Ln(dmpymt)4] (Ln = Pr (1), Nd (2), Sm (3), Eu (4)). Compounds 1−4 were characterized by elemental analysis, IR and 1H NMR spectroscopy, and single-crystal X-ray diffraction. X-ray diffraction analysis shows that the structures of 1−4 are similar and each eight-coordinate Ln(III) ion is chelated by four dmpymt ligands. Complexes 1−4 display excellent catalytic performance in the cyclodimerization of isocyanates to produce substituted ureas via elimination of CO, which represents the first example of lanthanide thiolates exhibiting a high catalytic activity and a high selectivity in the cyclodimerization of isocyanates. The effects of the solvents, temperatures, catalyst loadings, and rare-earth metals on the catalytic activities of the complexes were examined.
Co-reporter:He-Ming Wang, Hong-Xi Li, Xiang-Yang Yu, Zhi-Gang Ren, Jian-Ping Lang
Tetrahedron 2011 67(8) pp: 1530-1535
Publication Date(Web):
DOI:10.1016/j.tet.2010.12.069
Co-reporter:Zhong-Lin Xu, Hong-Xi Li, Zhi-Gang Ren, Wei-Yuan Du, Wei-Chang Xu, Jian-Ping Lang
Tetrahedron 2011 67(29) pp: 5282-5288
Publication Date(Web):
DOI:10.1016/j.tet.2011.05.025
Co-reporter:Hong-Xi Li, Zhi-Gang Ren, Dong Liu, Yang Chen, Jian-Ping Lang, Zhen-Ping Cheng, Xiu-Lin Zhu and Brendan F. Abrahams
Chemical Communications 2010 vol. 46(Issue 44) pp:8430-8432
Publication Date(Web):11 Oct 2010
DOI:10.1039/C0CC03027A
Reactions of Cu(OAc)2·H2O with dmnpzH in EtOH produce a heptanuclear copper(II) pyrazolate complex [Cu7(OH)2(OAc)6(dmnpz)6(EtOH)6], which is able to undergo a SCSC structural transformation from a lower symmetry structure to a higher symmetry structure via replacement of ligated-EtOH molecules with MeOH; both complexes along with the solvent-free species exhibit high catalytic activity in the polymerization of MMA.
Co-reporter:Wen-Hua Zhang, Dong Liu, Hong-Xi Li, Zhi-Gang Ren, Yong Zhang and Jian-Ping Lang
Crystal Growth & Design 2010 Volume 10(Issue 1) pp:3
Publication Date(Web):December 2, 2009
DOI:10.1021/cg9006636
Reactions of (NH4)2[MoOS3] with [Cu(MeCN)4](ClO4) and bis(3,5-dimethylpyrazolyl)methane (dmpzm) (molar ratio = 1:3:3) in MeCN produced a cationic cluster [MoOS3Cu3(dmpzm)3](ClO4) (1). 1 consists of a unique 3D hydrogen-bonded network with empty C3-symmetry cavities. A set of C3 (cyclohexane) or non-C3-symmetry solvent molecules (aniline, N,N′-dimethylformamide, formamide, and water) could recognize these C3-symmetry cavities and smartly fit themselves into them by converting themselves into C3-symmetry species through intriguing ways of symmetry-oriented molecular disorder and trimerlization.
Co-reporter:Dong Liu, Hong-Xi Li, Lei-Lei Liu, He-Ming Wang, Ni-Ya Li, Zhi-Gang Ren and Jian-Ping Lang
CrystEngComm 2010 vol. 12(Issue 11) pp:3708-3716
Publication Date(Web):07 Jul 2010
DOI:10.1039/C005322H
Four 1,3-benzenedicarboxylic acid derivatives, with substituted R (OH, COOH, NO2, Me) groups at the 5-position, were employed to explore their effect on the construction of supramolecular assemblies. Four coordination polymers, [Zn(OH2)(5-HO-1,3-BDC)(1,4-bpeb)]n (1), [Zn(1,3,5-HBTC)(1,4-bpeb)]n (2), {[Zn(5-NO2-1,3-BDC)(1,4-bpeb)]·2(H2O)0.5}n (3), and [Zn(5-Me-1,3-BDC)(1,4-bpeb)]n (4) (1,4-bpeb = 1,4-bis[2-(4-pyridyl)ethenyl]benzene, 5-HO-1,3-BDC = 5-hydroxy-1,3-benzenedicarboxylate, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylate, 5-NO2-1,3-BDC = 5-nitro-1,3-benzenedicarboxylate, 5-Me-1,3-BDC = 5-methyl-1,3-benzenedicarboxylate) were prepared by the hydrothermal reactions of Zn(NO3)2·6H2O with 1,4-bpeb and 5-HO-1,3-H2BDC, 1,3,5-H3BTC, 5-NO2-1,3-H2BDC or 5-Me-1,3-H2BDC. All these compounds were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of 1 has a 3D H-bonded structure derived from linking 1D comb-like [Zn(OH2)(5-HO-1,3-BDC)(1,4-bpeb)]n chains via intermolecular H-bonding interactions between the coordinated H2O molecule and 1,4-bpeb or one COO− group and between the OH group and the other COO− group. 2 has a 3D H-bonded net based on holding 2D [{Zn2(1,3,5-HBTC)2}4]n layers through intermolecular H-bonding interactions between 1,4-bpeb and the uncoordinated COOH group. 3 could be considered as a 6-fold interpenetrating 3D H-bonded supramolecular framework constructed by linking 2D [Zn4(5-NO2-1,3-BDC)4(1,4-bpeb)4]n networks through intermolecular H-bonding interactions between the water solvent molecules and the NO2 group. 4 has a 3-fold interpenetrating 3D framework in which each 2D (4,4) [Zn4(5-Me-1,3-BDC)4(1,4-bpeb)4]n network is interpenetrated by two other equivalent nets. The Schläfli symbols for the four supramolecular frameworks are 41263, (4·62)2(426687), (63)(658) and 4462, respectively. The thermal stability and photoluminescent properties of 1–4 were also investigated.
Co-reporter:Dong Liu, Zhi-Gang Ren, Hong-Xi Li, Yang Chen, Jing Wang, Yong Zhang and Jian-Ping Lang
CrystEngComm 2010 vol. 12(Issue 6) pp:1912-1919
Publication Date(Web):05 Feb 2010
DOI:10.1039/B924647A
Hydrothermal reactions of Zn(NO3)2·6H2O with 1,3-benzenedicarboxylic acid (1,3-H2BDC) and 1,4-bis[2-(4-pyridyl)ethenyl]benzene (1,4-bpeb) under pH = 2.5 or 8.0 gave rise to two coordination polymers {[Zn6(μ-OH2)(1,3-BDC)6(1,4-bpeb)4]·MeCN}n (1) and {[Zn8(1,3-BDC)8(1,4-bpeb)4]·2H2O}n (2). Both compounds were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compound 1 has two types of dinuclear zinc cores as nodes and displays an intriguing three-dimensional (3D) three-fold interpenetrating (4,6)-connected network with an unprecedented (3264)(3244687)2 topology. Compound 2 exhibits an unusual 3D two-fold interpenetrating pcu net with a Schlafli symbol 41263. The formation of 1 and 2 provided an interesting insight into the effect of pH values on the construction of coordination polymers under solvothermal conditions. Thermal stability and photoluminescence properties of 1 and 2 were also investigated.
Co-reporter:Ling-Ling Li, Rong-Xin Yuan, Lei-Lei Liu, Zhi-Gang Ren, Ai-Xia Zheng, Hong-Jian Cheng, Hong-Xi Li and Jian-Ping Lang
Crystal Growth & Design 2010 Volume 10(Issue 4) pp:1929-1938
Publication Date(Web):February 24, 2010
DOI:10.1021/cg100028y
Solvothermal reactions of bulk CuSCN with six flexible benzimidazolyl-based ligands with different spacer lengths [(bzim)(CH2)n(bzim)] (bzim = benzimidazolyl; n = 1, mbbm; n = 2, ebbm; n = 3, prbbm; n = 4, bbbm; n = 5, pbbm; n = 6, hbbm) afforded a series of new [CuSCN]n-supported coordination polymers, [(CuSCN)2(mbbm)]n (1), [(CuSCN)2(ebbm)2]n (2), [(Cu(SCN)2(prbbm)]n (3a), [{(CuSCN)2(prbbm)2}·2MeCN]n (3b), [(CuSCN)4(bbbm)3]n (4), [(CuSCN)2(pbbm)]n (5), and [(CuSCN)2(hbbm)]n (6), respectively. Compounds 1−6 were characterized by elemental analysis, IR, and X-ray crystallography. Compound 1, 3a, or 6 possesses the similar staircase-like [CuSCN]n chains that are bridged by mbbm, prbbm, or hbbm to form one one-dimensional (1D) chain with an oblong channel (3a) or two two-dimensional (2D) networks (1 and 6). Compound 2 or 3b consists of a dimeric [CuSCN]2 fragment that serves either as a 4-connecting node to link the other four equivalent ones via two pairs of ebbm bridges to form a 2D (4,4) network (2) or as a 2-connecting node to bridge its two adjacent ones via a pair of prbbm bridges to form a 1D chain (3b). Compound 4 contains a new kind of [CuSCN]n double chain that is connected by bbbm with two conformations to form a unique 2D network, while 5 consists of a [CuSCN]n single chain that is linked by pbbm to form the other kind of 1D chain with an oblong channel. In addition, the photoluminescent properties of 1−6 in solid state at ambient temperature were also investigated.
Co-reporter:Yang Chen, Zi-Ou Wang, Zhou Yang, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2010 vol. 39(Issue 40) pp:9476-9479
Publication Date(Web):13 Sep 2010
DOI:10.1039/C0DT00757A
Two unique low-dimensional benzyl viologen iodoplumbates [Pb13I38][B′V]6 (1) and [(Pb5I14)(BV)2]n (2) were prepared from solvothermal reactions of benzyl alcohol with 4,4′-bipy, PbI2, I2 and a small amount of water in acetonitrile. The semiconducting properties of the single crystals 1 and 2 along with Zn/Cl-doped samples 2a and 2b were investigated.
Co-reporter:Ling-Ling Li, Lei-Lei Liu, Ai-Xia Zheng, Yu-Jie Chang, Ming Dai, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2010 vol. 39(Issue 33) pp:7659-7665
Publication Date(Web):20 Jul 2010
DOI:10.1039/C0DT00249F
Solvothermal reactions of CuCN with a set of flexible bipyrazolyl-based ligands with different spacer lengths [(dmpz)(CH2)n(dmpz)] (dmpz = 3,5-dimethyl-pyrazolyl; n = 1–6) gave rise to six [CuCN]n-based coordination polymers [(CuCN)3L]n (1: L = dmpzm; 2: L = dmpze), [(CuCN)2L]n (3: L = dmpzpr; 4: L = dmpzb; 5: L = dmpzp; 6: L = dmpzh). Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. 1 or 2 exhibits a 1D scolopendra-like chain assembled from a rare 1D zigzag [CuCN]n chain with [CN–Cu–CN–Cu–L] (1: L = dmpzm; 2: L = dmpze) side arms. 3 or 4 shows a 2D (6,3) wave-like layer in which [Cu6(μ-CN)6L2]n (L = dmpzpr or dmpzb) double chains are interconnected by pairs of L bridges. 5 consists of two [CuCN]n single chains that are linked by dmpzp bridges to form a rare 1D chain with an oblong channel. 6 has a 3D network in which the 2D [Cu10(μ-CN)10(dmpzh)3]n layers are interconnected by pairs of dmpzh bridges. In addition, the photoluminescent properties of 1–6 in the solid state at ambient temperature were investigated.
Co-reporter:Ni-Ya Li, Zhi-Gang Ren, Dong Liu, Rong-Xin Yuan, Li-Pei Wei, Liang Zhang, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2010 vol. 39(Issue 17) pp:4213-4222
Publication Date(Web):24 Mar 2010
DOI:10.1039/B925081F
Reactions of N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) with K[Ag(CN)2], Ag(dca) (dca = dicyanamide), AgSCN, AgCl, AgBr or AgI gave rise to six [Ag2X2]-based (X = CN−, dca, SCN−, Cl−, Br− and I−) compounds, [{Ag2(CN)2(dppmapy)}·0.5CHCl3]n (1), [Ag2L2(dppmapy)2]n (2: L = dca; 3: L = SCN), [{Ag2L2(dppmapy)2}·sol]n (4: L = Cl, sol = 0.5MeOH·0.5CH2Cl2; 5: L = Br, sol = 2CHCl3), and [Ag2I2(dppmapy)4]·3MeOH (6). Complexes 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Compound 1 has a one-dimensional (1D) spiral chain constructed by bridging the [(CN)Ag(μ-CN)Ag] fragments via dppmapy ligands. In 2, 3 and 4, each [Ag2X2] (X = dca, SCN, Cl) fragment is linked by dppmapy bridges to the other two equivalent ones to form a 1D chain containing 16-membered rings (2) or a 1D double chain containing 20-membered rings (3) or a 1D spiral chain containing 20-membered rings (4). Compound 5 possesses a two dimensional (2D) (4,4) network consisting of 36-membered metallomacrocycles in which each [Ag2Br2] fragment acts as a unique planar four-connecting node to link the other four equivalent ones via dppmapy bridges. Complex 6 has a [Ag2I2] unit with a pair of monodentate dppmapy ligands coordinated at each Ag center. The photoluminescent properties of 1–6 in the solid state at ambient temperature were also investigated.
Co-reporter:Yang Chen;Zhou Yang;Cheng-Xin Guo;Chun-Yan Ni;Zhi-Gang Ren;Hong-Xi Li
European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 33) pp:5326-5333
Publication Date(Web):
DOI:10.1002/ejic.201000755
Abstract
Reactions of BiI3, KI, 4,4′-bipyridine (4,4′-bipy) and alcohols (methanol, benzyl alcohol, 2-propanol or propanol) in the presence of I2 and a small amount of water afforded four iodobismuthate complexes of N,N′-dialkyl-4,4′-bipyridinium (viologen, V2+), [MV][BiI5] (1, MV2+ = N,N′-dimethyl-4,4′-bipyridinium), [BzV]2[Bi2I8(μ-I)2] (2, BzV2+ = N,N′-dibenzyl-4,4′-bipyridinium), [iPV]2[Bi4I10(μ-I)4(μ3-I)2] (3, iPV2+ = N,N′-diisopropyl-4,4′-bipyridinium) and [PV]2[Bi4I8(μ-I)8] (4, PV2+ = N,N′-dipropyl-4,4′-bipyridinium) under solvothermal conditions. The V2+ dications were formed from iodine-induced C–O bond cleavage of alcohols followed by alkylation of 4,4′-bipy. The Bi centre of the [BiI5]2– anion of 1 adopts a square-pyramidal coordination geometry, whereas the [Bi2I10]4– anion of 2 consists of a dimeric structure comprising two edge-sharing BiI6 octahedra. The tetranuclear [Bi4I16]4– anion of 3 has an incomplete double cubane structure in which two incomplete [Bi3(μ-I)2(μ3-I)2] cubane-like fragments are fused by sharing two Bi and two μ3-I atoms, whereas that of 4 contains a bent Bi4 chain in which the [Bi2I10]4– anion of 2 is fused with two BiI6 units through six shared μ-I atoms. The optical, electrical conductivity and dielectric properties of 1–4 were also investigated.
Co-reporter:Huihui Wang;Hongxi Li;Zhigang Ren;Yang Chen;Jianping Lang
Chinese Journal of Chemistry 2010 Volume 28( Issue 8) pp:1373-1378
Publication Date(Web):
DOI:10.1002/cjoc.201090235
Abstract
Reactions of CuX (X=I, NCS) with bis(4-benzyl-3,5-dimethyl-1H-pyrazol-1-yl)methane (bzdmpzm) in MeCN resulted in the formation of one dimer [(bzdmpzm)Cu(µ-I)]2 (1) and one 1D polymer [(bzdmpzm)Cu(µ-NCS)]n (2) in high yields. 1 and 2 were characterized by elemental analysis, IR, 1H NMR spectra, powder X-ray diffraction and single-crystal X-ray diffraction. 1 consists of two scorpion-like [(bzdmpzm)Cu]+ fragments bridged by two iodides, forming a dimeric structure. 2 contains a unique 1D scolopendra-like chain of [(bzdmpzm)Cu]+ fragments linked by pairs of thiocyanates. The luminescence properties of 1 and 2 were also investigated.
Co-reporter:Leilei Liu;Zhigang Ren;Hongxi Li;Hai Shang; Dr. Jianping Lang
Chinese Journal of Chemistry 2010 Volume 28( Issue 10) pp:1829-1834
Publication Date(Web):
DOI:10.1002/cjoc.201090306
Abstract
Treatment of 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxy calix[4]arene (2) with HCl in DMF or NaOH in MeOH produced 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]-arene·4DMF (2·4DMF) and 5,11,17,23-tetrakis[(p-carboxyphenylsodium)azo]-25,26,27,28-tetrahydroxycalix[4]- arene (3), respectively, which were characterized by elemental analysis, IR, UV-vis, 1H NMR and 13C NMR. An X-ray analysis of 2·4DMF revealed that its calix[4]arene core adopts a flattened cone conformation in which opposed phenyl groups take parallel or sharply inclined positions. The intra- and intermolecular hydrogen-bonding interactions and the π···π interactions form a 2D hydrogen-bonded wavelike network. Compound 2 had a unique reversible color change in a wide pH range from 1 to 13.5 and showed interesting pH sensing properties.
Co-reporter:En Tang, Yu-Mei Dai, Yang Chen, Jian-Ping Lang, Yuan-Gen Yao, Ng-Seik Weng
Inorganic Chemistry Communications 2010 Volume 13(Issue 7) pp:887-890
Publication Date(Web):July 2010
DOI:10.1016/j.inoche.2010.04.021
The hydrothermal reactions of CuCl with 1,3-bis(4-pyridyl)propane (bpp), 1,3-benzenedicarboxylic acid (1,3-H2bdc), and KOH in water afforded {[Cu8Cl4(bpp)8][(1,3-Hbdc)4(H2O)9.5]}n (1). Single-crystal X-ray diffraction revealed that 1 has anionic [(1,3-Hbdc)4(H2O)9.5]n4n− water cluster chains that are encapsulated into the 1D channels of a 3-D [Cu8Cl4(bpp)8]n4n+ cationic framework. The thermal and luminescent properties of 1 in the solid state were also investigated.Graphical abstractReactions of CuCl with 1,3-bis(4-pyridyl)propane (bpp), 1,3-benzenedicarboxylic acid (1,3-H2bdc), KOH under hydrothermal conditions produced {[Cu8Cl4(bpp)8][(1,3-Hbdc)4(H2O)9.5]}n, in which anionic [(1,3-Hbdc)4(H2O)9.5]n4n− water cluster chains are enclosed into the 1D channels of a 3D [Cu8Cl4(bpp)8]n4n+ cationic framework.
Co-reporter:Dong Liu;Zhi-Gang Ren Dr.;Hong-Xi Li Dr. Dr.;Ni-Ya Li;BrendanF. Abrahams
Angewandte Chemie 2010 Volume 122( Issue 28) pp:4877-4880
Publication Date(Web):
DOI:10.1002/ange.201001551
Co-reporter:LingLing Li;ZhiGang Ren;Xue Lü;HeMing Wang;YuJie Chang
Science China Chemistry 2010 Volume 53( Issue 10) pp:2083-2090
Publication Date(Web):2010 October
DOI:10.1007/s11426-010-4044-6
Four new [CunIn]-based coordination polymers, [{ Cu4(µ3-I)4(mbbm)2}·2DMF]n (1), [(CuI)2(mbbm)2]n (2), [{Cu2(µ-I)2-(ebbm)2}·2MeCN]n (3), and [Cu2(µ-I)2(prbbm)2]n (4), were prepared from solvothermal reactions of CuI with three flexible ligands [(bzim)(CH2)n(bzim)] (bzim = benzimidazole; n = 1, mbbm; n = 2, ebbm; n = 3, prbbm). These compounds were characterized by elemental analysis, IR and X-ray crystallography. 1 consists of cubanelike [Cu4(µ3-I)4] fragments that link the neighboring ones via mbbm bridges to form a 1D ladder-type chain. 2 contains mononuclear [CuI] fragments that are bridged by mbbm ligands to yield a 1D zigzag chain. 3 or 4 contains a [Cu2(µ-I)2] dimeric fragment, which works as a four-connecting node to link its four equivalent ones to form a 2D (4,4) network (3) or acts as a two-connecting node to connect its two equivalent ones via two pairs of prbbm bridges to form a 1D double chain (4). The photoluminescent properties of 1–4 in the solid state at ambient temperature were investigated.
