Co-reporter:Ruo-Ting Dong, Xin-Li Chen, Xiao Cui, Su-Su Chen, Mo-Yuan Shen, Chu-Wen Li, Qian-Hong Li, Ming-Yuan Hu, Lan-Fen Huang and Hong Deng
CrystEngComm 2016 vol. 18(Issue 29) pp:5547-5561
Publication Date(Web):06 Jun 2016
DOI:10.1039/C6CE00637J
The first employment of 3-(3-pyridyl)acrylic acid (3-HPYA) in 3d–4f coordination chemistry is reported. Hydrothermal reactions of 3-HPYA with lanthanide oxides and copper halides led to the formation of 17 novel copper(I)–lanthanide(III) heterometallic coordination compounds with four structural types, namely, [Ln(3-PYA)3Cu3Cl3(H2O)2]·H2O [Ln = Dy (1), Eu (2), Gd (3), Tb (4)] (I), [Ln(3-PYA)3CuI(H2O)2]·0.5H2O [Ln = Dy (5), Gd (6), Tb (7), Sm (8)] (II), [Ln(3-PYA)3CuBr(H2O)2]·xH2O [Ln = La (9), Eu (10), x = 1; Sm (11), Nd (12), x = 0.5] (II), [LnCu2(3-PYA)2I2(ox)0.5(H2O)2]·(H2O)2 [Ln = Eu (13), Gd (14), Nd (15)] (III) and [LnCu2(3-PYA)2Br2(ox)0.5(H2O)]·(H2O) [Ln = Gd (16), Tb (17)] (IV) (ox = oxalate). These compounds were thoroughly characterized by single crystal and powder X-ray diffraction, as well as elemental analyses, FT-IR spectroscopy and thermal studies. All the compounds are constructed from halide-containing copper–inorganic motifs and Ln-containing motifs. Compounds of type I are constructed from 1D zigzag Dy–organic chains with [Cu6Cl6] ladder-like clusters, exhibiting a 2D binodal (5, 6)-connected topology. An unusual chemical rearrangement from [Cu6Cl6] to [Cu2Br2]/[Cu2I2] clusters occurs in the formation of type II structures. They are isostructural and exhibit a 3D coordination framework based on dinuclear [Dy2O2] subunits and [Cu2Br2]/[Cu2I2] clusters as nodes, possessing a binodal (4, 6)-connected net. In the type III structure, the Ln–organic motifs propagate along the b-axis, while the Cu–inorganic motifs propagate in the perpendicular direction along the a-axis, both of which are further interconnected to give unique 3D (3, 3, 4, 4, 6)-connected nets with {42·6}2{42·82·1010·12}{43·62·8}4{43}2 topologies. The type IV structure, based on structural analysis results, features a non-interpenetrated 3D coordination framework containing 2D Ln–organic layers and Cu2Br2 chains with a new 5-nodal (3, 3, 4, 4, 8)-connected topology net (point symbol: {42·6}2{43·63}4{43}2{46·610·810·102}). Our present work represents the first example of heterometallic Cu(I) halide–Ln(III)–organic frameworks utilizing 3-HPYA as an organic ligand. The diversity of the products demonstrates that the anion, pH value and reaction temperature have significant effects on the construction of the structures. Moreover, the photoluminescence properties of 2, 4, 7, 10, 12, 13, and 15 and the magnetic properties of 1, 5, and 16 were investigated.
Co-reporter:Guizhu Li, Yongcai Qiu, Yuan Hou, Hongfei Li, Lisha Zhou, Hong Deng and Yuegang Zhang
Journal of Materials Chemistry A 2015 vol. 3(Issue 3) pp:1103-1109
Publication Date(Web):12 Nov 2014
DOI:10.1039/C4TA04864D
A facile solvothermal method was used to synthesize V2O5 nanosheet hierarchical structures. Using different solvent systems, we obtained the hierarchical structures with different nanosheet thicknesses of <10 nm, 50–100 nm and 100–200 nm, respectively. A systematic investigation of their electrochemical properties showed that both the reversible lithium storage capacity and the cycling stability increased with the reduced thickness of nanosheets. In order to prevent the serious structural damage of the V2O5 electrodes during cycling, we employed a voltage-regulation charge/discharge scheme which led to a long cycle-life with an average capacity decay of 0.04% (2.0 to 3.0 V) and 0.10% per cycle (2.8 to 4.0 V) over 500 cycles.