Co-reporter:Dong Liu;Zhi-Gang Ren Dr.;Hong-Xi Li Dr. Dr.;Ni-Ya Li;BrendanF. Abrahams
Angewandte Chemie International Edition 2010 Volume 49( Issue 28) pp:4767-4770
Publication Date(Web):
DOI:10.1002/anie.201001551
Co-reporter:Xiao-Yan Tang, Rong-Xin Yuan, Zhi-Gang Ren, Hong-Xi Li, Yong Zhang and Jian-Ping Lang
Inorganic Chemistry 2009 Volume 48(Issue 6) pp:2639-2651
Publication Date(Web):February 19, 2009
DOI:10.1021/ic8021744
Reactions of [Hg(Tab)2](PF6)2 (1) with phen, 2,2′-bipy, py, N-Meim, N-iPrim, en, eten, tmen, dap, and dpt gave rise to a family of cationic mercury(II) thiolate complexes, [Hg(Tab)2(L)](PF6)2·S (2, L = phen, S = 2MeOH; 3, L = 2,2′-bipy, S = DMF), [Hg(Tab)2(L)2](PF6)2 (4, L = py; 5, L = N-Meim), [Hg(Tab)2(N-iPrim)](PF6)2 (6), [Hg(Tab)2(L)](PF6)2·0.5MeCN (7, L = en; 8, L = eten), and [Hg(Tab)2(L)](PF6)2 (9, L = tmen; 10, L = dap; 11, L = dpt). These complexes were characterized by elemental analysis, IR spectra, UV−vis spectra, 1H NMR, and single-crystal X-ray crystallography. The Hg atom in [Hg(Tab)2]2+ dications of 2−5 is further coordinated either by two N atoms from one phen or 2,2′-bipy ligand or by two N atoms from two py or N-Meim ligands, affording a distorted seesaw-shaped coordination geometry. In 6, the Hg atom of the [Hg(Tab)2]2+ dication is coordinated by one N atom of the N-iPrim ligand, forming a T-shaped coordination geometry, and these [Hg(Tab)2(N-iPrim)]2+ dications are further coordinated to another S atom of Tab from the adjacent unit, giving a chain structure. The Hg atoms in [Hg(Tab)2]2+ dications of 7−11 are chelated by two N atoms from one diamine molecule such as en in 7, eten in 8, tmen in 9, or dap in 10 or by two N atoms from the triamine molecule dpt in 11, forming a distorted seesaw-shaped coordination geometry. In all of these structures, the original trans configuration of the [Hg(Tab)2]2+ dication of 1 is changed via rotation and/or switching of the two Tab species along the S−Hg−S line together with the rotation of the phenyl groups of the Tab ligands. The results may provide interesting insight into mimicking of the interactions of the Hg(Cys)2 linear species in Hg-MerR and Hg-MT with various N-donor ligands encountered in nature and its potential changes in the structural chemistry (bond length, angles, configurations, etc.).
Co-reporter:Zhen-Hong Wei ; Hong-Xi Li ; Mei-Ling Cheng ; Xiao-Yan Tang ; Yang Chen ; Yong Zhang
Inorganic Chemistry 2009 Volume 48(Issue 7) pp:2808-2817
Publication Date(Web):February 24, 2009
DOI:10.1021/ic8019342
Assembly of a family of monomeric, dimeric, and polymeric W/Cu/S clusters from a precursor cluster [Et4N][Tp*W(μ3-S)3(CuBr)3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) and various N-donor ligands was reported. The treatment of 1 with pyridine (py) or aniline (ani) in the presence of NH4PF6 afforded a cationic cluster [Tp*W(μ3-S)3Cu3(py)3(μ3-Br)](PF6) (2) and a neutral cluster [{Tp*W(μ3-S)3(CuBr)3}(μ6-Br){Tp*W(μ3-S)3Cu3(ani)3}]·4ani·0.5Et2O (3·4ani·0.5Et2O). On the other hand, the treatment of 1 with excess 4,4′-bipyridine (4,4′-bipy) or 1,2-bis(4-pyridyl)ethylene (bpee) followed by the addition of NH4PF6 led to the formation of a polymeric cluster {[Tp*W(μ3-S)3Cu3(4,4′-bipy)3(μ3-Br)](PF6)·H2O}n (4) and a neutral cluster [{Tp*W(μ3-S)3Cu3Br2}2(bpee)]·0.5CH2Cl2 (5·0.5CH2Cl2). Meanwhile, analogous reactions of 1 with excess 1,2-bis(4-pyridyl)ethane (bpe) or 1,3-bis(4-pyridyl)propane (bpp) in DMF under the presence of NH4PF6 resulted in the formation of two polymeric clusters {[{Tp*W(μ3-S)3Cu3(μ3-Br)}2(bpe)3](PF6)2·MeCN}n (6) and {[Tp*W(μ3-S)3Cu3Br(μ3-Br)(bpp)]·DMF}n (7). Compounds 1−7 were characterized by elemental analysis, IR spectra, UV−vis spectra, 1H NMR, electrospray ionization mass spectra, and X-ray crystallography. The anion of 1 has an incomplete cubanelike [Tp*W(μ3-S)3(CuBr)3] structure, while the cation of 2 has a cubanelike [Tp*W(μ3-S)3Cu3(μ3-Br)] structure. Compound 3 may be viewed as having a corner-shared double cubanelike structure that consists of one [Tp*W(μ3-S)3Cu3(ani)3]2+ dication and one [Tp*W(μ3-S)3(CuBr)3]− anion linked by a μ6-Br bridge. For 4, each [Tp*W(μ3-S)3Cu3(μ3-Br)] unit works as a pyramidal three-connecting node to connect its equivalent ones via three 4,4′-bipy bridges to yield a 2D (6,3) cationic network. Compound 5 has a dimeric structure in which two incomplete cubanelike [Tp*W(μ3-S)3Cu3Br2] cores are bridged with one bpee ligand. For 6, each dimeric [{Tp*W(μ3-S)3Cu3(μ3-Br)}2(bpe)2] unit is interconnected via a pair of bpe bridges to form a 1D zigzag cationic chain. Compound 7 has a 1D spiral chain in which each [Tp*W(μ3-S)3Cu3Br(μ3-Br)] core is interlinked by a couple of bpp bridges. The formation of 2−7 from the precursor cluster 1 through various N-donor ligands offers a new way to the design and assembly of the W/Cu/S clusters with interesting molecular and supramolecular arrays.
Co-reporter:Jin-Xiang Chen, Xiao-Yan Tang, Yang Chen, Wen-Hua Zhang, Ling-Ling Li, Rong-Xin Yuan, Yong Zhang and Jian-Ping Lang
Crystal Growth & Design 2009 Volume 9(Issue 3) pp:1461
Publication Date(Web):January 12, 2009
DOI:10.1021/cg800896k
Assembly of different [MoOS3Cu3]-based coordination polymers from the same components ([(n-Bu)4N]2[MoOS3Cu3(NCS)3] (1) and 4,4′-bypyridine (4,4′-bipy)) via different synthetic approaches has been investigated. Treatment of 1 with 4,4′-bipy (molar ratio = 1:1) in aniline afforded {[{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)3]·6(ani)}n (ani = aniline) (2), while solid state reaction of 1 with equimolar 4,4′-bipy at ambient temperature followed by extraction with aniline yielded {[(n-Bu)4N]2[{MoOS3Cu3(NCS)2}2(4,4′-bipy)3]·2(ani)}n (3). Diffusion reactions of an aniline solution of 1 with an aniline solution of 4,4′-bipy in a straight or zigzag glass tube resulted in the formation of {[MoOS3Cu3(NCS)(4,4′-bipy)2.5]·3(ani)}n (4) and {[(MoOS3Cu3)2(NCS)(μ-NCS)(4,4′-bipy)4.5]·7(ani)}n (5), respectively. Compounds 2−5 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compounds 2 consists of a 1D zigzag chain in which the dimeric [{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)2] units are linked by single 4,4′-bipy bridges, while 3 possesses a one-dimensional spiral chain built of the dimeric [{MoOS3Cu3(NCS)2}2(4,4′-bipy)2] units bridged by 4,4′-bipy ligands. Compound 4 contains a three-dimensional (3D) 3-fold interpenetrated network in which each [MoOS3Cu3] core acts as a tetrahedral four-connecting node to interconnect four other equivalent ones via single and double 4,4′-bipy bridges. Compound 5 has a unique 3D 2-fold interpenetrated network in which the [MoOS3Cu3] cores work as trigonal-pyramidal four- and tetragonal-pyramidal five-connecting nodes to link other equivalent cores through single thiocyanate bridges and single and double 4,4′-bipy bridges. The results may provide interesting insights into effects of synthetic approaches on the construction of cluster-based coordination polymers.
Co-reporter:Yang Chen, Zi-Ou Wang, Zhi-Gang Ren, Hong-Xi Li, Duan-Xiu Li, Dong Liu, Yong Zhang and Jian-Ping Lang
Crystal Growth & Design 2009 Volume 9(Issue 11) pp:4963
Publication Date(Web):October 6, 2009
DOI:10.1021/cg9007608
Solvothermal reactions of CuI with 4,4′-dipyridyl disulfide (dpds) and oxalic acid in toluene and acetonitrile at three different time periods gave rise to three Cu/I/S-based coordination polymers, [Cu6(μ-4-SpyH)4I6]n (1), {[Cu2(μ-I)(μ-4-SpyH)3]I}n (2), and [Cu5(μ-4-SpyH)7(μ-I)I4]n (3). The preparation of 1−3 was involved in the in situ formation of the zwitterionic pyridium-4-thiolate (4-SpyH) molecule from the S−S cleavage of the dpds ligand. These compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), X-ray powder diffraction (XRPD), and single crystal X-ray diffraction. Compound 1 contains an adamantine-type [Cu6S4] core that links the neighboring ones via double iodide bridges to form a three-dimensional (3D) diamond-like net. Compound 2 has a one-dimensional (1D) cationic {[Cu2(μ-I)(μ-4-SpyH)3]n}n+ polymeric chain with disordered iodides embedded between chains. Compound 3 contains the [Cu5(μ-I)I4(μ-4-SpyH)7] species that is interconnected with its neighboring ones through two μ-4-SpyH ligands to form a 1D neutral chain. The formation of 1−3 provided an interesting example that different coordination polymers could be produced from the same components under solvothermal conditions at different time periods. In addition, optical absorption and electric conductivity experiments revealed that 1−3 exhibited good semiconducting performances.
Co-reporter:Ling-Ling Li, Hong-Xi Li, Zhi-Gang Ren, Dong Liu, Yang Chen, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009 (Issue 40) pp:8567-8573
Publication Date(Web):02 Sep 2009
DOI:10.1039/B908697H
Solvothermal reactions of CuI with four flexible N-heterocyclic ligands, 1,2-bis(4-pyridyl)ethane (bpe), 1,1′-(1,4-butanediyl)bis-1H-benzimidazole (bbbm), 1,1′-(1,4-butanediyl)bis-1H-benzotriazole (bbbt), and 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole (pbbm), afforded four new [CunIn]-based coordination polymers, [Cu3I(μ-I)(μ3-I)(bpe)3]n (1), {[CuI(bbbm)1.5]·0.25MeCN}n (2), and [Cu4(μ3-I)4L2]n (3: L = bbbt; 4: L = pbbm), respectively. Compounds 1–4 were characterized by elemental analysis, IR and X-ray crystallography. 1 consists of an unique 2D network in which 1D [CuI(bpe)]n zigzag chains are embroidered alternatively onto the two faces of a 2D [Cu4(μ-I)2(μ3-I)2(bpe)2]n layer through pairs of bpe bridges. 2 contains a 66-membered metallomacrocyclic [CuI(bbbm)1.5]6 unit that fuses with its neighbouring ones via sharing Cu atoms to form a 2D (6,3) layer network. 3 or 4 contains a cubanelike [Cu4(μ3-I)4] core, which works as a cross-shaped four-connecting node to link its four equivalent units to form a 2D (4,4) cross-shaped network (3) or acts as a Y-shaped three-connecting node to connect its three equivalent ones to form a 1D double chain (4). In addition, the photoluminescent properties of 1–4 in solid state at ambient temperature were also investigated.
Co-reporter:Zhen-Hong Wei, Hong-Xi Li, Zhi-Gang Ren, Jian-Ping Lang, Yong Zhang and Zhen-Rong Sun
Dalton Transactions 2009 (Issue 18) pp:3425-3433
Publication Date(Web):20 Mar 2009
DOI:10.1039/B822858B
Stepwise reactions of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1–4 equiv. of CuNCS (and Et4NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et4N][Tp*WS(μ-S)2(CuNCS)]·0.5CH2Cl2 (2·0.5CH2Cl2), [Et4N][Tp*W(μ3-S)(μ-S)2(CuNCS)2]·ClCH2CH2Cl (3·ClCH2CH2Cl), [Et4N]2[Tp*W(μ3-S)3(CuNCS)3(μ3-Br)]·1.5aniline (4·1.5aniline), and {[Et4N][Tp*W(μ3-S)3(Cu-μ-SCN)3(Cu-μ3-NCS)]}n (5). Compounds 2–5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 contains a [WS2Cu] core formed by addition of one CuNCS group onto the [Tp*WS3] species. The cluster anion of 3 has a butterfly-shaped [WS3Cu2] core constructed by addition of two CuNCS groups onto the [Tp*WS3] species. The cluster dianion of 4 consists of a cubane-like [Tp*WS3Cu3(μ3-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS3] species followed by filling a μ3-Br into the void of the incomplete cubane-like [Tp*WS3(CuNCS)3] fragment. 5 has a 2D cluster-supported layer network in which each [Tp*WS3Cu3] core acting as a pyramidal 3-connecting node interconnects with the [Cu(NCS)4] units through thiocyanate bridges. In addition, the third-order nonlinear optical (NLO) performances of 2–5 in DMF were also investigated by Z-scan techniques.
Co-reporter:Mei-Ling Cheng, Hong-Xi Li, Lei-Lei Liu, Hui-Hui Wang, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009 (Issue 11) pp:2012-2019
Publication Date(Web):29 Jan 2009
DOI:10.1039/B819637K
Protonolysis reactions of [Zn(dmpzm)Et2] (1) with acetic or formic acid in different molar ratios gave rise to four mononuclear zinc complexes [ZnEt(dmpzm)(L)] (2: L = OAc; 3: L = HCOO) and [Zn(dmpzm)(L)2] (4: L = OAc; 5: L = HCOO), one nonanuclear zinc complex [Zn(μ4-O)2(ZnEt)6(μ3-OAc)4(μ′3-OAc)2{Zn(dmpzm)Et}2] (6), and one tetranuclear zinc complex [Zn4(μ4-O)(dmpzm)3Et3] (7). Compounds 1–7 were characterized by elemental analysis, IR spectra, 1H NMR spectra, and the crystal structures of 1, 3, 4, 6, and 7 were determined by single-crystal X-ray crystallography. In the structures of 1, 3, and 4, the central Zn atom is tetrahedrally coordinated by two N atoms of one dmpzm and two C atoms of two Et groups (1), or one C atom of one Et group and one O atom of formate ligand (3), or two O atoms of two acetates (4). In the structure of 6, a heptanuclear [Zn(μ4-O)2(ZnEt)6(μ3-OAc)4] core is connected with two [Zn(dmpzm)Et]+ fragments via a pair of μ′3-OAc ligands. Compound 7 consists of a Zn4(μ4-O) tetrahedron in which three Zn atoms are further saturated by two N atoms from dmpzm ligands and an ethyl group while one Zn center is coordinated by three C atoms from the methylene group of the three dmpzm ligands.
Co-reporter:Yu-Jian Huang, Ying-Lin Song, Yang Chen, Hong-Xi Li, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009 (Issue 8) pp:1411-1421
Publication Date(Web):14 Jan 2009
DOI:10.1039/B816312J
The reactions of a precursor cluster [Et4N]4[WS4Cu4I6] (1) with two equiv. of 1,1′-(1,4-butanediyl)bis(3,5-dimethyl-pyrazole) (bbd) or 1,3,5-tris(3,5-dimethyl-pyrazolyl-1-ylmethyl)-2,4,6-trimethylbenzene (tdtb) in MeCN/DMF afforded the dimeric clusters [WS4Cu3I(μ-bbd)]2 (2) and [{WS4Cu3(tdtb)}2(μ-I)2]·2DMF (3·2DMF), respectively. Solvothermal reactions of 1 with two equiv. of bbd in MeCN/DMF at 90 °C for 24 h resulted in the formation of the dimeric cluster [Et4 N]6[{WS4Cu5(μ-I)2I4}2(μ-bbd)] (4) while those of 1 with two equiv. of 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titb) in DMF at 120 °C afforded the polymeric cluster {[WS4Cu2(titb)]·0.5H2O}n (5). Compounds 2–5 were characterized by elemental analysis, IR, UV-vis, 1H NMR and single-crystal X-ray crystallography. Compound 2 has a double nido-shaped structure in which two nido-shaped [WS4Cu3] cores are connected by a pair of bbd ligands while 3 has a double butterfly-shaped structure in which two [WS4Cu3(tdtb)] fragments are linked by two bridging iodides. Compound 4 has a double-double half-open cubane-like structure in which a couple of double half-open cubane-like [WS4Cu5] cores are bridged by one bbd ligand. Compound 5 has a unique two-fold interpenetrated 3D (102·12)core(102·12)titb network in which each linear [WS4Cu2] core acts as a T-shaped 3-connecting node and each titb ligand works as a trigonal pyramidal 3-connecting node. The core structures of 2–5 are different from the saddle-shaped [WS4Cu4] core of 1, which may be attributed to the degradation or expansion of the cluster core of 1 during the reactions. In addition, the third-order non-linear optical (NLO) properties of 1–4 in DMF were also investigated by using Z-scan techniques at 532 nm.
Co-reporter:Dong Liu, Hong-Xi Li, Zhi-Gang Ren, Yang Chen, Yong Zhang, and Jian-Ping Lang
Crystal Growth & Design 2009 Volume 9(Issue 10) pp:4562-4566
Publication Date(Web):July 21, 2009
DOI:10.1021/cg900576j
Acidification (pH = 3) of a solution containing AgNO3 with 1,4-benzenedicarboxylic acid (1,4-H2BDC) and 1,2-bis(4-pyridyl)ethylene (bpe) (molar ratio = 1:1:1) with 6 M HNO3 followed by hydrothermal treatment at 170 °C afforded a one-dimensional (1D) coordination polymer {[Ag2(bpe)2](1,4-BDC)·(1,4-H2BDC)}n (1). Photochemical [2 + 2] cycloaddition reaction of 1 through UV irradiation followed by dissolving the photolysis product in 6 M HNO3 and hydrothermal treatment at 170 °C led to the formation of a three-dimensional (3D) coordination polymer {[Ag4(4,4′-tpcb)3][(NO3)4(H2O)6]}n (4,4′-tpcb = tetrakis(4-pyridyl)-cyclobutane) (2). Compounds 1 and 2 were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 consists of a 1D linear chain extending along the [011] plane in which Ag(I) ions are bridged by bpe molecules. Compound 2 contains the 2-fold interpenetrating 3D cationic [Ag4(4,4′-tpcb)3]n4n+ net with the Schlafli symbol of (63)4(6284)3. Within the cages of this net occupy the uncommon nitrate-water cluster [(NO3)4(H2O)6]4− anions. The formation of such a cluster anion may provide some insight into the nature of hydration of nitrate in H2O.
Co-reporter:Jin-Xiang Chen;Xiao-Yan Tang;Zhi-Gang Ren;Yong Zhang
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 1) pp:38-41
Publication Date(Web):
DOI:10.1002/ejic.200800969
Abstract
A unique pentanuclear bismuth(III) zwitterionic thiolate complex, [Bi5(Tab)18](PF6)7(NO3)8]·6MeCN [1; Tab = 4-(trimethylammonio)benzenethiolato], was obtained from the reaction of Bi(NO3)3 with TabHPF6 in a 1:4 molar ratio in MeCN/MeOH in the presence of Et3N and structurally characterized. Single-crystal X-ray diffraction revealed that 1 consists of an unprecedented linear [Bi5(Tab)18]15+ cation, and both [PF6]– and [NO3]– anions in the crystal cooperatively work as anionic templates to form interesting anionic honeycomb-like cavities for encapsulating the [Bi5(Tab)18]15+cations.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Zhen-Hong Wei;Ling-Ling Li;Zhi-Gang Ren;Hong-Xi Li;Yong Zhang;Zhen-Rong Sun
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 28) pp:4240-4247
Publication Date(Web):
DOI:10.1002/ejic.200900424
Abstract
Reactions of the preformed cluster [Et4N][Tp*W(μ3-S)(μ-S)2(CuSCN)2] (1) with pyridine (py), 4,4′-bipyridine (4,4′-bipy), or 1,3-bis(4-pyridyl)propane (bpp) led to the formation of three neutral [Tp*W(μ3-S)(μ-S)2Cu2]-based compounds [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(py)2] (2), [{Tp*W(μ3-S)(μ-S)2Cu2(SCN)}2(4,4′-bipy)]·3.5H2O (3·3.5H2O), and [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(bpp)]2 (4), respectively. Compounds 2–4 were characterized by elemental analysis, IR spectra, UV/Vis spectra, 1H NMR, and X-ray analysis. There are two linkage isomers [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(py)2] and [Tp*W(μ3-S)(μ-S)2Cu2(NCS)(py)2], each of which has its own enantiomeric pair in the crystal of 2. Compound 3 has a double butterfly-shaped structure in which two [Tp*W(μ3-S)(μ-S)2Cu2(SCN)] fragments are linked with a single 4,4′-bipy bridge. For 4, the two butterfly-shaped [Tp*W(μ3-S)(μ-S)2Cu2(SCN)] fragments are interconnected by a pair of bpp bridges. The third-order nonlinear optical (NLO) performances of 2–4 in DMF were also investigated by Z-scan techniques.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Guang-Fei Liu;Ling-Ling Li;Zhi-Gang Ren;Hong-Xi Li;Zhen-Ping Cheng;Jian Zhu;Xiu-Lin Zhu
Macromolecular Chemistry and Physics 2009 Volume 210( Issue 19) pp:1654-1660
Publication Date(Web):
DOI:10.1002/macp.200900216
Co-reporter:Ni-Ya Li, Zhi-Gang Ren, Dong Liu, Jing Wang, Ming Dai, Hong-Xi Li, Jian-Ping Lang
Inorganic Chemistry Communications 2009 Volume 12(Issue 10) pp:1031-1034
Publication Date(Web):October 2009
DOI:10.1016/j.inoche.2009.08.014
Diffusion reactions of CuI with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine) (dppeda) and 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) in MeCN/toluene in a zigzag glass tube or solvothermal reactions of CuI and dppeda or dpppda in MeCN produced two [CuxIx]-based coordination polymers, [Cu2I2(dppeda)]·2MeCN (1·2MeCN) and [Cu4I4(dpppda)]·MeCN (2·MeCN), respectively. Both compounds were characterized by elemental analysis, IR spectroscopy, 1H and 31P{1H} NMR, ESI-MS and thermogravimetric analysis, and their structures were determined by single crystal X-ray diffraction. In 1, [Cu2I2] cores are interconnected by dppeda ligands in a μ-η2:η2end-to-end mode to form a 1D chain, while in 2 stair-like [Cu4I4] cores are linked by dpppda ligands in a unique Z-shaped μ-η2:η2side-by-side mode to produce the other kind of 1D chain.Two 1D [CuxIx]-based coordination polymers [Cu2I2(dppeda)]·2MeCN (dppeda = N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine)) and [Cu4I4(dpppda)]·MeCN (dpppda = 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine) were isolated from solvothermal reactions of CuI with dppeda or dpppda. Both complexes were structurally characterized by elemental analysis, IR, 1H and 31P{1H}, and X-ray crystallography and their stability in solution and in solid state were studied by ESI-MS and thermogravimetric analysis.
Co-reporter:Guang-Fei Liu, Ling-Ling Li, Yu-Shu Ren, Hong-Xi Li, Zhi-Gang Ren, Yong Zhang, Jian-Ping Lang
Inorganic Chemistry Communications 2009 Volume 12(Issue 6) pp:563-565
Publication Date(Web):June 2009
DOI:10.1016/j.inoche.2009.04.021
Co-reporter:Bing Wu, Zhi-Gang Ren, Hong-Xi Li, Ming Dai, Duan-Xiu Li, Yong Zhang, Jian-Ping Lang
Inorganic Chemistry Communications 2009 Volume 12(Issue 11) pp:1168-1170
Publication Date(Web):November 2009
DOI:10.1016/j.inoche.2009.09.020
Co-reporter:Li Li, Zhi-Gang Ren, Ni-Ya Li, Yong Zhang, Jian-Ping Lang
Inorganica Chimica Acta 2009 Volume 362(Issue 11) pp:3910-3914
Publication Date(Web):15 August 2009
DOI:10.1016/j.ica.2009.05.018
Co-reporter:Xiao-Yan Tang, Hong-Xi Li, Jin-Xiang Chen, Zhi-Gang Ren, Jian-Ping Lang
Coordination Chemistry Reviews 2008 Volume 252(18–20) pp:2026-2049
Publication Date(Web):October 2008
DOI:10.1016/j.ccr.2007.11.001
The chemistry of metal complexes of the zwitterionic ammonium thiolates has expanded dramatically in the recent years. This review is intended to summarize the synthesis and crystal structures of groups 11 and 12 metal zwitterionic ammonium thiolate complexes. Seven methods for the synthesis of these metal complexes of the zwitterionic ammonium thiolates are outlined: proton transfer reaction, precursor reaction, ligand exchange reaction, oxidation–reduction reaction, solid-state reaction, electrochemical reaction and hydro(solvo)thermal reaction. These metal complexes of the zwitterionic ammonium thiolates are classified according to the number of metal atoms; their specific structures are briefly discussed.
Co-reporter:Wen-Hua Zhang, Ying-Lin Song, Zhen-Hong Wei, Ling-Ling Li, Yu-Jian Huang, Yong Zhang and Jian-Ping Lang
Inorganic Chemistry 2008 Volume 47(Issue 12) pp:5332-5346
Publication Date(Web):May 17, 2008
DOI:10.1021/ic8003454
The construction of a new set of [(η5-C5Me5)MoS3Cu3]-based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(η5-C5Me5)MoS3(CuX)3] (X = Br (1a), NCS (1b)) with 1,2-bis(4-pyridyl)ethane (bpe) and 1,3-bis(4-pyridyl)propane (bpp) is presented. Reactions of 1a with bpe in different molar ratios afforded {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3.5Br4]·MeCN}n (2), {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3Br4]·Sol}n (3a: Sol = DMSO·3MeCN; 3b: Sol = 2aniline·3MeCN), {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)3(bpe)Br4]·0.35DMF}n (4), and {[{(η5-C5Me5)MoS3Cu3}2(μ-bpe)2(μ-Br)(μ3-Br)Br2]·DMF·MeCN}n (5). On the other hand, treatment of 1a or 1b with bpp produced [(η5-C5Me5)MoS3Cu3(μ-bpp)(μ-Br)Br]n (6) and {[{(η5-C5Me5)MoS3Cu3}2(μ-bpp)3(μ-NCS)2(NCS)](NCS)}n (7). Compounds 2−7 have been characterized by elemental analysis, UV−vis spectroscopy, IR spectroscopy, 1H NMR, and X-ray analysis. In 2, each [(η5-C5Me5)MoS3Cu3] core serves as an angular two-connecting node to link other equivalent cores by single and double bpe bridges to form a 1D “Great Wall”-like chain. In 3a and 3b, the [(η5-C5Me5)MoS3Cu3] cores are linked alternatively by single and double bpe bridges to give a 1D zigzag chain. In 4, six cluster cores (two as a two-connecting node and four as a three-connecting node) are connected by four single bpe and two double bpe bridges to form a cyclohexane-shaped repeating unit, which is further fused with other units to generate a 1D double-stranded chain. Compound 5 has a simple 1D zigzag chain consisting of the cluster cores linked by single bpe bridges. In 6, the cluster cores are linked by single bpp bridges to give a 1D helical chain, which further holds two symmetry-related chains through C−H···Br hydrogen-bonding interactions, thereby forming a 1D H-bonded triple-stranded chain. Compound 7 has a rare 1D quadruple chain, in which the [(η5-C5Me5)MoS3Cu3] cores work as planar four- and five-connecting nodes to interconnect other equivalent cores through single bpp bridges and single and double thiocyanate bridges. In addition, the third-order nonlinear optical properties of 1a, 2, 3a, and 4−7 in aniline were also investigated by using the Z-scan technique with a 4.5 ns pulse laser at 532 nm.
Co-reporter:Zhen-Hong Wei ; Hong-Xi Li ; Wen-Hua Zhang ; Zhi-Gang Ren ; Yong Zhang ; Jian-Ping Lang ;Brendan F. Abrahams
Inorganic Chemistry 2008 Volume 47(Issue 22) pp:10461-10468
Publication Date(Web):October 14, 2008
DOI:10.1021/ic801100g
Treatment of [Et4N]2[(edt)2Mo2S2(μ-S)2] (1) (edt = ethanedithiolate) with equimolar CuBr afforded an anionic hexanuclear cluster [Et4N]2[(edt)2Mo2(μ-S)3(μ3-S)Cu]2·2CH2Cl2 (2·2CH2Cl2). On the other hand, reactions of 1 with 2 equiv of CuBr in the presence of 1,2-bis(diphenylphosphino)methane (dppm) and pyridine (Py) ligands gave rise to two neutral tetranuclear clusters [(edt)2Mo2O2(μ-S)2Cu2(dppm)2] (3) and [(edt)2Mo2O(μ3-S)(μ-S)2Cu2(Py)4] (4), respectively. The reaction of 1 with 2 equiv of CuBr followed by the addition of a mixture of dppm and Py (molar ratio = 1:2) yielded another neutral tetranuclear cluster [(edt)2Mo2(μ-S)2(μ3-S)2Cu2(dppm)(Py)]·Py (5·Py). Compounds 2−5 have been characterized by elemental analysis, UV−vis spectra, IR spectra, 1H NMR, and X-ray analysis. The structure of the dianion of 2 can be viewed as having a [Mo4S8Cu2] core in which two chemically equivalent [Mo2(μ-S)3(μ3-S)(edt)2Cu]− anions are linked by two extra Cu−Sedt bonds. The molecular structure of 3 may be visualized as being built of one [(edt)2Mo2X2(μ-S)2]2− dianion and one [Cu2(dppm)2]2+ dication that are connected by a pair of M−μ-Sedt bonds. Compound 4 is formed by the affiliation of two Cu(I) atoms only at one end of the [(edt)2Mo2S2(μ-S)2] moiety, connecting with the St atoms and the Sedt atom. Cluster 5·Py can be viewed as being constructed from the addition of one Cu atom onto the incomplete cubanelike [Mo2S4Cu] framework through one terminal sulfur and one edt sulfur. Among the four clusters, 3 and 4 have internal mirror symmetry or pseudo mirror symmetry, respectively, while 2 and 5 are asymmetric clusters with racemic formation.
Co-reporter:Wen-Hua Zhang, Jian-Ping Lang, Yong Zhang and Brendan F. Abrahams
Crystal Growth & Design 2008 Volume 8(Issue 2) pp:399
Publication Date(Web):January 11, 2008
DOI:10.1021/cg701131t
Reactions of [Et4N]2[MoS4(CuCN)2]·H2O with bis-(4-pyridyl)propane (bpp) and [Cu(MeCN)4][ClO4] in aniline produced [MoS4Cu4(bpp)2(CN)2]·1.5(aniline) (1a). 1a consists of a new three-dimensional [MoS4Cu4]-supported open coordination polymer which has a relatively large channel with a volume of ca. 618 Å3 per unit cell. 1a underwent a two-step host–guest process in which the aniline molecules residing in its channels could be partly exchanged with MeCN molecules in 3d and then completely with dimethylformamide molecules in a month, forming {[MoS4Cu4(bpp)2(CN)2]·(aniline)·(MeCN)}n (1b) and {[MoS4Cu4(bpp)2(CN)2]·(DMF)·(MeCN)}n (1c), respectively.
Co-reporter:Wen-Hua Zhang, Ying-Lin Song, Yong Zhang and Jian-Ping Lang
Crystal Growth & Design 2008 Volume 8(Issue 1) pp:253
Publication Date(Web):November 27, 2007
DOI:10.1021/cg070235n
Reaction of a cluster precursor [Et4N]2[MoOS3(CuCN)] (1) with equimolar [Cu(MeCN)4](PF6) in MeCN/aniline gave rise to an interesting polymeric cluster {[Et4N]2[MoOS3Cu2(μ-CN)]2·2aniline}n (2), while treatment of 1 in MeCN with 2 equiv of CuCN and KCN in H2O afforded the other polymeric cluster {[Et4N]4[MoOS3Cu3CN(μ′-CN)]2(μ-CN)2}n (3). Generated by addition of one or two Cu+ onto the [MoOS3Cu] cluster core in 1, the butterfly shaped [MoOS3Cu2] fragment in 2 or the incomplete cubanelike [MoOS3Cu3] fragment in 3 was dimerized into a prismatic [MoOS3Cu2]2 cage core or a double incomplete cubanelike [MoOS3Cu3]2 core. These two expanded cores serve as a unique planar 4-connecting node (2) or a rare chairlike 4-connecting node (3) to link equivalent nodes via cyanide bridges, forming two kinds of different 2D (4,4) networks. The third-order nonlinear optical (NLO) properties of 1−3 in DMF were also investigated.
Co-reporter:Yang Chen, Hong-Xi Li, Dong Liu, Lei-Lei Liu, Ni-Ya Li, Huan-Ying Ye, Yong Zhang and Jian-Ping Lang
Crystal Growth & Design 2008 Volume 8(Issue 10) pp:3810-3816
Publication Date(Web):August 13, 2008
DOI:10.1021/cg8004568
Four [Cu2I2]- or [Cu4I4]-based coordination polymers, [CuI(bpp)]n (1), {[Cu3I3(bpp)3]·2aniline·MeCN}n (2), {[Cu2I2(bpp)2]·2aniline}n (3), and [Cu4I4(bpp)2]n (4), were prepared by solvothermal reactions of CuI or Cu2(OH)2CO3 with 1,3-bis(4-pyridyl)propane (bpp) in different solvent systems. The preparation of 2 or 3 is involved in the in situ formation of aniline molecules and the reduction of Cu(II) to Cu(I). These compounds were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 consists of [Cu2I2] dimeric cores that link the neighboring ones via bpp bridges to form a one-dimensional double-bridged polymeric chain. Compound 2 or 3 has a similar chain structure in which the shape and size of the [Cu2I2(bpp)2]2 cavities that are occupied by MeCN/aniline or aniline solvent molecules are different from those of 1. Compound 4 has an intriguing two-dimensional 4-fold interpenetrated network in which each cubanelike [Cu4I4] core acts as a rare “seesaw”-shaped four-connecting node to interconnect four other equivalent ones via bpp bridges. The results did provide interesting insights into solvent effects on the construction of cluster-based coordination polymers. In addition, the photoluminescent properties of 1−4 in the solid state at ambient temperature were also investigated.
Co-reporter:Xiao-Yan Tang;Jin-Xiang Chen;Guang-Fei Liu;Zhi-Gang Ren;Yong Zhang
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 16) pp:2593-2600
Publication Date(Web):
DOI:10.1002/ejic.200800121
Abstract
The complex [Hg(Tab)2](PF6)2 [Tab = 4-(trimethylammonio)benzenethiolate] (1) reacts with one or two equivalents of NaCl to afford the mononuclear complex [Hg(Tab)2Cl](PF6) (2) and the dinuclear complex [{Hg(μ-Tab)(Tab)Cl}2]Cl2·H2O (3·H2O), respectively. Similar reactions of 1 with NaCl and NaX (molar ratio = 1:1) produce the dinuclear species [{Hg(μ-Tab)(Tab)Cl}2]X2 [X = NO2 (4), NO3 (5)], while those with NaNO2 or NaNO3 give rise to [{Hg(μ-Tab)(Tab)X}2]X2 [X = NO2 (6), NO3 (7)]. Complexes 2–7 have been characterised by elemental analysis, IR, UV/Vis, and 1H NMR spectroscopy, and X-ray crystallography. The Hg atom of the [Hg(Tab)2Cl]+ cation in 2 adopts a T-shaped coordination geometry. Two [Hg(Tab)2Cl]+ cations in 3·H2O, 4, and 5 are linked by a pair of weak Hg–S bonds to form a dimeric [Hg(μ-Tab)(Tab)Cl]22+ dication, and the centrosymmetric [Hg(μ-Tab)(Tab)X]22+ dication in 6 and 7 consists of two [Hg(Tab)2X]+ cations linked by a couple of weak Hg–S bonds. The hydrogen-bonding interactions in 2–7 lead to the formation of interesting 2D (5, 7) or 3D (2–4, 6) hydrogen-bonded networks.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:, Dong LIU;Hong-Xi LI;Yang CHEN;Yong ZHANG
Chinese Journal of Chemistry 2008 Volume 26( Issue 12) pp:2173-2178
Publication Date(Web):
DOI:10.1002/cjoc.200890387
Abstract
Hydrothermal reactions of Zn(NO3)2·6H2O with 1,2-di(4-pyridyl)ethylene (dpe) and 1,4-benzenedicarboxylate (1,4-BDC) or 1,3-benzenedicarboxylate (1,3-BDC) in water gave rise to two new metal-organic coordination polymers, [Zn(1,4-BDC)(dpe)]n (1) and [Zn4O(1,3-BDC)3(dpe)]n (2). Both compounds were characterized by elemental analysis and IR spectroscopy, and their structures were determined by single crystal X-ray diffraction. 1 displays a rare 5-fold interpenetrating 66-diamondoid framework while 2 possesses an interlocked 3D network formed by inclined interpenetration of 2D (4,4) networks that are constructed by µ4-oxo tetrazinc Zn4O cores and the bridging dpe and 1,3-BDC ligands. Thermal and photoluminescent properties of 1 and 2 were also investigated.
Co-reporter:Hua-Zhou Wu, Hong-Xi Li, Mei-Ling Cheng, Wen-Hua Zhang, Yong Zhang, Jian-Ping Lang
Inorganic Chemistry Communications 2008 Volume 11(Issue 1) pp:8-10
Publication Date(Web):January 2008
DOI:10.1016/j.inoche.2007.09.031
Complex [Zn(dmpzdtc)2] (1) (dmpzdtc = 3,5-dimethylpyrazole-1-dithiocarboxylate) in MeCN and pyridine underwent unique CS2 elimination and C–S bond cleavage reactions to afford a novel cyclic octanuclear zinc sulfide complex [Zn4(μ-dmpz)5(μ-OH) (μ3-S)(py)]2 · py (2 · py) dmpz = 3,5-dimethylpyrazolate). Single-crystal X-ray diffraction revealed that 2 consists of two [Zn4(μ-dmpz)3(μ-OH)(μ3-S)(py)] fragments linked by two pairs of μ-dmpz ligands, forming an unique metallocyclic structure. The luminescent property of this complex in solid state was also investigated.One cyclic octanuclear Zn(II) sulfide complex, [Zn4(μ-dmpz)5(μ-OH)(μ3-S)(py)]2 · py was isolated from CS2 elimination and C–S bond cleavage reactions of [Zn(dmpzdtc)2] in MeCN and pyridine. This complex was structurally characterized by elemental analysis, IR, and X-ray crystallography and their luminescent properties were studied.
Co-reporter:Yang Chen, You Song, Yong Zhang, Jian-Ping Lang
Inorganic Chemistry Communications 2008 Volume 11(Issue 5) pp:572-575
Publication Date(Web):May 2008
DOI:10.1016/j.inoche.2008.02.015
A tricobalt(II) coordination polymer {Na0.5[Co3(μ4-Mtta)1.5(μ2-OAc)3(μ3-OAc)(μ3-OH)]}n (1) (Mtta = 5-methyl tetrazolate) was prepared from the solvothermal reaction of Co(OAc)2 · 4H2O with NaN3 in MeCN in the presence of water. Complex 1 was characterized by elemental analysis, IR, and X-ray crystallography. 1 consists of a unprecedented 3D hydrogen-bound supramolecular structure in which a 2D layer with unusual (326272) topology holds the adjacent layers together in a ABAB sequence via unusual O–H⋯Na pseduo–agostic interactions. Complex 1 displayed the characteristics of a weak antiferromagnetic exchange interactions between Co2+ ions in the system of Co3(Mtta)3 trigonal unit.A novel 3D coordination polymer {Na0.5[Co3(μ4-Mtta)1.5(μ2-OAc)3(μ3-OAc)(μ3-OH)]}n (1) (Mtta = 5-methyl tetrazolate) was prepared by reactions of Co(OAc)2 · 4H2O with NaN3 in MeCN in the presence of water under the solvothermal conditions. The molecular structure of 1 was characterized by elemental analysis, IR, and X-ray crystallography and its magnetic properties were studied.
Co-reporter:Qiao-Yun Li, Xiao-Yan Tang, Wen-Hua Zhang, Jing Wang, Zhi-Gang Ren, Hong-Xi Li, Yong Zhang, Jian-Ping Lang
Journal of Molecular Structure 2008 Volume 879(1–3) pp:119-129
Publication Date(Web):15 May 2008
DOI:10.1016/j.molstruc.2007.08.022
Reactions of CoX2·6H2O (X = Cl−, ClO4−) with bis(3,5-dimethylpyrazolyl)methane (dmpzm) and formic acid, acetic acid, benzoic acid, salicylic acid, maleic acid, or fumaric acid under the presence of KOH solution produced a new family of Co(II)/dmpzm complexes, [Co(dmpzm)2L]X·nH2O (1: L = O2CH, X = Cl, n = 2; 2: L = OAc, X = Cl, n = 3; 3: L = benzoate, X = ClO4, n = 1/3; 4: L = salicylate, X = ClO4, n = 1/3) and [Co2(dmpzm)4L](ClO4)2·nSolv (5: L = maleate, n = 3, Solv = H2O; 6: L = fumarate, n = 2, Solv = MeOH). These compounds were structurally characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Compounds 1–4 are mononuclear while 5–6 are binuclear. Each cobalt atom of 1–6 is hexacoordinate, with a distorted octahedral CoN4O2 coordination geometry incorporating two N,N′-bidentate dmpzm ligands and one O,O′-bidentate carboxylate ligand. There are rich intra- and intermolecular hydrogen bonds in the crystals of 1–6, thereby forming either 2D hydrogen-bonded networks (1 and 2) or 3D hydrogen-bonded networks (3–6). In addition, the thermal behaviors of 1–6 were also investigated.