Co-reporter:Ruo Ting Dong, Zhao Ying Ma, Li Xin Chen, Lan Fen Huang, Qian Hong Li, Ming Yuan Hu, Mo Yuan Shen, Chu Wen Li and Hong Deng
CrystEngComm 2015 vol. 17(Issue 30) pp:5814-5831
Publication Date(Web):22 Jun 2015
DOI:10.1039/C5CE00939A
Seven zinc and cadmium coordination frameworks, {[Zn2(TE)2]·H2O} (1a); {[Cd2(TE)(SO4)(OH)(H2O)]} (1b); TE = 2-(1H-tetrazol-5-yl)-ethanol, {[Zn1.5(TA)(INA)]·4H2O} (2a); {[Cd4.5(TA)3(N3)(OH)2(H2O)2]·H2O} (2b); {[Zn(MT)(INA)]·H2O} (2c); TA = (1H-tetrazol-5-yl)-acetic acid, MT = 5-methyl-tetrazole, INA = isonicotinic acid, {[Cd(BTMA)]·H2O} (3a); [Cd2(TTMA)(OH)] (3b); BTMA = bis-(1H-tetrazol-5-ylmethyl)-amine; TTMA = tris-(1H-tetrazol-5-ylmethyl)-amine, were obtained through in situ tetrazole synthesis and have been structurally characterized by single crystal and powder X-ray diffraction, as well as elemental analyses, FT-IR spectroscopy and thermal studies. Interestingly, by varying the reaction conditions of hydrothermal synthesis, the unprecedented in situ generation of TA and MT for 2 based on cyanoacetamide or BTMA and TTMA for 3 based on iminodiacetonitrile was observed, respectively. Compound 1a represents a very interesting example of three-dimensional (3D) frameworks containing hexagonal channels and meso-helical chains (P + M) alternately trapped by Zn–TE coordination interactions; compound 1b possesses a two-dimensional (2D) layered structure constructed from infinite organic chains and sulfate anions. Compounds 2a and 2b both crystallize in 3D frameworks containing infinite rod-shaped SBUs; compound 2c displays a two-fold diamondoid network constructed by the interconnection of Zn–MT–INA honeycomb layers and INA ligands. Compound 3a shows a 3D framework consisting of cyclic [Cd2(BTMA)2] dimer subunits, possessing an 8-connected network topology. Compound 3b shows a 3D binodal (4,8)-connected net based on tetranuclear [Cd4O2] polyoxometalates (POMs) as nodes. Furthermore, the luminescence properties of these compounds were investigated. Notably, compound 1b crystallizes in an acentric space group representing significant second harmonic generation (SHG) efficiencies.
Co-reporter:Ruoting Dong, Xinli Chen, Qianhong Li, Mingyuan Hu, Lanfen Huang, Chuwen Li, Moyuan Shen and Hong Deng
CrystEngComm 2015 vol. 17(Issue 6) pp:1305-1317
Publication Date(Web):15 Dec 2014
DOI:10.1039/C4CE01981D
Six novel transition metal coordination complexes, [Cu(3TMP)] (1), [Zn(3TMP)Cl] (2), [Cd3(3TMP)4(N3)2]·0.38H2O (3), [Zn3(4TMP)2(OH)2(H2O)]·2(NO3) (4) and [M2(4TMP)(OH) (H2O)(SO4)] (M = Zn (5), M = Cd (6)) (3HTMP = 3-((1H-tetrazol-5-yl) methyl) pyridine; 4HTMP = 4-((1H-tetrazol-5-yl) methyl) pyridine), have been hydrothermally synthesized through in situ tetrazole synthesis. These complexes have been structurally characterized by single crystal and powder X-ray diffraction elemental analyses, Fourier transform infrared spectroscopy as well as thermal studies. Complexes 1–6 are two or three-dimensional (3D) frameworks with structural diversity owing to the versatile coordination modes of the in situ generated flexible ligands. Complex 1 presents a reticular structure consisting of two-dimensional (2D) layers formed by the linkage between the pyridine rings and [Cu–tetrazole–Cu] wave-like chains. Complex 2 features a 3D framework built up by two kinds of helical chains composed of Zn(II) and the flexible ligand 3TMP. Complex 3 exhibits a 3D framework built up from 3TMP ligands and trinuclear [Cd3(N3)2] building units. Complex 4 crystallizes as a 3D coordination complex constructed from two-dimensional layers and the linkers of 4TMP ligands, with NO3− anions situated in the channels. Complexes 5 and 6 exhibit a 3D framework constructed from {M2(4TMP)(OH)}nn− (M = Zn (5), M = Cd (6)) layers and sulfate anions. In addition, the counterions, such as the Cl terminal ligand in 2, the N3 terminal ligand in 3, the μ2-OH bridging ligand in company with free NO3− anions in 4, and the μ3-OH bridging ligand in company with free SO42− anions in 5 and 6, have decisive influence on the dimensionality and functionality of the final complexes. Furthermore, the solid state luminescence properties of these complexes have been investigated.