Co-reporter:Ling-Ling Li, Zhi-Gang Ren, Jing Wang, Zhen-Hong Wei, Yu-Jian Huang, Yong Zhang, Jian-Ping Lang, Li Deng, Zhen-Rong Sun
Journal of Molecular Structure 2008 Volume 886(1–3) pp:121-127
Publication Date(Web):27 August 2008
DOI:10.1016/j.molstruc.2007.11.005
Reactions of {[PPh4][WS4M]}n (1: M = Ag; 2: M = Cu) with equimolar 1,2-bis(diphenylphosphino)ethane (dppe) in CH2Cl2 produced two tetranuclear anionic clusters [PPh4]2[(WS4)M(μ-dppe)2M(WS4)]·2CH2Cl2 (3: M = Ag; 4: M = Cu). Both clusters were characterized by elemental analysis, IR, UV–vis, 1H NMR and single-crystal X-ray analysis. The centrosymmetric structure of the cluster dianion of 3 or 4 consists of two [WS4M] cluster fragments linked by a pair of dppe ligands. The third-order nonlinear optical (NLO) properties of 3 and 4 in solution were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80-fs pulsed laser at 800 nm. Both compounds exhibited strong NLO performances with χ(3) = 3.30 × 10−14 esu (3) or 2.89 × 10−14 esu (4), and γ = 1.064 × 10−31 esu (3) or 1.059 × 10−31 esu (4).
Co-reporter:Yang Chen, Zhi-Gang Ren, Hong-Xi Li, Xiao-Yan Tang, Wen-Hua Zhang, Yong Zhang, Jian-Ping Lang
Journal of Molecular Structure 2008 Volume 875(1–3) pp:339-345
Publication Date(Web):17 March 2008
DOI:10.1016/j.molstruc.2007.05.007
The solvothermal reactions of AgNO3, NaN3, with benzonitrile or 4-cyanopyridine in methanol/water yield two novel metal–organic coordination polymers, [Ag(μ3-phtta)]n (1) (phtta = 5-phenyltetrazolate) and {Ag[μ4-(4-pytta)]}n (2) [4-pytta = 5-(4-pyridyl)tetrazolate], respectively. The two reactions were involved in the in situ formation of 5-aryl-substituted tetrazolate ligands (phtta and pytta) through [2 + 3] cycloaddition reactions of azide anion with benzonitrile or 4-cyanopyridine. Compounds 1 and 2 were characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compound 1 has a one-dimensional double-chain structure in which centrosymmetric dimeric [Ag(phtta)]2 units are interconnected by four Ag–N bonds. These double-chains are further stacked into a 2D layer network through π–π interactions between tetrazolyl rings and interactions between Ag+ and phenyl group or tetrazolyl ring. Compound 2 has an intriguing 3D non-interpenetrated supramolecular structure in which a 2D layer network with (4.82)Ag(4.82)pytta topology holds the adjacent layers together via interactions of Ag+ ions in one layer with 4-N atoms of pytta ligands in the other. Photoluminescence studies revealed that solids 1 and 2 exhibit strong blue fluorescent emissions at λmax = 422 and 390 nm (λex = 345 nm), respectively, at ambient temperature.
Co-reporter:Hong-Xi Li, Hua-Zhou Wu, Wen-Hua Zhang, Zhi-Gang Ren, Yong Zhang and Jian-Ping Lang
Chemical Communications 2007 (Issue 47) pp:5052-5054
Publication Date(Web):27 Sep 2007
DOI:10.1039/B710787K
Dissolution of a mononuclear complex [Zn(dmpzdtc)2] in BrCH2CH2Br or DMF saturated with water followed by CS2 elimination led to the formation of two unique high-nuclearity metallamacrocyclic complexes, [Zn4(μ-dmpz)6(μ-OH)2]2 and [Zn4(μ-dmpz)6(μ-OH)2]4.
Co-reporter:Guang-Fei Liu;Zhi-Gang Ren;Hong-Xi Li;Yang Chen;Qiu-Hong Li;Yong Zhang
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 35) pp:
Publication Date(Web):17 OCT 2007
DOI:10.1002/ejic.200700657
Reactions of three CuII complexes of 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmpp), [Cu(bdmpp)(MeCN)2](ClO4)2 (1), [Cu(bdmpp)(N3)2]·1.5H2O (2·1.5H2O), and [Cu(bdmpp)(N3)(μ-N3)]2·2MeOH (3·2MeOH), with 4,4′-bipy, dicyanamide (dca), azide, and MCl2 (M = Cu, Co, Ni) yield a series of homo- and heterometallic coordination oligomers and polymers, [{Cu(bdmpp)(ClO4)}2(μ-4,4′-bipy)](ClO4)2 (4), {[Cu(bdmpp)(μ-dca)](ClO4)}n (5), {[Cu(bdmpp)(μ-N3)](ClO4)·MeCN}n (6), [{Cu(N3)(bdmpp)}2(μ-N3)2Cu(N3)2] (7), and [{Cu(μ-N3)(bdmpp)(μ-N3)M(μ-N3)(X)}2·eMeCN]n (8: M = Co, X = N3, e = 0; 9: M = Ni, X = Cl; e = 4). Compounds 1–9 have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray crystallography. Compound 4 has a centrosymmetric dimeric dication structure in which two [Cu(bdmpp)(ClO4)]+ fragments are bridged by one 4,4′-bipy. Compounds 5 and 6 have a 1D linear or spiral chain extending along the b axis in which each [Cu(bdmpp)]2+ fragment is linked through bridging dca or azide anions, respectively. Compound 7 has a trinuclear sandwich structure in which two molecules of 2 link a Cu(N3)2 species through two end-on bridging azide anions. Compounds 8 and 9 have a similar 1D chain structure extending along the c axis in which [Cu(μ-N3)(bdmpp)(μ-N3)M(μ-N3)(X)]2 (M = Co, Ni) molecules are linked by end-to-end azide anions (8) or end-on azide anions (9). In addition, the electrochemical properties of 1–9 in DMF were investigated by cyclic voltammetry. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Mei-Ling Cheng;Hong-Xi Li;Wen-Hua Zhang;Zhi-Gang Ren;Yong Zhang
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 13) pp:
Publication Date(Web):22 MAR 2007
DOI:10.1002/ejic.200601132
Reactions of [(Me3Si)2N]3Ln(μ-Cl)Li(thf)3 (1: Ln = Pr; 2: Ln = Sm) with an equimolar amount of tBuSH or EtSH gave rise to four amidolanthanide alkylthiolate complexes [{(Me3Si)2N}2Ln(μ-StBu)]2 (3: Ln = Pr; 4: Ln = Sm) and [Li(thf)4][{(Me3Si)2N}4Ln4(μ4-SEt)(μ-SEt)8] (5: Ln = Pr; 6: Ln = Sm). Compounds 3–6 were characterized by elemental analysis, IR and 1H NMR spectroscopy and single-crystal X-ray diffraction, and their catalytic properties were also investigated. Compounds 3 and 4 are thiolate-bridged dimers in which each Ln atom adopts a distorted tetrahedral coordination. Compounds 5 and 6 contain a Ln4 square plane, which is capped by a μ4-SEt– ligand. The edges of the square are bridged by four pairs of SEt– ligands on both sides of the Ln4 plane. Each Ln atom has a distorted octahedral geometry. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Bing Wu, Wen-Hua Zhang, Hong-Xi Li, Zhi-Gang Ren, Jian-Ping Lang, Yong Zhang, Ying-Lin Song
Journal of Molecular Structure 2007 Volume 829(1–3) pp:128-134
Publication Date(Web):17 March 2007
DOI:10.1016/j.molstruc.2006.06.016
Reaction of (NH4)2[WOS3] with 2 equiv. of CuI in 4-tert-butylpyridine (4-tBuPy) and methanol afforded a hexanuclear neutral cluster [WOS3Cu2(4-tBuPy)2]2. This compound was characterized by elementary analysis, IR, UV–vis, 1H NMR, thermogravimetric analysis, and its crystal structure was determined by X-ray single crystal diffraction. The compound contains a hexagonal prismatic cage structure in which two butterfly-shaped [WOS3Cu2(4-tBuPy)2] cluster fragments are interlinked through four CuS bonds. The nonlinear optical properties were studied with a 30 ps pulsed laser at 532 nm. The compound exhibited strong nonlinear absorption effect with α2 = 2.5 × 10−10 mW−1, χ(3) = 8.5 × 10−14 esu, and γ = 4.8 × 10−30 esu.
Co-reporter:Hong-Xi Li, Yan-Jun Zhu, Mei-Ling Cheng, Zhi-Gang Ren, Jian-Ping Lang, Qi Shen
Coordination Chemistry Reviews 2006 Volume 250(15–16) pp:2059-2092
Publication Date(Web):August 2006
DOI:10.1016/j.ccr.2006.02.005
The chemistry of lanthanide chalcogenolate complexes has expanded dramatically in the recent years. This review summarized the syntheses and crystal structures of the lanthanide chalcogenolate complexes and their applications in organic chemistry. Four methods for the synthesis of lanthanide chalcogenolate complexes were outlined: protonolysis, metathesis, oxidation–reduction, and insertion reaction. The lanthanide chalcogenolate complexes were classified according to the ancillary ligands coordinated to lanthanide atoms and the number of lanthanide atoms, and some specific structures were briefly described. The reactivity and catalytical property of some lanthanide chalcogenolate complexes in organic and polymer synthesis along with their luminescent properties are highlighted.
Co-reporter:Qiao-Yun Li;Wen-Hua Zhang;Hong-Xi Li;Xiao-Yan Tang;Yong Zhang;Xin-Yi Wang;Song Gao
Chinese Journal of Chemistry 2006 Volume 24(Issue 12) pp:
Publication Date(Web):4 DEC 2006
DOI:10.1002/cjoc.200690321
Reaction of CoCl2·6H2O with equimolar bis(3,5-dimethylpyrazolyl)methane (dmpzm) produced a mononuclear adduct [Co(dmpzm)Cl2] (1). Treatment of 1 with sodium dicyanamide (dca) afforded a polymeric complex [Co(dmpzm)(μ-dca)2]∞ (2). 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network (extended along the bc plane) in which the {[Co(dmpzm)(μ-dca)]2}2n+n chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated.
Co-reporter:Qiao-Yun Li;Wen-Hua Zhang;Hong-Xi Li;Zhi-Gang Ren;Yong Zhang
Chinese Journal of Chemistry 2006 Volume 24(Issue 6) pp:811-816
Publication Date(Web):7 JUN 2006
DOI:10.1002/cjoc.200690154
Reactions of lead(II) nitrate or perchlorate with bis(3,5-dimethylpyrazolyl)methane (dmpzm), produced two new Pb(II) chelated complexes [Pb(dmpzm)2X2] (X=NO−31, ClO−42). Both compounds were structurally characterized by elemental analysis, IR spectroscopy, thermal analysis, and single crystal X-ray diffraction. Both compounds are mononuclear with a distorted square antiprismatic PbN4O4 coordination geometry incorporating a pair of O,O′-bidentate anions and N,N′-bidentate dmpzm ligands. In the crystals of 1 or 2, the methyl or methylene groups of dmpzm ligand interact with the oxygen atoms of nitrates or perchlorates to afford intra- and intermolecular hydrogen bonding, thereby forming a two-dimensional network 1 or a three-dimensional structure 2.
Co-reporter:Hong Yu, Mei-Ling Cheng, Wen-Hua Zhang, Zhi-Gang Ren, Jian-Ping Lang
Inorganica Chimica Acta 2006 Volume 359(Issue 11) pp:3507-3514
Publication Date(Web):1 August 2006
DOI:10.1016/j.ica.2006.01.022
Reactions of [PPh4][(η5-C5Me5)WS3] with equimolar M′Cl2 (M′ = Zn, Cd) in MeCN or 0.5 equiv. of HgCl2 in DMF afforded two binuclear clusters [PPh4][(η5-C5Me5)WS3(M′Cl2)] (1: M′ = Zn; 2: M′ = Cd) and one trinuclear cluster [{(η5-C5Me5)WS3}2Hg] (3). Compounds 1–3 were characterized by elemental analysis, IR, UV–Vis, 1H NMR and X-ray crystallography. Compound 1 may be viewed as a 1:1 composite of [PPh4][(η5-C5Me5)WS3] and ZnCl2, in which one [(η5-C5Me5)WS3]− anion binds a ZnCl2 moiety via two μ-S atoms. In the structure of 3, two [(η5-C5Me5)WS3]− anions coordinate the central Hg atom via two μ-S atoms, forming an unique bent linear structure. In addition, internal redox reactions of [PPh4][(η5-C5Me5)WS3] under the presence of M′Cl2 (M′ = Zn, Cd, Hg) in high concentrations were discussed.Two binuclear clusters [PPh4][(η5-C5Me5)WS3(M′Cl2)] (1: M′ = Zn; 2: M′ = Cd) and one trinuclear cluster [{(η5-C5Me5)WS3}2Hg] (3) were isolated from reactions of [PPh4][(η5-C5Me5)WS3] with M′Cl2 (M′ = Zn, Cd, Hg) in MeCN. The structures of 1–3 were characterized by elemental analysis, IR, UV–Vis, 1H NMR and X-ray crystallography.
Co-reporter:Hong-Xi Li;Yong Zhang;Zhi-Gang Ren;Mei-Ling Cheng;Jing Wang
Chinese Journal of Chemistry 2005 Volume 23(Issue 11) pp:
Publication Date(Web):30 NOV 2005
DOI:10.1002/cjoc.200591499
Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [(THF)3I2- Sm(μ-SAr)]2 [Ar=Ph (1), 4-Me2NC6H4 (2)] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group and a=0.95705(13) nm, b=1.22287(14) nm, c=1.26450(14) nm, α=64.194(11)°, B=78.491(13)°, γ=76.176(12)°, V=1.2860(3) nm3, Z=1, μ=4.783 mm−1, Dc=1.964 Mg/m3, M=1521.19, S=1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordination geometry.
Co-reporter:Hong Yu, Wen-Hua Zhang, Zhi-Gang Ren, Jin-Xiang Chen, Chun-Lan Wang, Jian-Ping Lang, Hendry Izaac Elim, Wei Ji
Journal of Organometallic Chemistry 2005 Volume 690(Issue 17) pp:4027-4035
Publication Date(Web):1 September 2005
DOI:10.1016/j.jorganchem.2005.06.003
Treatment of a preformed cluster {(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 (1) in MeCN with excess pyridine afforded a tetranuclear cationic cluster [(η5-C5Me5)WS3Cu3(Py)6](PF6)2 (2). On the other hand, reactions of 1 with excess PPh3 under the presence of LiBr gave rise to the other tetranuclear cationic cubane-type cluster [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6) (3) while analogous reactions of 1 with dppm and LiCl followed by addition of excess pyridine generated an intriguing pentanuclear cationic cluster [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2 (4). Compounds 2–4 were fully characterized by spectroscopy and X-ray crystallography. The cluster dication of 2 adopts an incomplete WS3Cu3 cubane-like structure while the cluster cation of 3 contains a WS3Cu3Br cubane-like structure. The structure of the cluster dication of 4 consists of an unique WS3Cu4Cl framework in which an open cubane-like WS3Cu3Cl fragment and a Cu(dppm)2 fragment are connected by one Cu–Cl bond and two Cu–dppm–Cu bridges. The optical limiting (OL) properties of the MeCN solutions of 1–4 were investigated with 7-ns laser pulses at 532 nm.Three new W/Cu/S clusters [(η5-C5Me5)WS3Cu3(Py)6](PF6)2, [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6), and [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2 were prepared from reactions of [{(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 with pyridine, PPh3 and dppm. The structures of the three compounds were characterized by X-ray crystallography and their optical limiting properties in solution were studied.
Co-reporter:Yan-Jun Zhu, Jin-Xiang Chen, Wen-Hua Zhang, Zhi-Gang Ren, Yong Zhang, Jian-Ping Lang, Seik-Weng Ng
Journal of Organometallic Chemistry 2005 Volume 690(Issue 14) pp:3479-3487
Publication Date(Web):15 July 2005
DOI:10.1016/j.jorganchem.2005.04.041
Reactions of Ln2O3 and trans-4-pyridylacrylic acid (4-Hpya) in EtOH/H2O or MeOH/H2O produced two new lanthanide/4-pya complexes [Ln(4-pya)3(H2O)2]2 (1: Ln = Eu; 2: Ln = La) in low yields. However, reactions of LnCl3 · 6H2O with 4-Hpya/aqueous ammonia in EtOH/H2O or MeOH/H2O gave rise to 1 or 2 in higher yields. Both compounds were structurally characterized by elemental analysis, IR spectroscopy and X-ray analysis. Compounds 1 · 2EtOH · 2H2O and 2 · 2MeOH · 2H2O were confirmed to possess one-dimensional polymeric chain structures. In the structure of 1, each Eu(III) adopts a monocapped square-antiprism coordination geometry and each dimer [Eu(4-pya)3(H2O)2]2 within the chain is interconnected by two pairs of different bridging 4-pya ligands. On the other hand, each La(III) of 2 takes a bicapped square-antiprism coordination geometry and each dimer [La(4-pya)3(H2O)2]2 within the chain is linked by two pairs of tridentate bridging 4-pya ligands. The luminescent properties of 1 and 2 in the solid state were investigated.Two new lanthanide/4-pya complexes [Ln(4-pya)3(H2O)2]2 (1: Ln = Eu; 2: Ln = La) were isolated either from reactions of Ln2O3 and trans-4-pyridylacrylic acid (4-Hpya) or from reactions of LnCl3 · 6H2O with 4-Hpya/aqueous ammonia in EtOH/H2O or in MeOH/H2O. The structures of both compounds were characterized by X-ray crystallography and their luminescent properties in solid state were studied.
Co-reporter:Wen-Hua Zhang, Jin-Xiang Chen, Hong-Xi Li, Bin Wu, Xiao-Yan Tang, Zhi-Gang Ren, Yong Zhang, Jian-Ping Lang, Zhen-Rong Sun
Journal of Organometallic Chemistry 2005 Volume 690(Issue 2) pp:394-402
Publication Date(Web):17 January 2005
DOI:10.1016/j.jorganchem.2004.09.052
Co-reporter:Jian-Ping Lang;Qing-Feng Xu;Wei Ji;Hendry Izaac Elim;Kazuyuki Tatsumi
European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 1) pp:
Publication Date(Web):23 OCT 2003
DOI:10.1002/ejic.200300204
Reactions of [PPh4][(η5-C5Me5)WS3] with two equivalents of CuCN in MeCN produced a novel trinuclear butterfly-shaped cluster [PPh4][(η5-C5Me5)WS3(CuCN)2] (1) in a 70% yield. Treatment of 1 with excess PPh3 or Py gave rise to two different hexanuclear clusters [(η5-C5Me5)WS3Cu2(PPh3)(μ-CN)]2 (2) and [PPh4][{(η5-C5Me5)WS3Cu2(CN)(Py)}2(μ-CN)] (3), respectively. Compounds 1−3 were fully characterized by spectroscopy and X-ray crystallography. The structure of the cluster anion of 1 contains a butterfly-like WS3Cu2 fragment in which each Cu atom is coordinated to one μ-S atom, one μ3-S atom, and one terminal CN group. The neutral compound 2 has a double butterfly-shaped structure in which two WS3Cu2 fragments are interconnected by two Cu−μ-CN−Cu bridges. The anion of 3 adopts another type of double butterfly-shaped structure in which the two WS3Cu2 fragments are linked by a single Cu−μ-CN−Cu bridge. Compared with C60 in terms of the optical limiting (OL) properties measured under identical conditions, 1 and 2 exhibit a relatively good OL performance, whereas the OL effect is not observed for 3. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Co-reporter:Jin-Xiang Chen;Qing-Feng Xu;Ying Xu;Yong Zhang;Zhong-Ning Chen
European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 21) pp:
Publication Date(Web):26 AUG 2004
DOI:10.1002/ejic.200400193
The room-temperature solid-state reaction of silver acetate with TabHPF6 [Tab = 4-(trimethylammonio)benzenethiolate] followed by recrystallization from MeCN afforded a unique octadecanuclear silver thiolate complex [Ag9(Tab)8(MeCN)8]2(PF6)18·4MeCN (1). An X-ray analysis of 1 revealed that the structure of [Ag9(Tab)8(MeCN)8]218+ contains an unprecedented tubular motif in which one central saddle-shaped Ag6S6 fragment and two identical Ag5S6 fragments are interconnected by a pair of Ag atoms and four Ag−S bonds. The solid-state product was assumed to be [Ag9(Tab)8]2(PF6)18 and might have the Ag18S16 core structure of 1 based on elemental analysis, IR spectroscopy, 1H NMR spectroscopy, luminescence spectra, XRD and TGA measurements. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Co-reporter:Hong-Xi Li, Qing-Feng Xu, Jin-Xiang Chen, Mei-Ling Cheng, Yong Zhang, Wen-Hua Zhang, Jian-Ping Lang, Qi Shen
Journal of Organometallic Chemistry 2004 Volume 689(Issue 21) pp:3438-3448
Publication Date(Web):15 October 2004
DOI:10.1016/j.jorganchem.2004.07.044
Reactions of anhydrous lanthanide(III) trichloride (Ln = Nd, Sm, Eu, Ho, Yb) with one or two equiv. of LiN(SiMe3)2 in THF produced a family of lanthanide(III) bis(trimethylsilyl)amide chloride complexes: [{((Me3Si)2N)2Nd(μ′-Cl)Li(THF)3}(μ-Cl)]2 (1), [{((Me3Si)2N)2Ln(μ′-Cl)Li(THF)2}(μ3-Cl)]2 (Ln = Eu (2); Ln = Ho (3)), and [{(Me3Si)2NLn(μ′-Cl)2Li(THF)2}(μ-Cl)]2 (Ln = Nd (4); Ln = Sm (5); Ln = Eu (6); Ln = Ho (7); Ln = Yb (8)). On the other hand, reactions of the monosubstituted silylamido complexes [{(Me3Si)2NLn(μ′-Cl)2Li(THF)2}(μ-Cl)]2 (Ln = Nd (4); Sm (5); Eu (6); Ho (7)) with 2 equiv. of LiN(SiMe3)2 in THF afforded the corresponding disubstituted complexes [{((Me3Si)2N)2Ln(μ′-Cl)Li(THF)3}(μ-Cl)]2 (Ln = Nd (1); Sm (9)), [{((Me3Si)2N)2Ln(μ′-Cl)Li(THF)2}(μ3-Cl)]2 (Ln = Sm (9), Eu (2); Ho (3)). These complexes were characterized by melting point determination, elemental analysis and IR spectra. Single-crystal X-ray diffraction studies revealed that these compounds are chloride-bridged dimers, in which Ln metals in 1–3 display a distorted trigonal bipyramidal coordination geometry while those in 5, 6 and 8 a distorted octahedral coordination geometry. Complexes 1–9 exhibited catalytic activity for the ring-opening polymerization of ε-caprolactone.A family of lanthanide(III) bis(trimethylsilyl)amide chloride complexes, [{((Me3Si)2N)2Nd(μ′-Cl)Li(THF)3}(μ-Cl)]2 (1), [{((Me3Si)2N)2Ln(μ′-Cl)Li(THF)2}(μ3-Cl)]2 (Ln = Eu (2); Ln = Ho (3)), and [{(Me3Si)2NLn(μ′-Cl)2Li(THF)2}(μ-Cl)]2 (Ln = Nd (4); Ln = Sm (5); Ln = Eu (6); Ln = Ho (7); Ln = Yb (8)) were produced from reactions of LnCl3 (Ln = Nd, Sm, Eu, Ho, Yb) with one or two equiv. of LiN(SiMe3)2 in THF. These complexes were characterized by melting point determination, elemental analysis, IR spectra and single-crystal X-ray analysis. They exhibited catalytic activity for the ring-opening polymerization of ε-caprolactone.
Co-reporter:Jin-Xiang Chen, Qing-Feng Xu, Yong Zhang, Zhong-Ning Chen, Jian-Ping Lang
Journal of Organometallic Chemistry 2004 Volume 689(Issue 6) pp:1071-1077
Publication Date(Web):15 March 2004
DOI:10.1016/j.jorganchem.2004.01.016
Reactions of Ag(PPh3)2Cl with equimolar TabHPF6 (TabH=4-(trimethylammonio)benzenethiol) under the presence of Et3N in CH3OH/CH2Cl2 afforded a mononuclear complex [Ag(tab)2](PF6) (1). Treatment of 1 with excess Na2S in CH3CN/DMF gave rise to a unusual one-dimensional polymer {[Ag3(tab)4](PF6)3 · 2DMF}n (2) as a major product and a netradecanuclear cage-like cluster [Ag14(μ6-S)(Tab)12(PPh3)8](PF6)12 (3) as a minor product. Compounds 1 and 2 were characterized by elemental analysis, IR, UV–Vis, and X-ray analysis. The Ag atom of the [Ag(Tab)2]+ cation of 1 adopts a linear AgS2 coordination geometry. Compound 2 has an one-dimensional chain structure in which the repeating [Ag6(Tab)8]6+ units are interconnected by four Ag–S bonds with [PF6]− anions and DMF solvated molecules located between the polymeric chains. The structure of the [Ag14(μ6-S)(tab)12(PPh3)8]12+ dodecation of 3 consists of a μ6-sulfur atom encapsulated by an Ag14S12 cage. The luminescence properties of 1 and 2 in solution and in the solid state at room temperature are also reported.A new mononuclear complex [Ag(tab)2](PF6) (1) was prepared by reactions of [Ag(PPh3)2Cl] with TabHPF6 (TabH=4-(trimethylammonio)benzenethiol) and Et3N in CH3OH/CH2Cl2. Treatment of 1 with Na2S in CH3CN/DMF gave rise to an unique 1D polymer {[Ag3(tab)4](PF6)3 · 2DMF}n(2) and a netradecanuclear cage-like cluster [Ag14(μ6-S)(Tab)12(PPh3)8](PF6)12 (3). The crystal structures of 1, 2, and 3 have been characterized by X-ray crystallography.
Co-reporter:Jian-Ping Lang ;Qing-Feng Xu Dr.;Rong-Xin Yuan Dr.;Brendan F. Abrahams Dr.
Angewandte Chemie 2004 Volume 116(Issue 36) pp:
Publication Date(Web):7 SEP 2004
DOI:10.1002/ange.200460076
Eine ungewöhnliche supramolekulare Verbindung der Zusammensetzung {[WS4Cu4(4,4′-bpy)4][WS4Cu4I4(4,4′-bpy)2]}∞ (siehe Bild; 4,4′-bpy=4,4′-Bipyridyl) wurde durch Selbstorganisation des Mischmetallsulfidclusters [NEt4]4[WS4Cu4I6] erhalten. Das supramolekulare Aggregat besteht aus vier verzahnten Netzwerken vom Diamanttyp (zwei kationischen und zwei anionischen) und ist von Kanälen durchzogen, an deren Wänden sich Rezeptorstellen für Iodmoleküle befinden.
Co-reporter:Jian-Ping Lang ;Qing-Feng Xu Dr.;Rong-Xin Yuan Dr.;Brendan F. Abrahams Dr.
Angewandte Chemie International Edition 2004 Volume 43(Issue 36) pp:
Publication Date(Web):7 SEP 2004
DOI:10.1002/anie.200460076
An unusual supramolecular compound {[WS4Cu4(4,4′-bpy)4][WS4Cu4I4(4,4′-bpy)2]}∞ (see picture) was obtained from the self-assembly of a preformed mixed-metal sulfide cluster, [NEt4]4[WS4Cu4I6]. The product consists of four interpenetrating diamond-type nets (two cationic and two anionic) and has large open channels that are lined with “receptor sites” for guest iodine molecules. 4,4′-bpy=4,4′-bipyridyl.
Co-reporter:Jian-Ping Lang, Shun-Jun Ji, Qing-Feng Xu, Qi Shen, Kazuyuki Tatsumi
Coordination Chemistry Reviews 2003 Volume 241(1–2) pp:47-60
Publication Date(Web):June 2003
DOI:10.1016/S0010-8545(02)00309-0
The use of mononuclear metal sulfide ligands to construct heterometallic sulfide clusters is an area of inorganic chemistry that has received ever-increasing attention in recent years. This article reviews the advances that have been made in the synthesis and coordination chemistry of organometallic trithio complex, [PPh4][(η5-C5Me5)MS3] (M=W, Mo). From a set of 24 W(Mo) ∣ Cu(Ag, Au, Pd) ∣ S clusters containing (η5-C5Me5)MS3 moiety, three basic cluster fragments along with a rare fragment are topologically outlined. Each specific structure is briefly discussed and particular emphasis is put upon how the specific cluster array is assembled via these fragments or their certain combination is highlighted.
Co-reporter:Zhen-Hong Wei, Qing-Feng Xu, Hong-Xi Li, Jin-Xiang Chen, Jian-Ping Lang
Journal of Organometallic Chemistry 2003 Volume 687(Issue 1) pp:197-202
Publication Date(Web):1 December 2003
DOI:10.1016/j.jorganchem.2003.08.026
Co-reporter:Hong Yu;Qing-Feng Xu;Shun-Jun Ji;Zhen-Rong Sun
Chinese Journal of Chemistry 2003 Volume 21(Issue 12) pp:
Publication Date(Web):26 AUG 2010
DOI:10.1002/cjoc.20030211215
Reaction of [PPh4][η5-C5Me5)WS3] with Cul, CuBr and bis-(diphenylphosphino)methane (dppm) (molar ratio = 1:2:1:1) in MeCN gave rise to [PPh4][(η5-C5Me5)WS3 (CuBr)(Cul)2-(μ-dppm)] (1) in high yield. Compound 1 crystallizes in the monoclinic, space group P21/n with lattice parameters: a = 1.2906(4) nm, b = 1.5006(8) nm, c = 3.1484(6) nm, β = 92.12(2)°, V = 6.093(3) nm3, Z = 4. The structure of the anion of 1 contains an incomplete WS3Cu3 cubane-like core in which two Cul units are bridged by a dppm ligand. The W-Cu distances vary in the range of 0.2644(1)–0.2793(1) nm. The optical limiting (OL) properties of 1 in MeCN were measured with the laser pulse-width of 12-ns at 532 nm, and the nanosecond OL effect may be due to the reverse saturable absorption (RSA) related to the excited triplet states.
Co-reporter:Jian-Ping Lang, Zhen-Rong Sun, Qing-Feng Xu, Hong Yu, Kuzuyuki Tatsumi
Materials Chemistry and Physics 2003 Volume 82(Issue 2) pp:493-498
Publication Date(Web):15 November 2003
DOI:10.1016/S0254-0584(03)00322-5
Reactions of [PPh4][(η5-C5Me5)WS3] with CuBr and EPh3 (E=As,P) in MeCN gave rise to [(η5-C5Me5)WS3Cu3Br2(EPh3)2] (1: E=As; 2: E=P) in high yield. Single-crystal X-ray analysis revealed that the structure of 1 or 2 consists of a half-open cubane-like [WS3Cu3Br] cluster core where one Cu–Br bond is broken. The optical limiting properties for 1 and 2 in CH2Cl2 were studied with 12 ns and 35 ps laser pulses at 532 nm. The linear transmittance and thresholds at 532 nm laser light for 1 and 2 are 58% and 2.1 J cm−2, and 41% and 1.9 J cm−2, respectively. The optical limiting properties of 1 and 2 are compared with those of known closed cubane-like and nest-like clusters derived from [MS4]2−, [MOS3]2− (M=Mo,W), and [MoSe4]2− anions.
Co-reporter:Jian-Ping Lang, Hong Yu, Shun-Jun Ji, Kazuyuki Tatsumi
Inorganica Chimica Acta 2003 Volume 344() pp:169-173
Publication Date(Web):20 February 2003
DOI:10.1016/S0020-1693(02)01284-7
Reactions of [PPh4][(η5-C5Me5)WS3] with 1/2 equiv. of [M′(CH3CN)6](ClO4)2 (M′=Ni, Mn) in CH3CN afforded two novel trinuclear clusters [{(η5-C5Me5)WS3}]2Ni] (1) and [{(η5-C5Me5)WS3}]2Mn(CH3CN)] (2), respectively. Compounds 1 and 2 were fully characterized by spectroscopy and X-ray analysis. The central Ni(II) atom of 1 was tetrahedrally coordinated by two (η5-C5Me5)WS3 groups to form a linear WNiW structure, while 2 consists of a bent WMnW structure, in which the coordination geometry of the Mn(II) atom is a distorted square-pyramidal with a N (CN3CN) and four μ2-S atoms.Two new heterobimetallic sulfide clusters [{(η5-C5Me5)WS3}]2Ni] (1) and [{(η5-C5Me5)WS3}]2Mn(CH3CN)] (2) have been synthesized by reactions of [PPh4][(η5-C5Me5)WS3] with [M′(CH3CN)6](ClO4)2 (M′=Ni, Mn) in CH3CN. The molecular structures of 1 and 2 have been characterized by X-ray crystallography.
Co-reporter:Quan Liu;Qing-Feng Xu;Yong Zhang;Jin-Xiang Chen;Zhi-Feng Zhou
Chinese Journal of Chemistry 2002 Volume 20(Issue 12) pp:
Publication Date(Web):26 AUG 2010
DOI:10.1002/cjoc.20020201225
Reaction of (NH4)2MoS4 with [Cu(MeCN)4] (BF4) and (n-Bu)4NBr in CH2Cl2 afforded a new hexanuclear cluster [(n-Bu)4N]3[MoS4Cu5Br6] (1). 1 crystallizes in the monoclinic system, space group P21/c, with lattice parameters a = 1.17383(4) nm, b = 2.40136(4) nm, c = 2.64112(5) nm, β = 94.2020(5)°, V = 7.4247(5) nm3 and Z = 4. The structure of the [MoS4Cu5Br6]3- trianion of 1 is composed of one nido-like [MoS3Cu3] core and one half-open cubane-like [MoS3Cu3Br] core, which are interconnected by sharing the same MoSCuS plane. The MoCu distances vary in the range of 0.2622(6)-0.2692(5) nm.
Co-reporter:Hong Yu, Qing-Feng Xu, Zhen-Rong Sun, Shun-Jin Ji, Jin-Xiang Chen, Quan Liu, Jian-Ping Lang and Kazuyuki Tatsumi
Chemical Communications 2001 (Issue 24) pp:2614-2615
Publication Date(Web):16 Nov 2001
DOI:10.1039/B107251J
Reaction of (NH4)2[WS4], [Ag(MeCN)4](PF6) and dppm (molar ratio = 1∶2∶4) in the solid state at 110 °C followed by extraction with CH2Cl2 yielded a hexanuclear neutral cluster [(WS4)2Ag4(dppm)3] 1, while the same materials when mixed directly in CH2Cl2 produced a tetranuclear cluster salt [WS4Ag3(dppm)4](PF6) 2; both compounds showed modest third-order optical nonlinearities.
Co-reporter:Dong Liu ; Jian-Ping Lang ;Brendan F. Abrahams
Journal of the American Chemical Society () pp:
Publication Date(Web):June 30, 2011
DOI:10.1021/ja203053y
The three-dimensional crystalline porous metal–organic framework [Ni2(μ2-OH2)(1,3-BDC)2(tpcb)]n (1) [1,3-H2BDC = 1,3-benzenedicarboxylic acid; tpcb = tetrakis(4-pyridyl)cyclobutane] was used to separate a solid mixture of naphthalene and anthracene at room temperature via selective adsorption of naphthalene. The process involved a single-crystal-to-single-crystal transformation. The guest naphthalene molecules could be exchanged with ethanol, and the host, 1, could be regenerated by removal of the guest ethanol molecules.
Co-reporter:Fan Wang, Chun-Yan Ni, Quan Liu, Fu-Ling Li, Jing Shi, Hong-Xi Li and Jian-Ping Lang
Chemical Communications 2013 - vol. 49(Issue 81) pp:NaN9250-9250
Publication Date(Web):2013/07/30
DOI:10.1039/C3CC45066J
Ambient temperature solid-state reaction of Pb(OAc)2 with TabHPF6 afforded an intermediate product [Pb(Tab)2]2(PF6)4, which further reacted with 4,4′-bipy in the solid state to generate a unique 2D cationic coordination polymer [Pb(Tab)2(4,4′-bipy)](PF6)2 in quantitative yield. Both complexes possess a low dielectric constant and low dielectric loss in the high electric field frequency range.
Co-reporter:Xi Chen, Hong-Xi Li, Zhi-Yuan Zhang, Wei Zhao, Jian-Ping Lang and Brendan F. Abrahams
Chemical Communications 2012 - vol. 48(Issue 37) pp:NaN4482-4482
Publication Date(Web):2012/03/14
DOI:10.1039/C2CC30581J
Solvothermal reactions of [Et4N][Tp*WS3(CuCl)3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with CuCN and KCu(CN)2 afforded two [Tp*WS3Cu3]-based coordination polymers [Tp*WS3Cu3(μ3-DMF){Cu(CN)3}]2 (2) and K[Tp*WS3Cu3(μ3-DMF){Cu2(CN)4.5}]2 (3). The third-order NLO and PL responses of 1 were activated and greatly amplified through its assembly via the [Cu(CN)3]2− and [Cu4(CN)9]5− species in 2 and 3.
Co-reporter:Fei-Long Hu, Hui-Fang Wang, Dong Guo, Hui Zhang, Jian-Ping Lang and Jonathon E. Beves
Chemical Communications 2016 - vol. 52(Issue 51) pp:NaN7993-7993
Publication Date(Web):2016/05/03
DOI:10.1039/C6CC03256G
A 3D coordination polymer {[Cd(L1)(L2)]2}n (1) spontaneously resolves into enantiomorphic crystals of 1P and 1M without any chiral source. Bulk quantities of 1P and 1M can be predictably and reliably obtained by using chiral cyclohexane-1,2-diamine. 1 can be transformed into {[Cd(L1)(L3)0.5]2}n (2) by highly selective [2+2] photodimerization of L2 ligands. The reverse process can be achieved by microwave irradiation. The cycloreversion/cycloaddition cycles result in chiroptical switching behavior.
Co-reporter:Dong Liu, Jian-Ping Lang and Brendan F. Abrahams
Chemical Communications 2013 - vol. 49(Issue 26) pp:NaN2684-2684
Publication Date(Web):2013/02/14
DOI:10.1039/C3CC39286D
The SCSC transformation of a 1D polymer [Cd(1,3-bdc)(4-spy)2]n produced a 2D polymer [Cd(1,3-bdc)(4-spy)(HT-ppcb)0.5]n through the [2+2] photodimerization reaction. Hydrothermal reactions of HT-ppcb with CdCl2, 1,3-H2bdc and H2O2 afforded another 2D polymer {[Cd(H2O)(1,3-bdc)(bpbpf)]·H2O}n in which HT-ppcb underwent in situ oxidation to form a unique furan-based ligand bpbpf.
Co-reporter:Bing Wu, Wen-Hua Zhang, Zhi-Gang Ren and Jian-Ping Lang
Chemical Communications 2015 - vol. 51(Issue 80) pp:NaN14896-14896
Publication Date(Web):2015/08/18
DOI:10.1039/C5CC05990A
Instant adsorption of Congo Red (CR) by a 1D coordination polymer, [(H2L)0.5][Zn(1,2,3-BTA)(H2O)]·2H2O (1·2H2O), leads to the formation of a unique dye composite 1·0.75CR·6H2O, which demonstrates a remarkably enhanced photocurrent response compared to that of its precursor.
Co-reporter:Yan-Qiu Yuan, Feng-Ling Yuan, Fei-Long Li, Zhi-Min Hao, Jun Guo, David J. Young, Wen-Hua Zhang and Jian-Ping Lang
Dalton Transactions 2017 - vol. 46(Issue 22) pp:NaN7158-7158
Publication Date(Web):2017/05/08
DOI:10.1039/C7DT01579H
Cuboidal [Ni4O4] clusters supported by a pyridine alkoxide ligand have been developed. One of these clusters was selected as a precursor for carbon-hosted Ni nanoparticles (NiNPs/C) which were efficient catalysts for the conversion of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) at room temperature.
Co-reporter:Sha Sun, Zhi-Gang Ren, Ju-Hua Yang, Run-Tian He, Fan Wang, Xin-Yi Wu, Wei-Jie Gong, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2012 - vol. 41(Issue 27) pp:NaN8454-8454
Publication Date(Web):2012/05/23
DOI:10.1039/C2DT30860F
The reaction of [Ag(MeCN)4]ClO4 with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in CH2Cl2/MeOH afforded an unexpected cationic binuclear complex [Ag2(L1)2(η,η-μ-ClO4)2](ClO4)2 (L1 = N,N′-bis(diphenylphosphanylmethyl)-3H-4,5-dihydroimidazole-1-ium) (1). Compound 1 was also prepared in high yield from reactions of [Ag(MeCN)4]ClO4 with N,N′-bis(diphenylphosphanylmethyl)ethylenediamine (bdppeda) in the presence of formaldehyde (HCHO) or formic acid (HCOOH). Analogous reactions of AgCl with bdppeda and HCHO resulted in the formation a neutral binuclear complex [Ag2(L2)2(μ-Cl)2] (L2 = N,N-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) (2). Treatment of 1 with concentrated HCl gave rise to a partially anion-exchanged product [Ag2(L1)2(μ-Cl)2](ClO4)2 (3). Compounds 1 and 3 have a similar cationic binuclear structure, in which a [Ag2(η,η-μ-ClO4)2] or [Ag2(μ-Cl)2] ring is sandwiched by two in situ-formed cationic L1 ligands. The L1 ligand may be generated by the Ag(I)-assisted condensation reaction between bdppeda and HCHO or HCOOH. Compound 2 holds a neutral binuclear structure, in which a [Ag2(μ-Cl)2] ring is connected by two in situ-formed L2 ligands from its top and bottom sites. The neutral ligand L2 may be produced from another Ag(I)-assisted condensation reaction between bdppeda and HCHO. The in situ formation of the L1 and L2 ligands provides a new route to the N-heterocyclic diphosphine ligands, and an interesting insight into the coordination chemistry of their metal complexes.