Co-reporter:Ying-Zhao Ma, Li-Min Zhang, Guo Peng, Chong-Jian Zhao, Ruo-Ting Dong, Cheng-Feng Yang and Hong Deng
CrystEngComm 2014 vol. 16(Issue 4) pp:667-683
Publication Date(Web):22 Oct 2013
DOI:10.1039/C3CE42025F
By the control of experimental parameters such as anions, pH value and reaction temperature, five different types of three-dimensional (3D) 3d–4f cyanide heterometallic coordination polymers (HCPs), namely [Ln3Cu7(ina)8(OAc)2(CN)6]·xH2O [x = 0, Ln = Nd (I-A); x = 1, Ln = Eu (I-B), Ln = Gd (I-C), Ln = Tb (I-D), Ln = Dy (I-E), ina = isonicotinate, OAc = acetate], [Ln2Cu6.5(ina)7(Cl)3(CN)2.5(H2O)6]·2H2O [Ln = Tb (II-A), Ln = Dy (II-B)], [Ln2Cu2.5(ina)3(F)2.5(SO4)0.5(CN)2(H2O)0.5] [Ln = Tb (III-A), Ln = Dy (III-B)], [Ln3Cu4.5(OH)2(ina)6(OAc)2(CN)3.5]·H2O [Ln = Tb (IV-A), Ln = Dy (IV-B)] and [Ln2Cu5.(ina)6(OAc)(CN)4(H2O)2] [Ln = Tb (V-A), Ln = Dy (V-B)] have been hydrothermally synthesized and structurally characterized. All the compounds are constructed from cyano-containing copper–inorganic motifs and Ln-containing motifs. In the type I structures, the copper–inorganic motifs can be viewed as double-stranded {Cu(CN)}∞ ribbons with projecting sidearms, and the Ln–organic motifs are zigzag chains. In the type II structures, the copper–inorganic motifs are two-dimensional (2D) {CuCl(CN)}∞ layers, while the Ln–organic motifs can be described as two kinds of very similar one-dimensional (1D) chains possessing a parallel and alternating arrangement. In type III structures, the copper–inorganic motifs are 2D layers whereas the Ln–organic/inorganic motifs are fluoride-bridging 2D layers. In the type IV structures, the copper–inorganic motifs contain two unique types of 0D copper–cyanide units, while the Ln–organic counterparts are 1D chain structures linked by OH− groups. In type V structures, the copper–inorganic motifs and the Ln–organic motifs are 2D layers that can both be topologically simplified to (4, 4) networks. Moreover, the photoluminescence of I-A, I-B, I-D, II-A, III-A, IV-A and V-A, and the magnetism of I-E, II-B, III-B, IV-B and V-B were investigated.