Co-reporter:Xin-Yi Wu, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2014 - vol. 43(Issue 4) pp:NaN1723-1723
Publication Date(Web):2013/10/11
DOI:10.1039/C3DT52412D
Reactions of the tetraphosphine ligand N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine) (dppeda) or 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) with NiCl2, ancillary ligand (C2H5)2NCS2Na (Na(dtc)) and NH4PF6 afforded two binuclear complexes [(dtc)Ni(dppeda)Ni(dtc)](PF6)2 (1) and [(dtc)Ni(dpppda)Ni(dtc)](PF6)2 (2). Compounds 1 and 2 were characterized by elemental analyses, IR spectra, 1H, 13C{1H} NMR and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, thermogravimetric (TGA) experiments and single crystal X-ray diffraction. The Ni(II) atoms in both compounds form a square planar coordination geometry while the ligands hold a similar end-to-end coordination mode. Both products can catalyze the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) while 1 exhibited a higher catalytic activity than 2. Influencing aspects such as solvent, temperature, the ratio of ε-CL to catalyst, the presence of benzyl alcohol, concentration of ε-CL and reaction intervals were investigated.
Co-reporter:Da-Wei Tan, Jing-Bo Xie, Qi Li, Hong-Xi Li, Jun-Chi Li, Hai-Yan Li and Jian-Ping Lang
Dalton Transactions 2014 - vol. 43(Issue 37) pp:NaN14071-14071
Publication Date(Web):2014/07/30
DOI:10.1039/C4DT01765J
Reactions of a pincer ligand 2-(1H-pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine (pzpypzH) with Cu(NO3)2, Cu(ClO4)2, CuSO4, CuCl2 or CuI produced three dinuclear Cu(II) complexes [{Cu(NO3)}(μ-pzpypz)]2 (1), [{Cu(ClO4)}(μ-pzpypz)]2 (2), [Cu2(μ-SO4)(μ-pzpypz)2]·2MeOH (3·2MeOH), one mononuclear Cu(II) complex [CuCl2(pzpypzH)] (4) and one trinuclear Cu(I)/Cu(II) complex [(ICu)(μ-I)2Cu2(μ-pzpypz)2] (5), respectively. Treatment of 4 with two equiv. of AgNO3 in DMF also gave rise to 1. Complexes 1–5 were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Complex 1 or 2 has a dimeric structure in which two {Cu(X)} (X = NO3, ClO4) fragments are interconnected by two μ-pzpypz− ligands. 3 also adopts a dimeric structure in which two Cu(II) centers are interconnected by a pair of μ-pzpypz− ligands and one μ-SO42− ion. The Cu(II) center in 4 is five-coordinated by three N atoms of the pzpypzH ligand and two Cl atoms. In 5, two Cu(II) centers are bridged by two μ-pzpypz− ligands and one CuI32− unit, forming a unique trinuclear structure. Complexes 1–5 displayed high catalytic activity toward the ammoxidation of alcohols to nitriles and the aerobic oxidation of alcohols to aldehydes in H2O. The nitrile or aldehyde products could be readily separated from the catalytic system by extraction and the residual aqueous solution containing 1 retained good activity for several cycles.
Co-reporter:Li-Kuan Zhou, Quan Liu, Xin Zhao, Fei-Long Hu, Shu-Chen Liu, Zhi-Gang Ren, Zhen-Rong Sun and Jian-Ping Lang
Dalton Transactions 2014 - vol. 43(Issue 12) pp:NaN4744-4744
Publication Date(Web):2014/01/07
DOI:10.1039/C3DT53320D
Treatment of [Et4N][Tp*WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with CuX (X = Br, SCN) and PPh3 or 1,1-bis(diphenylphosphino)methane (dppm) produced two neutral trinuclear clusters [Tp*W(μ3-S)(μ-S)2Cu2Br(PPh3)] (2) and [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(dppm)]2·MeCN·Et2O (3·MeCN·Et2O). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6 and 1,3-bis(diphenylphosphino)propane (dppp), N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy), N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda), or 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzenediamine (dpppda) afforded four clusters containing butterfly-shaped [Tp*WS3Cu2] cores, [Tp*W(μ3-S)(μ-S)2Cu2(dpppds)](PF6)·1.25MeCN (dpppds = 1,3-bis(diphenylphosphino)propane disulfide) (4·1.25MeCN), [Tp*W(μ3-S)(μ-S)2Cu2(bdppmapy)](PF6)·3MeCN (5·3MeCN) and {[Tp*W(μ3-S)(μ-S)2Cu2]2(L)]}(PF6)2·Sol (6·Et2O: L = dppeda, Sol = Et2O; 7·1.25MeCN: L = dpppda, Sol = 1.25MeCN). Compounds 2–7 were characterized by elemental analysis, IR, UV-Vis, 1H and 31P{1H} NMR spectra, electrospray ion mass spectra (ESI-MS) and single-crystal X-ray diffraction. Compound 2 or 3 has a butterfly-shaped [Tp*WS3Cu2] core in which one [Tp*WS3] unit binds two Cu(I) centers via one μ3-S and two μ-S atoms. In the cationic structure of 4 or 5, one in situ-formed dpppds or bdppmapy combines with the [Tp*WS3Cu2] core via each of its two S atoms or two P atoms coordinated at each Cu(I) center. In the bicationic structure of 6 or 7, two [Tp*WS3Cu2] cores are linked by one dppeda or dpppda bridge to form a bicyclic structure. The isolation of 2–7 with unstable [Tp*WS3Cu2] cores may be ascribed to the coordination of P- or S-donor ligands at Cu(I) centers of these cores. The third-order nonlinear optical (NLO) properties of 2–7 in DMF were also investigated by using the femtosecond degenerate four-wave mixing (DFWM) technique at 800 nm.
Co-reporter:Run-Tian He, Jian-Feng Wang, Hui-Fang Wang, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2014 - vol. 43(Issue 25) pp:NaN9794-9794
Publication Date(Web):2014/04/30
DOI:10.1039/C4DT00815D
Reaction of PdCl2 with N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) afforded a mononuclear complex [(bdppmapy)PdCl2] (1). Compound 1 was characterized by elemental analysis, IR, 1H, 13C and 31P NMR, electrospray ion mass spectra (ESI-MS) and X-ray single crystal crystallography. The Pd(II) center in 1 is chelated by bdppmapy, showing a cis-square planar geometry. With the assistance of additive Cu2O, complex 1 exhibited good catalytic activity toward the decarboxylative cross-coupling reactions between 4-picolinic acid and aryl bromides. In the presence of only 2 mol% catalyst, a family of 4-aryl-pyridines could be isolated in up to 83% yield.
Co-reporter:Yu-Ting Wang, Bin-Bin Gao, Fan Wang, Shi-Yuan Liu, Hong Yu, Wen-Hua Zhang and Jian-Ping Lang
Dalton Transactions 2017 - vol. 46(Issue 6) pp:NaN1839-1839
Publication Date(Web):2017/01/04
DOI:10.1039/C6DT04599E
The integration of a geometrically rigid Pd(II), a coordinatively monotonous N-heterocyclic carbene 1,3-dimethylimidazoline-2-ylidene (IMe), and a flexible zwitterionic thiolate 4-(trimethylammonio)benzenethiolate (Tab) affords a class of Pd–IMe–Tab complexes with various nuclearities, namely, trans-[Pd(IMe)2(Tab)2](OTf)2 (2, mononuclear), cis-[Pd(IMe)2(Tab)2](OTf)(Cl) (3a, mononuclear), cis-[Pd(IMe)2(Tab)2](PF6)2·MeCN (3b·MeCN, mononuclear), [Pd2(IMe)4(Tab)2](PF6)4·2MeCN (4·2MeCN, dinuclear) and [Pd4(IMe)4(Tab)6](OTf)6(Cl)2 (5, tetranuclear). Further presence of Ag(I) in the assembly provides a heterometallic octanuclear cluster of [Pd4Ag4(IMe)8(Tab)10](PF6)12 (6). Compounds 2–6 are formed by the reaction of trans-Pd(IMe)2Cl2 (1) with various additional reagents via different reaction pathways. These compounds are characterized by means of FT-IR, 1H and 13C NMR, ESI-MS, elemental analysis and X-ray crystallography. Notably, the skeleton of compound 5 features a [Pd4S4] parallelogram wherein each of the four Pd(II) centers bisects the edge defined by the S atoms. The main skeleton of compound 6 is an oval-shaped Pd4Ag4S10 unit, featuring an edge-fused norbornane-like (Pd2Ag4S6) framework appended by two additional PdS2 motifs at the polar positions. Compounds 5 and 6 also feature Pd⋯Pd (5), Pd⋯Ag and Ag⋯Ag (6) interactions. Compound 5 as a representative example is highly effective at catalyzing Suzuki–Miyaura couplings in water, highlighting the potential of applying these types of homo- and heterometallic clusters as catalysts for organic transformations in environmentally benign media.
Co-reporter:Wen-Hua Zhang, Zhi-Gang Ren and Jian-Ping Lang
Chemical Society Reviews 2016 - vol. 45(Issue 18) pp:NaN5019-5019
Publication Date(Web):2016/05/13
DOI:10.1039/C6CS00096G
The investigation of heterometallic Mo(W)–M′–S clusters (M′ = transition metals) has its genesis in the late 1970s with the identification of the nitrogenase iron–molybdenum cofactor (FeMoco) featuring a Mo–Fe–S double-cubane cluster core. This has led to the generation of a library of cluster skeletons subsequently used as building blocks for oligomers (OGs) and polymers, merging this field with the fascinating developments in supramolecular chemistry and coordination polymers (CPs). While resembling the general metal–ligand assembly to form CPs in one-pot, cluster-based OGs or CPs are conventionally prepared from Mo(W)–S synthons and Cu(I) salts in the presence of bridging ligands. This review summarizes the synthesis of Mo(W)–Cu–S cluster-supported OGs and CPs through a two-step strategy involving preformed clusters. This stepwise approach facilitates clean conversion, and is amenable to exquisite design protocols and yields products otherwise inaccessible via a direct one-pot method. We review the synthesis of OGs and CPs by cluster core upgrading, downgrading, ligand substitution, and cluster aggregation reactions, together with the optical and host–guest properties of the products. In doing so, we demonstrate the power and generality of this strategy for assembling these unique materials and offer clues on how to adapt this less practiced method to preparing extended molecular assemblies with potentially intriguing properties.
Co-reporter:Yi-Xiang Shi, Wu-Xiang Li, Huan-Huan Chen, David James Young, Wen-Hua Zhang and Jian-Ping Lang
Chemical Communications 2017 - vol. 53(Issue 40) pp:NaN5518-5518
Publication Date(Web):2017/04/27
DOI:10.1039/C7CC02704D
A protonated mononuclear complex [Zn(Hbpvp)Cl3] (1) is assembled by solvothermal reaction of Zn(NO3)2·6H2O with 3,5-bis-(2-(pyridin-4-yl)vinyl)pyridine (bpvp) in DMF/H2O with a few drops of concentrated HCl added. Hydrogen-bonded zigzag chains of 1 crystallize over time to form large-size hollow hexagonal tubular crystals whose evolution from irregular crystal seeds is monitored by SEM and PXRD. Upon UV light irradiation, single crystals of 1 undergo a stereoselective [2+2] photocycloaddition while its Methyl Blue-coated crystals keep intact.
Co-reporter:Fei-long Hu, Yi-Xiang Shi, Huan-Huan Chen and Jian-Ping Lang
Dalton Transactions 2015 - vol. 44(Issue 43) pp:NaN18803-18803
Publication Date(Web):2015/09/24
DOI:10.1039/C5DT03094C
One coordination polymer [Zn2(L)2(bpe)2(H2O)2] (1) (L = 4,4′-((1,2-phenylenebis(methylene))bis(oxy))dibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethene) was prepared and structurally determined. Compound 1 has a chain structure in which its pair of bpe ligands is arranged in a head-to-tail manner with their CC bonds being close enough for a [2 + 2] cycloaddition reaction. Upon exposure to UV light, compound 1 undergoes a single-crystal-to-single-crystal (SCSC) [2 + 2] photodimerization to generate one 2D coordination polymer [Zn(L)(rctt-tpcb)0.5(H2O)] (1a) (rctt (regio cis, trans, trans)-tpcb = tetrakis(4-pyridyl)cyclobutane). The tpcb ligands in the crystals of 1a show an intriguing in situ thermal isomerisation. The nanospheres of 1 can be obtained by recrystallization in DMSO/alcohol. The nanospheres of 1a can also be readily produced from the corresponding nanospheres of 1 by the photocyclodimerization method. Compared with those of 1a, the nanospheres of 1 display highly selective sensing of Fe3+ ions over mixed metal ions through fluorescence quenching. Moreover, the nanospheres of 1a can rapidly adsorb CR (congo red), MB (methylene blue) or RhB (rhodamine B) over MO (methyl orange) from aqueous solutions. This work offers a new photoinduced post-synthetic method for the synthesis of multifunctional MOFs, which show luminescence sensing of Fe3+ ions and dye adsorption properties.
Co-reporter:Dong Liu, Hui-Fang Wang, Brendan F. Abrahams and Jian-Ping Lang
Chemical Communications 2014 - vol. 50(Issue 24) pp:NaN3175-3175
Publication Date(Web):2014/02/03
DOI:10.1039/C3CC49749F
A 2D network [Zn4(OH)2(5-NO2-1,3-BDC)2(5-NO2-1,3-HBDC)2(ppene)2]n underwent a highly selective [2+2] photodimerization reaction upon UV irradiation. The coordination polymer retains its single crystallinity after photoreaction.
Co-reporter:Hong-Xi Li, Wei Zhao, Hai-Yan Li, Zhong-Lin Xu, Wen-Xia Wang and Jian-Ping Lang
Chemical Communications 2013 - vol. 49(Issue 39) pp:NaN4261-4261
Publication Date(Web):2012/10/19
DOI:10.1039/C2CC36736J
The Cu(I)-mediated C–S bond cleavage of 5-methyl-4-(p-tolyl)pyrimidine-2-thiol (mtpmtH) gave one 30-nuclear cluster [Cu30I16(mtpmt)12(μ10-S4)], one polymeric complex [(bmtpms)Cu-(μ-I)]n and one tetranuclear complex [(bmptmds){Cu(μ-I)}2]2; the 30-nuclear cluster displayed excellent catalytic performances in the coupling reactions of N-heterocycles and arylboronic acids and could be recycled and reused.
Co-reporter:Zhen-Hong Wei, Chun-Yan Ni, Hong-Xi Li, Zhi-Gang Ren, Zhen-Rong Sun and Jian-Ping Lang
Chemical Communications 2013 - vol. 49(Issue 42) pp:NaN4838-4838
Publication Date(Web):2013/04/08
DOI:10.1039/C3CC41280F
Reactions of [Et4N][TpMoS(S4)] with three equiv. of CuI in MeCN or in pyridine gave rise to one dicubane and one tetracubane anionic clusters, [Et4N]2[{TpMo(μ3-S)3Cu3I}2(μ-I){Cu(μ-I)2(μ4-I)2}] and [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)], and their third-order nonlinear optical (NLO) responses were greatly enhanced relative to that of the precursor.
Co-reporter:Lei-Lei Liu, Hong-Xi Li, Li-Min Wan, Zhi-Gang Ren, Hui-Fang Wang and Jian-Ping Lang
Chemical Communications 2011 - vol. 47(Issue 39) pp:NaN11148-11148
Publication Date(Web):2011/09/02
DOI:10.1039/C1CC14262C
Reactions of [H4L][PF6]4 with 4 equiv. of Mn(OAc)2·4H2O in the presence of air gave rise to a mononuclear Mn(III)–superoxo complex [Mn(III)L(O2)(H2O)](PF6)2, which contains a bowl-shaped cationic structure with a D4d symmetry. It has an unprecedented linear end-on Mn(III)–O2 unit and exhibited good efficiency and selectivity in the catalytic oxidation of alkenes with O2 plus isobutyraldehyde under mild conditions.
Co-reporter:Hong-Xi Li, Zhi-Gang Ren, Dong Liu, Yang Chen, Jian-Ping Lang, Zhen-Ping Cheng, Xiu-Lin Zhu and Brendan F. Abrahams
Chemical Communications 2010 - vol. 46(Issue 44) pp:NaN8432-8432
Publication Date(Web):2010/10/11
DOI:10.1039/C0CC03027A
Reactions of Cu(OAc)2·H2O with dmnpzH in EtOH produce a heptanuclear copper(II) pyrazolate complex [Cu7(OH)2(OAc)6(dmnpz)6(EtOH)6], which is able to undergo a SCSC structural transformation from a lower symmetry structure to a higher symmetry structure via replacement of ligated-EtOH molecules with MeOH; both complexes along with the solvent-free species exhibit high catalytic activity in the polymerization of MMA.
Co-reporter:Hong-Xi Li, Hua-Zhou Wu, Wen-Hua Zhang, Zhi-Gang Ren, Yong Zhang and Jian-Ping Lang
Chemical Communications 2007(Issue 47) pp:NaN5054-5054
Publication Date(Web):2007/09/27
DOI:10.1039/B710787K
Dissolution of a mononuclear complex [Zn(dmpzdtc)2] in BrCH2CH2Br or DMF saturated with water followed by CS2 elimination led to the formation of two unique high-nuclearity metallamacrocyclic complexes, [Zn4(μ-dmpz)6(μ-OH)2]2 and [Zn4(μ-dmpz)6(μ-OH)2]4.
Co-reporter:Jian-Feng Wang, Shi-Yuan Liu, Chun-Yu Liu, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2016 - vol. 45(Issue 22) pp:NaN9306-9306
Publication Date(Web):2016/05/04
DOI:10.1039/C6DT01211F
Reactions of a P–N hybrid ligand, N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy), with silver oxysalts including AgNO3, AgOAc, AgBz (Bz = benzoate) and AgSal (Sal = salicylate) under different reaction conditions give rise to seven coordination compounds {[Ag4(μ–η,η-NO3)2(μ–η,η2-NO3)2](3-bdppmapy)2}n (1), {[Ag4(μ–η,η2-NO3)4](3-bdppmapy)2}n (2), {[Ag2(μ–η2-OAc)(μ–η,η2-OAc)]2(3-bdppmapy)2}n (3), [Ag2(Bz)(μ–η,η2-Bz)(H2O)]2(3-bdppmapy)2 (4), {[Ag4(μ–η2-Bz)2(μ–η,η2-Bz)2](3-bdppmapy)2}n (5), {Ag(Sal)(3-bdppmapy)}n (6) and {[Ag4(Sal)2(μ–η,η2-Sal)2](3-bdppmapy)2}n (7). Single crystal X-ray analyses reveal that 1, 5 and 7 have similar 1D chain structures constructed by [Ag4(μ–η2-Ox)2(μ–η,η2-Ox)2] units (1: Ox− = NO3−; 5: Ox− = Bz−) or [Ag4(Sal)2(μ–η,η2-Sal)2] units (7) and double 3-bdppmapy bridges. Compound 2 has a 2D layer structure derived from [Ag4(μ–η,η2-NO3)4] units and single 3-bdppmapy bridges. 3 displays another 2D layer structure formed by [Ag2(μ–η2-OAc)(μ–η,η2-OAc)] units and double 3-bdppmapy bridges. 4 shows a discrete tetranuclear structure formed by two [Ag2(Bz)(η,η2,μ-Bz)(H2O)] units and a pair of 3-bdppmapy bridges, while 6 adopts a 1D chain composed by [AgSal] units and single 3-bdppmapy bridges. 6 and 7 as representative samples display high catalytic activity toward the photodegradation of rhodamine B (RhB) in water. Compound 7 shows a better photocatalytic performance than that of 6, which correlates well with the differences in their anodic photocurrent responses and their HOMO–LUMO energy gaps derived from the density function theory (DFT) calculations. The formation of 6 and 7 from AgSal and 3-bdppmapy provides a new approach to the design and assembly of Ag(I)-supported CPs with interesting structural architectures and higher photocatalytic activity.
Co-reporter:Quan Liu, Zhi-Gang Ren, Li Deng, Wen-Hua Zhang, Xin Zhao, Zhen-Rong Sun and Jian-Ping Lang
Dalton Transactions 2015 - vol. 44(Issue 1) pp:NaN137-137
Publication Date(Web):2014/10/09
DOI:10.1039/C4DT02725F
We herein describe a coordination polymer system built upon the reactions of a W/Cu/S cluster precursor [Et4N][Tp*WS3(CuBr)3] (1, Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with three equivalents of CuCN through solvent modulation. Four coordination polymers, namely, [Tp*WS3Cu3(μ3-DMF)(CN)3Cu(Py)] (2), [Tp*WS3Cu3(μ3-DMF)(CN)3Cu] (3), [Tp*WS3Cu3(μ3-DMF)(CN)3Cu]·4aniline (4·4aniline) and [Tp*WS3Cu3(μ3-DMF)(CN)3Cu]·2(DMF)0.5 (5·2(DMF)0.5), are isolated in different solvent systems and characterized by means of elemental analysis, FT-IR, UV-Vis, ESI-MS and single-crystal X-ray diffraction. Compounds 2–5 feature μ3-DMF association with the nest-shaped [WS3Cu3] cluster cores, yielding cubane-type [WS3Cu3O] clusters which are further linked to single Cu(I) ions through CN bridges to provide 1D or 2D structures. Compounds 3–5 have identical chemical compositions in their main fragments but with distinctively different structural features, and are therefore topological isomers. Compound 2 has a ladder-type structure in which the side rails contain alternately linked cluster cores and Cu(I) ions. Compound 3 has a 2D (6,3) network with alternately arranged cluster cores and Cu(I) ions. Both 4 and 5 have 2D structures with 4·82 topology. In 4, a pair of cluster cores and Cu(I) ions form a 4-membered ring which is further linked to four equivalent rings through four CN ligands via a cluster core-to-Cu arrangement; while in the structure of 5, the same 4-membered rings as those in 4 are extended to equivalent rings via a cluster core-to-cluster and Cu-to-Cu arrangement. The hyperpolarizabilities (γ) of the polymeric networks exhibit an enhancement of more than 10 times compared to their parent cluster, 1.
Co-reporter:Hai-Xiao Qi, Jian-Feng Wang, Zhi-Gang Ren, Jin-Jiao Ning and Jian-Ping Lang
Dalton Transactions 2015 - vol. 44(Issue 12) pp:NaN5671-5671
Publication Date(Web):2015/02/10
DOI:10.1039/C5DT00167F
Solvothermal reactions of HAuCl4·4H2O with a P–S hybrid ligand N,N-bis(diphenylphosphanylmethyl)-amino-thiocarbamide (dppatc) at 80 °C and 115 °C produced two Au–P–S complexes, [Au2(dppatc)2]Cl2 (1) and [Au2(dppmt)2]n (2) (dppmtH = (diphenylphosphino)methanethiol). 1 and 2 were characterized by elemental analyses, IR and UV-vis spectra, thermal-gravity analyses, powder X-ray diffraction and single crystal X-ray diffraction analyses. Compound 1 contains a dinuclear [Au2(dppatc)2]2+ dication, while 2 has a one-dimensional chain formed by Au⋯Au aurophilic interactions. Compounds 1 and 2 exhibited excellent catalytic activity toward the photodegradation of nitrobenzene, p-nitrophenol and 2,4-dinitrophenol in aqueous solutions. The degradation reactions followed the zero-order kinetic model, in which the three nitroaromatics could be converted into CO2 and H2O in 92–96% yields.
Co-reporter:Zhi-Gang Ren, Sha Sun, Min Dai, Hui-Fang Wang, Chun-Ning Lü, Jian-Ping Lang and Zhen-Rong Sun
Dalton Transactions 2011 - vol. 40(Issue 33) pp:NaN8398-8398
Publication Date(Web):2011/07/22
DOI:10.1039/C1DT10685F
Reactions of the preformed cluster [(η5-C5Me5)2Mo2(μ3-S)4Cu2(MeCN)2](ClO4)2 (1) with two tetraphosphine ligands, 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) and N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), produced two bicyclic clusters {[(η5-C5Me5)2Mo2(μ3-S)4Cu2]2(L)}(ClO4)4 (3: L = dpppda; 4: L = dppeda). Analogous reactions of 1 or [(η5-C5Me5)2Mo2(μ3-S)4Cu2(MeCN)2](PF6)2 (2) with two N,P mixed ligands, N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) and N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy), afforded two monocyclic clusters {[(η5-C5Me5)2Mo2(μ3-S)4Cu2]2(L)2}X4 (5: L = bdppmapy, X = ClO4; 6: L = dppmapy, X = PF6). Compounds 3–6 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, 1H and 31P{1H} NMR spectra, ESI-MS and single-crystal X-ray crystallography. In the tetracations of 3–6, two cubane-like [Mo2(μ3-S)4Cu2] cores are linked either by one dpppda or dppeda bridge to form a bicyclic structure or by a pair of bdppmapy or dppmapy bridges to afford a monocyclic structure. The third-order nonlinear optical (NLO) properties of 1 and 3–6 in MeCN were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 50 fs pulse width at 800 nm. Compounds 3–6 exhibited enhanced third-order NLO performances relative to that of 1.
Co-reporter:Ling-Ling Li, Lei-Lei Liu, Ai-Xia Zheng, Yu-Jie Chang, Ming Dai, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2010 - vol. 39(Issue 33) pp:NaN7665-7665
Publication Date(Web):2010/07/20
DOI:10.1039/C0DT00249F
Solvothermal reactions of CuCN with a set of flexible bipyrazolyl-based ligands with different spacer lengths [(dmpz)(CH2)n(dmpz)] (dmpz = 3,5-dimethyl-pyrazolyl; n = 1–6) gave rise to six [CuCN]n-based coordination polymers [(CuCN)3L]n (1: L = dmpzm; 2: L = dmpze), [(CuCN)2L]n (3: L = dmpzpr; 4: L = dmpzb; 5: L = dmpzp; 6: L = dmpzh). Compounds 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. 1 or 2 exhibits a 1D scolopendra-like chain assembled from a rare 1D zigzag [CuCN]n chain with [CN–Cu–CN–Cu–L] (1: L = dmpzm; 2: L = dmpze) side arms. 3 or 4 shows a 2D (6,3) wave-like layer in which [Cu6(μ-CN)6L2]n (L = dmpzpr or dmpzb) double chains are interconnected by pairs of L bridges. 5 consists of two [CuCN]n single chains that are linked by dmpzp bridges to form a rare 1D chain with an oblong channel. 6 has a 3D network in which the 2D [Cu10(μ-CN)10(dmpzh)3]n layers are interconnected by pairs of dmpzh bridges. In addition, the photoluminescent properties of 1–6 in the solid state at ambient temperature were investigated.
Co-reporter:Dong Liu, Ni-Ya Li and Jian-Ping Lang
Dalton Transactions 2011 - vol. 40(Issue 10) pp:NaN2172-2172
Publication Date(Web):2010/11/09
DOI:10.1039/C0DT00931H
Photochemical single-crystal to single-crystal transformation of one 1D polymer [Cd(bpe)(CBA)2]n afforded a new 1D polymer [Cd(rctt-tpcb)0.5(CBA)2]n which underwent hydrothermal reaction in strong acidic solution to form a 3D coordination polymer {[Cd(rtct-tpcb)Cl2]·2H2O}n.
Co-reporter:Ni-Ya Li, Zhi-Gang Ren, Dong Liu, Rong-Xin Yuan, Li-Pei Wei, Liang Zhang, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2010 - vol. 39(Issue 17) pp:NaN4222-4222
Publication Date(Web):2010/03/24
DOI:10.1039/B925081F
Reactions of N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) with K[Ag(CN)2], Ag(dca) (dca = dicyanamide), AgSCN, AgCl, AgBr or AgI gave rise to six [Ag2X2]-based (X = CN−, dca, SCN−, Cl−, Br− and I−) compounds, [{Ag2(CN)2(dppmapy)}·0.5CHCl3]n (1), [Ag2L2(dppmapy)2]n (2: L = dca; 3: L = SCN), [{Ag2L2(dppmapy)2}·sol]n (4: L = Cl, sol = 0.5MeOH·0.5CH2Cl2; 5: L = Br, sol = 2CHCl3), and [Ag2I2(dppmapy)4]·3MeOH (6). Complexes 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Compound 1 has a one-dimensional (1D) spiral chain constructed by bridging the [(CN)Ag(μ-CN)Ag] fragments via dppmapy ligands. In 2, 3 and 4, each [Ag2X2] (X = dca, SCN, Cl) fragment is linked by dppmapy bridges to the other two equivalent ones to form a 1D chain containing 16-membered rings (2) or a 1D double chain containing 20-membered rings (3) or a 1D spiral chain containing 20-membered rings (4). Compound 5 possesses a two dimensional (2D) (4,4) network consisting of 36-membered metallomacrocycles in which each [Ag2Br2] fragment acts as a unique planar four-connecting node to link the other four equivalent ones via dppmapy bridges. Complex 6 has a [Ag2I2] unit with a pair of monodentate dppmapy ligands coordinated at each Ag center. The photoluminescent properties of 1–6 in the solid state at ambient temperature were also investigated.
Co-reporter:Xue Lü, Xi Chen, Zhi-Gang Ren, Jian-Ping Lang, Dong Liu and Zhen-Rong Sun
Dalton Transactions 2011 - vol. 40(Issue 31) pp:NaN7992-7992
Publication Date(Web):2011/07/06
DOI:10.1039/C1DT10230C
Treatment of [Et4N][Tp*W(μ3-S)3(CuBr)3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with an excess of α-methylpyridine (α-MePy) and NH4PF6 in CH2Cl2 afforded a cationic cluster [Tp*W(μ3-S)3Cu3(α-MePy)3(μ3-Br)](PF6) (2) while the reaction of 1 with an excess of 1,4-pyrazine (1,4-pyz) and NH4PF6 in MeCN–CH2Cl2 at 65 °C produced a polymeric cluster [Tp*W(μ3-S)3Cu3(1,4-pyz)((1,4-pyz)0.5)2(μ3-Br)][Tp*W(μ3-S)3(CuBr)3] (3). Reactions of 1 with melamine (MA) in 1:1 or 1:2 gave rise to another polymeric cluster [{Tp*W(μ3-S)3Cu3Br(μ3-Br)}2(MA)2] (4) and a neutral cluster [Tp*W(μ3-S)3Cu3Br(μ3-Br)(MA)2] (5), respectively. Compounds 2–5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, electrospray ionization (ESI) mass spectra and X-ray crystallography. The cation of 2 has a cubane-like [Tp*W(μ3-S)3Cu3(μ3-Br)] structure with each α-MePy ligand coordinated at one Cu(I) center. For 3, each [Tp*W(μ3-S)3Cu3(μ3-Br)] core is interconnected by 1,4-pyz bridges to form a 1D cationic zigzag chain with the [Tp*W(μ3-S)3(CuBr)3]− anions arranged along its two sides. For 4, each [Tp*W(μ3-S)3Cu3(μ3-Br)] core is interlinked by MA bridges to afford a 1D spiral chain. 5 adopts a cubane-like [Tp*W(μ3-S)3Cu3(μ3-Br)] structure in which one terminal Br and two MA ligands are coordinated at three Cu centers. The third-order nonlinear optical (NLO) properties of 1–5 in DMF were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Compounds 1–5 exhibit good NLO responses, and 3 and 4 possess the largest second-order hyperpolarizability γ values among the known W/Cu/S clusters bearing the [Tp*WS3] unit.
Co-reporter:Wang Yao, Wei-Jie Gong, Hong-Xi Li, Fei-Long Li, Jun Gao and Jian-Ping Lang
Dalton Transactions 2014 - vol. 43(Issue 42) pp:
Publication Date(Web):
DOI:10.1039/C4DT01856G
Co-reporter:Zhi-Yuan Zhang, Wei-Jie Gong, Fan Wang, Min-Min Chen, Li-Kuan Zhou, Zhi-Gang Ren, Zhen-Rong Sun and Jian-Ping Lang
Dalton Transactions 2013 - vol. 42(Issue 26) pp:NaN9504-9504
Publication Date(Web):2013/04/10
DOI:10.1039/C3DT50759A
Reactions of [Et4N][Tp*MoS(S)4] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with 3 equiv. of CuX (X = Cl, Br, I, CN) or [Cu(MeCN)4]ClO4 in CH2Cl2–MeCN or CH2Cl2–DMF afforded [Et4N]2[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] (2), [Et4N][Tp*Mo(μ3-S)3(CuX)3] (3: X = Br; 4: X = I), [Et4N][Tp*MoO(μ-S)2(CuX)] (5: X = I; 6: X = CN) and [Tp*Mo(μ3-S)3Cu3(μ3-S′)]4 (7). Compounds 2–7 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, electrospray ion mass spectra (ESI-MS) and X-ray crystallography. The cluster dianion of 2 has a complete cubane-like [Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] structure while the anion of 3 or 4 consists of an incomplete cubane-like [Tp*Mo(μ3-S)3(CuX)3] structure. The anion of 5 or 6 has a binuclear structure, in which one [Tp*MoO(μ-S)2] moiety and one CuX unit are linked by a pair of μ-S atoms. The structure of 7 may be considered as a supercube whose eight corners are occupied by four incomplete cubane-like [Tp*Mo(μ3-S)3Cu3] fragments and four μ3-S′ atoms. The third-order nonlinear optical (NLO) properties of 2–6 in DMF were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Compounds 2–6 exhibited good NLO performances and their NLO responses were enhanced relative to that of 1.
Co-reporter:Ling Wang, Bin Guo, Hong-Xi Li, Qi Li, Hai-Yan Li and Jian-Ping Lang
Dalton Transactions 2013 - vol. 42(Issue 44) pp:NaN15580-15580
Publication Date(Web):2013/09/10
DOI:10.1039/C3DT51970H
Reaction of Cu(OAc)2·H2O and 1H-pyrazole-3,5-dicarboxylic acid dimethyl ester (Hdcmpz) in MeOH at room temperature afforded one tetranuclear Cu(II)/pyrazolate complex [{Cu2(μ-OAc)2}2(μ-dcmpz)2(μ-OAc)2] (1) in 89% yield. The similar reaction in refluxing MeOH produced a hexanuclear metallamacrocyclic Cu(II)/pyrazolate complex [{Cu(μ-dcmpz)}2(μ-OMe)2]3 (2) in 85% yield. Treatment of the same components under solvothermal conditions resulted in the formation of another tetranuclear Cu(II)/pyrazolate/carboxylate complex [{Cu(MeOH)}4(μ-mcccpz)4] (3, Hmcccpz = 5(3)-(methoxycarbonyl)-1H-pyrazole-3(5)-carboxylic acid) in 30% yield. The mcccpz2− ion in 3 was in situ generated via the hydrolysis of one of two esters on dcmpz ligand. Complexes 1–3 were characterized by elemental analysis, IR and single-crystal X-ray diffraction. An X-ray analysis revealed that 1 contains two {Cu(μ-OAc)}2 fragments that are interconnected by two μ-η2,η2-dcmpz− ligands and two μ-η1,η1-OAc− ions, forming a unique tetrameric structure. Complex 2 is composed of three {Cu(μ-dcmpz)}2 fragments linked by three pairs of μ-OMe− anions, forming a metallamacrocyclic crown structure. 3 consists of four {Cu(MeOH)} fragments linked by two pairs of μ-η1,η2-mcccpz2− ligands, forming a tetrameric [2 × 2] grid-like structure. Complexes 1–3 displayed high catalytic activity toward the condensation of nitriles with 2-aminoalcohol under solvent-free conditions to produce various 2-oxazolines.
Co-reporter:Ai-Xia Zheng, Hong-Xi Li, Kai-Peng Hou, Jing Shi, Hui-Fang Wang, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2012 - vol. 41(Issue 9) pp:NaN2706-2706
Publication Date(Web):2012/01/20
DOI:10.1039/C2DT12219G
Reaction of MeHgI with Ag2O in H2O followed by addition of equimolar TabHPF6 in MeCN gave rise to a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF6 (1) (TabH = 4-(trimethylammonio)benzenethiol) in a high yield. Treatment of 1 with KI and KSCN afforded an anion exchange product [MeHg(Tab)]I·0.25H2O (2·0.25H2O) and [MeHg(Tab)]SCN (3), respectively, while that of 1 with equimolar Tab resulted in the formation of another MeHg/Tab compound [MeHg(Tab)2]PF6 (4). The cation of 2 or 3 shows an approximately linear structure in which the central Hg(II) is coordinated by one C atom of one CH3 group and one S atom of a Tab ligand. The Hg(II) center of the cation of 4 is trigonally coordinated by one C atom of the CH3 group and two S atoms of two Tab ligands. The analogous reaction of 1 with NH4SCN led to the cleavage of the Hg–C bond of 1 and the formation of a known four-coordinated Hg(II)/Tab complex [Hg(Tab)2(SCN)2] (5). When 4 was treated with 4,6-Me2pymSH or EtSH, another four-coordinated Hg(II)/Tab complex [Hg(Tab)4]3(PF6)6 (6) was generated in a high yield. The Hg(II) center of each cation of 6 is tetrahedrally coordinated by four S atoms of four Tab ligands. The results suggested that cleavage of the Hg–C bond in the methylmercury complex 1 could be completed by increasing the coordination number of its Hg(II) center by S-donor ligands and protonating the methyl group by weak acids.
Co-reporter:Ai-Xia Zheng, Hui-Fang Wang, Chun-Ning Lü, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2012 - vol. 41(Issue 2) pp:NaN566-566
Publication Date(Web):2011/11/02
DOI:10.1039/C1DT11663K
Reactions of Cd(NO3)2·4H2O with TabHPF6 (TabH = 4-(trimethylammonio)benzenethiol) and Et3N in the presence of NH4SCN and five other N-donor ligands such as 2,2′-bipyridine (2,2′-bipy), phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), 2,6-bis(pyrazd-3-yl)pyridine (bppy) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy) gave rise to a family of Cd(II)/thiolate complexes of N-donor ligands, {[Cd2(μ-Tab)4(NCS)2](NO3)2·MeOH}n (1), [Cd2(μ-Tab)2(L)4](PF6)4 (2: L = 2,2′-bipy; 3: L = phen), [Cd(Tab)2(L)](PF6)2 (4: L = 2,9-dmphen; 5: L = bppy), and [Cd2(μ-Tab)2(Tab)2(bdmppy)]2(PF6)8·H2O (6·H2O). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. For 1, each [Cd(NCS)]+ fragment is connected to its equivalents via a pair of Tab bridges to a one-dimensional chain. For 2 and 3, two [Cd(2,2′-bipy)2]2+ or [Cd(phen)2]2+ units are linked by a pair of Tab bridges to form a cationic dimeric structure. The Cd atom in [Cd(Tab)2(L)]2+ dication of 4 or 5 is coordinated by two Tab ligands and chelated by two N atoms from 2,9-dmphen (4) or three N atoms from bppy (5), forming a distorted tetrahedral (4) or trigonal bipyramidal (5) coordination geometry. For 6, each of two [Cd(Tab)(bdmppy)] fragments is linked to one [(Tab)Cd(μ-Tab)2Cd(Tab)] fragment via two Tab bridges to generate a unique cationic zigzag tetrameric structure where the Cd centers take a tetrahedral or a trigonal bipyramidal coordination geometry. The results may provide an interesting insight into mimicking the coordination spheres of the Cd(II) sites of metallothioneins and their interactions with various N-donor ligands encountered in nature.
Co-reporter:Ai-Xia Zheng, Zhi-Gang Ren, Ling-Ling Li, Hai Shang, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2011 - vol. 40(Issue 3) pp:NaN596-596
Publication Date(Web):2010/11/30
DOI:10.1039/C0DT00620C
Reactions of a gold(I) thiolate complex [Au(Tab)2]2(PF6)2 (Tab = 4-(trimethylammonio)benzenethiolate) with equimolar 1,2-bis(diphenylphosphine)ethane (dppe), 1,3-bis-(diphenylphosphine)propane (dppp) or 1,4-bis-(diphenylphosphine)butane (dppb) in MeOH–DMF–CH2Cl2 gave rise to three polymeric complexes [Au2(Tab)2(dppe)]2(PF6)4·2MeOH (1·2MeOH), [Au2(Tab)2(dppp)]Cl2·0.5MeOH·4H2O (2·0.5MeOH·4H2O), and [Au4(μ-Tab)2(Tab)2(dppb)](PF6)4·4DMF (3·4DMF), respectively. Analogous reaction of 1 with dppb in DMF/C2H4Cl2 produced one tetranuclear complex [Au2(μ-Tab)(Tab)2]2Cl4·2DMF·4H2O (4·2DMF·4H2O). Complexes 1–4 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H and 31P{1H} NMR and single crystal X-ray analysis. Compounds 1 and 2 consist of [Au(Tab)]2 dimeric fragments that are bridged by dppe or dppp ligands to form a 1D linear chain extending along the a axis. For 3, each [Au4(Tab)2(μ-Tab)2] fragment is linked by a pair of dppb ligands to afford another 1D chain extending along the c axis. For 4, the four [Au(Tab)]+ fragments are linked by two Au–Au bonds and two doubly bridging Tab ligands to form a {[Au(Tab)]4(μ-Tab)2} chair-like cyclohexane structure. Hydrogen-bonding interactions in 2 and 4 lead to the formation of interesting 2D hydrogen-bonded networks. The luminescent properties of 1–4 in solid state were also investigated.
Co-reporter:Li-Li Miao, Hong-Xi Li, Miao Yu, Wei Zhao, Wei-Jie Gong, Jun Gao, Zhi-Gang Ren, Hui-Fang Wang and Jian-Ping Lang
Dalton Transactions 2012 - vol. 41(Issue 12) pp:NaN3430-3430
Publication Date(Web):2012/02/03
DOI:10.1039/C2DT12145J
Treatment of [CuCl2(bppyH2)] (1, bppyH2 = 2,6-di(1H-pyrazol-3-yl)pyridine) with 2 equiv. of AgNO3 in DMF gave rise to a binuclear Cu(II) complex [Cu2(bppyH)2(NO3)2] (bppyH = 2-(pyrazol-3-yl)-6-(pyrazolate)pyridine) (2). Complex 2 was characterized by elemental analysis, IR and single crystal X-ray diffraction. Complex 2 has a dimeric structure in which the two Cu(II) centers are bridged by a couple of the in situ-generated bppyH− anions. Each Cu(II) center is further coordinated by one O atom of a NO3− anion and three N atoms of one bppyH− anion. Complex 2 exhibited a higher catalytic activity in the polymerization of methyl methacrylate (MMA) than the precursor complex 1. Even though the ratio of catalyst to MMA was raised up to 1:1500, the PDI for 2 (reaction time was fixed at 4 h) is 1.63 and the conversion is up to 72%. The effects of solvent, reaction temperature and the ratio of MMA to catalyst were also investigated.
Co-reporter:Zhi-Gang Ren, Jun-Yi Yang, Ying-Lin Song, Ni-Ya Li, Hong-Xi Li, Yang Chen, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009(Issue 14) pp:NaN2587-2587
Publication Date(Web):2009/02/17
DOI:10.1039/B819240E
Reactions of trans-[(η5-C5Me5)2Mo2S2(μ-S)2] (1) with 2 equiv. of [Cu(MeCN)4]X (X = PF6−, ClO4−) produced two acetonitrile-coordinated cubane-like cationic clusters [(η5-C5Me5)2Mo2(μ3-S)4Cu2(MeCN)2]X2 (X = PF6− (2), ClO4− (3)). Treatment of 2 or 3 with 4,4′-bipyridine (4,4′-bipy) or trans-1,2-bis(4-pyridyl)ethylene) (bpee) afforded two polymeric clusters {[(η5-C5Me5)2Mo2(μ3-S)4Cu2(L)]X2}n (4: L = 4,4′-bipy, X = PF6−; 5: L = bpee, X = ClO4−), while analogous reactions of 2 or 3 with 1,2-bis(4-pyridyl)ethane (bpea), 1,2-bis(diphenylphosphine)ethane (dppe), or 1,4-bis-(diphenylphosphine)butane) (dppb) formed three dimeric clusters [(η5-C5Me5)2Mo2(μ3-S)4Cu2(L)]2X4 (6: L = bpea; X = PF6−; 7: L = dppe, X = ClO4−; 8: L = dppb, X = ClO4−). Clusters 2–8 consist of a cubane-like [(η5-C5Me5)2Mo2(μ3-S)4Cu2] core with each Cu being coordinated by one labile MeCN molecule (2, 3) or by bridging dipyridyl or diphosphino ligands (4–8). 4 or 5 has a 1D zigzag chain structure while 6–8 contain cyclic dimeric structures. The third-order non-linear optical (NLO) properties of 2–8 in MeCN were investigated by Z-scan technique at 532 nm. These compounds showed strong third-order NLO absorption effects and self-defocusing properties, and their NLO performances were remarkably enhanced relative to those of 1.
Co-reporter:Xiao-Yan Tang, Rong-Xin Yuan, Jin-Xiang Chen, Wei Zhao, Ai-Xia Zheng, Miao Yu, Hong-Xi Li, Zhi-Gang Ren and Jian-Ping Lang
Dalton Transactions 2012 - vol. 41(Issue 20) pp:NaN6172-6172
Publication Date(Web):2012/03/09
DOI:10.1039/C2DT30313B
Reactions of TabHPF6 (Tab = 4-(trimethylammonio)benzenethiolate) with three equiv. of M(OAc)2·2H2O (M = Zn, Cd) gave rise to two tetranuclear adamantane-like compounds, [M4(μ-Tab)6(Tab)4](PF6)8·S (1·S: M = Zn, S = DMF·4H2O; 2·S: M = Cd, S = DMF·5H2O). The similar reactions of MCl2 (M = Zn, Cd, Hg) with four equiv. of TabHPF6 in the presence of Et3N afforded three mononuclear compounds [M(Tab)4](PF6)2·S (3·S: M = Zn, S = 2(H2O)0.5; 4·S: M = Cd, S = 2(H2O)0.5; 5·S: M = Hg, S = 2DMF). Treatment of the precursor complex 3 or 5 with equimolar MCl2 and two equiv. of TabHPF6 and Et3N produced one dinuclear compounds [M(μ-Tab)(Tab)2]2(PF6)4·2DMF·2H2O (6·2DMF·2H2O: M = Zn; 8·2DMF·2H2O: M = Hg) while analogous reactions of 4 with CdCl2·2H2O gave rise to [Cd(μ-Tab)2(Tab)]2(PF6)4·2DMF (7·2DMF). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR and single-crystal X-ray crystallography. In 1 or 2, four M2+ ions and six S atoms of Tab ligands constitute an adamantane-like [M4(μ-S)6] cage in which each M2+ ion is tetrahedrally coordinated by one terminal S and three bridged S atoms from four different Tab ligands. In 3–5, each M2+ center of the [M(Tab)4]2+ dication is tetrahedrally coordinated by four S atoms of Tab ligand. Two [M(Tab)2]2+ dications in 6 or 8 are further bridged by a pair of Tab ligands to form a dimeric [M(μ-Tab)(Tab)2]24+ structure. Each dimeric [(Tab)Cd(μ-Tab)2Cd(Tab)]4+ unit in 7 is linked to its two neighboring units via two couples of bridging Tab ligands, thereby generating a unique 1D cationic chain. These results may provide useful information on interpreting structural data of MTs containing group 12 metals.
Co-reporter:Mei-Ling Cheng, Hong-Xi Li, Lei-Lei Liu, Hui-Hui Wang, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009(Issue 11) pp:NaN2019-2019
Publication Date(Web):2009/01/29
DOI:10.1039/B819637K
Protonolysis reactions of [Zn(dmpzm)Et2] (1) with acetic or formic acid in different molar ratios gave rise to four mononuclear zinc complexes [ZnEt(dmpzm)(L)] (2: L = OAc; 3: L = HCOO) and [Zn(dmpzm)(L)2] (4: L = OAc; 5: L = HCOO), one nonanuclear zinc complex [Zn(μ4-O)2(ZnEt)6(μ3-OAc)4(μ′3-OAc)2{Zn(dmpzm)Et}2] (6), and one tetranuclear zinc complex [Zn4(μ4-O)(dmpzm)3Et3] (7). Compounds 1–7 were characterized by elemental analysis, IR spectra, 1H NMR spectra, and the crystal structures of 1, 3, 4, 6, and 7 were determined by single-crystal X-ray crystallography. In the structures of 1, 3, and 4, the central Zn atom is tetrahedrally coordinated by two N atoms of one dmpzm and two C atoms of two Et groups (1), or one C atom of one Et group and one O atom of formate ligand (3), or two O atoms of two acetates (4). In the structure of 6, a heptanuclear [Zn(μ4-O)2(ZnEt)6(μ3-OAc)4] core is connected with two [Zn(dmpzm)Et]+ fragments via a pair of μ′3-OAc ligands. Compound 7 consists of a Zn4(μ4-O) tetrahedron in which three Zn atoms are further saturated by two N atoms from dmpzm ligands and an ethyl group while one Zn center is coordinated by three C atoms from the methylene group of the three dmpzm ligands.
Co-reporter:Ling-Ling Li, Hong-Xi Li, Zhi-Gang Ren, Dong Liu, Yang Chen, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009(Issue 40) pp:NaN8573-8573
Publication Date(Web):2009/09/02
DOI:10.1039/B908697H
Solvothermal reactions of CuI with four flexible N-heterocyclic ligands, 1,2-bis(4-pyridyl)ethane (bpe), 1,1′-(1,4-butanediyl)bis-1H-benzimidazole (bbbm), 1,1′-(1,4-butanediyl)bis-1H-benzotriazole (bbbt), and 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole (pbbm), afforded four new [CunIn]-based coordination polymers, [Cu3I(μ-I)(μ3-I)(bpe)3]n (1), {[CuI(bbbm)1.5]·0.25MeCN}n (2), and [Cu4(μ3-I)4L2]n (3: L = bbbt; 4: L = pbbm), respectively. Compounds 1–4 were characterized by elemental analysis, IR and X-ray crystallography. 1 consists of an unique 2D network in which 1D [CuI(bpe)]n zigzag chains are embroidered alternatively onto the two faces of a 2D [Cu4(μ-I)2(μ3-I)2(bpe)2]n layer through pairs of bpe bridges. 2 contains a 66-membered metallomacrocyclic [CuI(bbbm)1.5]6 unit that fuses with its neighbouring ones via sharing Cu atoms to form a 2D (6,3) layer network. 3 or 4 contains a cubanelike [Cu4(μ3-I)4] core, which works as a cross-shaped four-connecting node to link its four equivalent units to form a 2D (4,4) cross-shaped network (3) or acts as a Y-shaped three-connecting node to connect its three equivalent ones to form a 1D double chain (4). In addition, the photoluminescent properties of 1–4 in solid state at ambient temperature were also investigated.
Co-reporter:Yang Chen, Zi-Ou Wang, Zhou Yang, Zhi-Gang Ren, Hong-Xi Li and Jian-Ping Lang
Dalton Transactions 2010 - vol. 39(Issue 40) pp:NaN9479-9479
Publication Date(Web):2010/09/13
DOI:10.1039/C0DT00757A
Two unique low-dimensional benzyl viologen iodoplumbates [Pb13I38][B′V]6 (1) and [(Pb5I14)(BV)2]n (2) were prepared from solvothermal reactions of benzyl alcohol with 4,4′-bipy, PbI2, I2 and a small amount of water in acetonitrile. The semiconducting properties of the single crystals 1 and 2 along with Zn/Cl-doped samples 2a and 2b were investigated.
Co-reporter:Yu-Jian Huang, Ying-Lin Song, Yang Chen, Hong-Xi Li, Yong Zhang and Jian-Ping Lang
Dalton Transactions 2009(Issue 8) pp:NaN1421-1421
Publication Date(Web):2009/01/14
DOI:10.1039/B816312J
The reactions of a precursor cluster [Et4N]4[WS4Cu4I6] (1) with two equiv. of 1,1′-(1,4-butanediyl)bis(3,5-dimethyl-pyrazole) (bbd) or 1,3,5-tris(3,5-dimethyl-pyrazolyl-1-ylmethyl)-2,4,6-trimethylbenzene (tdtb) in MeCN/DMF afforded the dimeric clusters [WS4Cu3I(μ-bbd)]2 (2) and [{WS4Cu3(tdtb)}2(μ-I)2]·2DMF (3·2DMF), respectively. Solvothermal reactions of 1 with two equiv. of bbd in MeCN/DMF at 90 °C for 24 h resulted in the formation of the dimeric cluster [Et4 N]6[{WS4Cu5(μ-I)2I4}2(μ-bbd)] (4) while those of 1 with two equiv. of 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titb) in DMF at 120 °C afforded the polymeric cluster {[WS4Cu2(titb)]·0.5H2O}n (5). Compounds 2–5 were characterized by elemental analysis, IR, UV-vis, 1H NMR and single-crystal X-ray crystallography. Compound 2 has a double nido-shaped structure in which two nido-shaped [WS4Cu3] cores are connected by a pair of bbd ligands while 3 has a double butterfly-shaped structure in which two [WS4Cu3(tdtb)] fragments are linked by two bridging iodides. Compound 4 has a double-double half-open cubane-like structure in which a couple of double half-open cubane-like [WS4Cu5] cores are bridged by one bbd ligand. Compound 5 has a unique two-fold interpenetrated 3D (102·12)core(102·12)titb network in which each linear [WS4Cu2] core acts as a T-shaped 3-connecting node and each titb ligand works as a trigonal pyramidal 3-connecting node. The core structures of 2–5 are different from the saddle-shaped [WS4Cu4] core of 1, which may be attributed to the degradation or expansion of the cluster core of 1 during the reactions. In addition, the third-order non-linear optical (NLO) properties of 1–4 in DMF were also investigated by using Z-scan techniques at 532 nm.
Co-reporter:Zhen-Hong Wei, Hong-Xi Li, Zhi-Gang Ren, Jian-Ping Lang, Yong Zhang and Zhen-Rong Sun
Dalton Transactions 2009(Issue 18) pp:NaN3433-3433
Publication Date(Web):2009/03/20
DOI:10.1039/B822858B
Stepwise reactions of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1–4 equiv. of CuNCS (and Et4NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et4N][Tp*WS(μ-S)2(CuNCS)]·0.5CH2Cl2 (2·0.5CH2Cl2), [Et4N][Tp*W(μ3-S)(μ-S)2(CuNCS)2]·ClCH2CH2Cl (3·ClCH2CH2Cl), [Et4N]2[Tp*W(μ3-S)3(CuNCS)3(μ3-Br)]·1.5aniline (4·1.5aniline), and {[Et4N][Tp*W(μ3-S)3(Cu-μ-SCN)3(Cu-μ3-NCS)]}n (5). Compounds 2–5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 contains a [WS2Cu] core formed by addition of one CuNCS group onto the [Tp*WS3] species. The cluster anion of 3 has a butterfly-shaped [WS3Cu2] core constructed by addition of two CuNCS groups onto the [Tp*WS3] species. The cluster dianion of 4 consists of a cubane-like [Tp*WS3Cu3(μ3-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS3] species followed by filling a μ3-Br into the void of the incomplete cubane-like [Tp*WS3(CuNCS)3] fragment. 5 has a 2D cluster-supported layer network in which each [Tp*WS3Cu3] core acting as a pyramidal 3-connecting node interconnects with the [Cu(NCS)4] units through thiocyanate bridges. In addition, the third-order nonlinear optical (NLO) performances of 2–5 in DMF were also investigated by Z-scan techniques.
Co-reporter:Wang Yao, Fei-Long Li, Hong-Xi Li and Jian-Ping Lang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 8) pp:NaN4585-4585
Publication Date(Web):2015/01/08
DOI:10.1039/C4TA06378C
We report the synthesis of unique Au–Pd bimetallic alloy nanoparticles (NPs) supported on a hollow Cu2O–CuO core–shell heterostructure via the galvanic replacement method, which represents the first example of Au–Pd alloy nanoparticles immobilized on hollow Cu2O@CuO nanocubes. The morphological evolution can be controlled by the reaction time. The morphology, composition, and structure of the as-prepared Cu2O@CuO/(Au–Pd) material are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), elemental analysis (EDS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The size of the Au–Pd bimetallic NPs deposited onto the Cu2O@CuO nanocubes is ca. 15 nm. These bimetallic NPs showed a high catalytic activity towards the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in water at room temperature. Significantly, the strong synergistic effect between Au and Pd, and the high specific surface area of Cu2O@CuO enhance the catalytic efficiency. The catalytic system can be reused for several cycles without any obvious decay of the catalytic efficiency.
Co-reporter:Fan Wang, Fu-Ling Li, Miao-Miao Xu, Hong Yu, Jian-Guo Zhang, Hai-Tao Xia and Jian-Ping Lang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 11) pp:NaN5916-5916
Publication Date(Web):2015/02/03
DOI:10.1039/C5TA00302D
Ambient temperature solid state reaction of a preformed compound {[Pb(Tab)2]2(PF6)4}n (1) (TabH = 4-(trimethylammonio)benzenethiol) with two equiv. of 1,2-bis(4-pyridyl)ethylene (bpe) quantitatively produces a unique two-dimensional coordination polymer {[Pb(Tab)2(bpe)]2(PF6)4}n (2). The Ag(I)-doped coordination polymer {[Pb(Tab)2(bpe)]2(PF6)4·1.64AgNO3}n (2a) is readily prepared by immersing 2 into AgNO3 aqueous solution. Compared with its two precursors 1 and 2, 2a exhibits greatly enhanced catalytic activity towards the photodegradation of a family of 12 azo dyes within a short period of time under UV light irradiation and excellent adaptability on the elimination of azo dyes in water. It is anticipated that the ‘Ag(I)-doping’ synthetic strategy reported in this work may be applicable to other coordination polymer systems containing thiolate ligands for the preparation of various metal ion-doped multidimensional coordination polymers with new topological structures and better catalytic performances in the photodecomposition of azo dyes in industrial wastewater.
Co-reporter:Yang Chen, Zhou Yang, Xin-Yi Wu, Chun-Yan Ni, Zhi-Gang Ren, Hui-Fang Wang and Jian-Ping Lang
Physical Chemistry Chemical Physics 2011 - vol. 13(Issue 13) pp:NaN5667-5667
Publication Date(Web):2011/02/10
DOI:10.1039/C0CP02431G
The solvothermal reactions of BiI3, KI, I2, 4,4′-bipyridine (4,4′-bipy), and a small amount of water in alcohol and acetonitrile produced four bipyridinium iodobismuthates {[MQ]3[Bi2I6(μ-I)3][Bi2I6(μ-I)2(MQ)2]3} (1, MQ+ = N-methyl-4,4′-bipyridinium), {[EQ]3[Bi2I6(μ-I)3][Bi2I6(μ-I)2(EQ)2]3} (2, EQ+ = N-ethyl-4,4′-bipyridinium), [MV][BiI5] (Eur. J. Inorg. Chem., 2010, 5326) (3, MV2+ = N,N′-dimethyl-4,4′-bipyridinium), and [EV]2[Bi4I10(μ-I)4(μ3-I)2] (4, EV2+ = N,N′-diethyl-4,4′-bipyridinium). In these reactions, 4,4′-bipy was partly or completely alkylated by alkyl groups generated from the cleavage of C–O bond of alcohols, forming the N-alkyl-4,4′-bipyridinium cation (Q+) and the N,N′-dialkyl-4,4′-bipyridinium dication (V2+), respectively. Compounds 1–4 were characterized by elemental analysis, IR, 1H NMR and single-crystal X-ray diffraction analysis. The optical, electrical conductive and dielectric properties of these compounds were investigated. The dielectric constants of the Q+-based compounds were larger than the values of the V2+-based ones, which showed that the weak electrostatic interactions in the structures may benefit the polarizability of molecules, thereby resulting in a larger dielectric response of the structures under an external electric field, while the strong electrostatic interactions between the positive and negative charge units would lead to a low dielectric constant (low-k) behavior of these compounds.
Co-reporter:Yang Chen, Zhou Yang, Xin-Yi Wu, Chun-Yan Ni, Zhi-Gang Ren and Jian-Ping Lang
Physical Chemistry Chemical Physics 2011 - vol. 13(Issue 22) pp:NaN10786-10786
Publication Date(Web):2011/05/06
DOI:10.1039/C1CP20422J
Solvothermal reactions of CuI with isopropanol, 4,4′-bipyridine, I2 and a small amount of water in MeCN produced one coordination compound [isopropylviologen][CuI3] (isopropylviologen = N,N′-diisopropyl-4,4′-bipyridinium) (1). The dielectric constants of the single crystal of 1 along the three crystal axes are different with the largest diversity ratio of ∼3.3, showing dielctric anisotropic behavior. Under low temperature (<273 K) or medium electric field frequency range (1 KHz–1 MHz), the dielectric constant of the title compound is nearly unchanged, exhibiting a temperature/frequency-independent characteristics. The crystalline powder of 1 has a low dielectric constant and low dielectric loss in the medium electric field frequency range, which is comparable to the traditional low-k material SiO2.
Co-reporter:Yang-Yang Fang, Wei-Jie Gong, Xiu-Juan Shang, Hong-Xi Li, Jun Gao and Jian-Ping Lang
Dalton Transactions 2014 - vol. 43(Issue 22) pp:NaN8289-8289
Publication Date(Web):2014/03/19
DOI:10.1039/C4DT00475B
The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be utilized as a pre-catalyst to initiate the ring-opening polymerization of ε-caprolactone in the presence of alcohol but 2 did not work. The 1/alcohol system displayed characteristics of a well-controlled polymerization with the resulting poly(ε-caprolactone) having low molecular weight distributions, a linear tendency of molecular weight evolution with conversion, and polymer growth observed for the sequential additions of ε-caprolactone monomer to the polymerization reaction. The polymerization was completely turned off by the in situ reduction of the catalytic Fe center via Cp2Co and then turned back upon the addition of [Cp2Fe]PF6. The rate of polymerization was modified by switching in situ between the Fe(III) and Fe(II) species.