Co-reporter:Ying-Zhao Ma, Ruo-Ting Dong, Chu-Wen Li, Mo-Yuan Shen, Chong-Jian Zhao, Cheng-Feng Yang, Hong Deng
Inorganic Chemistry Communications 2014 Volume 46() pp:172-175
Publication Date(Web):August 2014
DOI:10.1016/j.inoche.2014.05.021
•Three 3D Ln–Cu heterometallic coordination polymers (HCPs) have been synthesized.•Being an extremely rare example, glycolic acid (ga) was used as auxiliary ligand.•All ga ligands are deprotonated to adopt a μ3-kO:kO,O′:kO′,O″ coordination mode.•Copper–cyanide-system has been successfully incorporated as Cu-inorganic motifs.•HCP 1 shows antiferromagnetic behaviors.A series of unusual three-dimensional (3D) 3d–4f cyanide heterometallic coordination polymers (HCPs), namely [Ln1.5Cu3(ina)3(ga)(CN)1.5(X)(H2O)] [Ln = Dy, X = Cl (1), Ln = Tb, X = Br (2), Ln = Dy, X = Br (3); ina = isonicotinic acid; ga = glycolic acid] have been synthesized via hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analyses, FT–IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). X-ray structural analysis reveals that HCPs 1 to 3 are constructed from the linkage between Ln–organic layer motifs and double-stranded cyano-containing Cu-inorganic ribbon motifs. In these complexes, the carboxyl group and hydroxyl group of H2ga are all deprotonated and the coordinated ga ligands adopt a very interesting μ3-kO:kO,O′:kO′,O″ coordination mode. Moreover, magnetic properties of HCP 1 were investigated.The linkage between Dy-organic layer motifs and double-stranded cyano-containing Cu-inorganic ribbon motifs gives the 3-dimensional heterometallic coordination polymers.
Co-reporter:Chongjian Zhao, Chuwen Li, Moyuan Shen, Lanfen Huang, Qianhong Li, Mingyuan Hu, Hong Deng
Inorganic Chemistry Communications 2014 Volume 48() pp:30-35
Publication Date(Web):October 2014
DOI:10.1016/j.inoche.2014.08.005
•Four Coordination Polymers based on bifunctional ligands have been synthesized.•Compound 1 is constructed by Cd-btm2- layers and large bridging metalloligands.•It is notable that btm2- takes on six different coordination modes in 1 and 2.•Compounds 1–4 show luminescence behaviours.By employing Cd(II) salt, NaN3, and CN–(CH2)n–NC (n = 1, 2) and with the absence or presence of secondary ligands, four new cadmium coordination frameworks, named, {[Cd4(btm)4(H2O)2]·3H2O}n (1); [Cd2(btm)2(H2O)]n (2); [Cd2(bte)(PMA)0.5(H2O)]n (3); and [Cd(tzp)(2,2′-bipy)]n (4) (H2btm = bis(tetrazole) methane: H2bte = 1,2-bis(tetrazole-5-yl)ethane; H2tzp = 1H-tetrazolate-5-propionic acid; bipy = bipyridine; PMA = 1,2,4,5-benzenetetracarboxylic acid) were synthesized via in situ hydrothermal reaction. Single crystal X-ray diffraction reveals that compounds 1–3 are all three-dimensional (3D) frameworks. Compound 1 is constructed by Cd1– and Cd3–btm2 − layers and large bridging metalloligands. Compound 2 exhibits a 3D framework with two-dimensional (2D) Cd–btm2 − (adopting μ6:κN1, N1′: κN2: κN3: κN4: κN3′: κN4′coordination mode) layers pillared by μ3:κN1, N1′: κN2: κN4′ btm2 −. Compound 3 is built up by the Cd–bte2 − layers and the linker PMA, with left- and right-handed helical chains arranged alternately. It is notable that btm2 − takes on six different coordination modes in 1 and 2. Compound 4 represents a 2D layered framework, which can be simplified into a Shubnikov plane net (4.8^2) topological network with 3-connected T shape linker tzp2 − ligands. In addition, the research results show that compounds 1–4 exhibit different fluorescent behaviors and thermal stabilities.Four new cadmium coordination frameworks {[Cd4(btm)4(H2O)2]·3H2O}n (1); [Cd2(btm)2(H2O)]n (2); [Cd2(bte)(PMA)0.5(H2O)]n (3); and [Cd(tzp)(2,2′-bipy)]n (4) (H2btm = bis(tetrazole) methane: H2bte = 1,2-bis(tetrazole-5-yl)ethane; H2tzp = 1H-tetrazolate-5-propionic acid; bipy = bipyridine; PMA = 1,2,4,5-benzenetetracarboxylic acid) were synthesized via in situ hydrothermal reaction.
Co-reporter:Li Liang, Chengfeng Yang, Yingzhao Ma and Hong Deng
CrystEngComm 2013 vol. 15(Issue 2) pp:365-375
Publication Date(Web):29 Oct 2012
DOI:10.1039/C2CE26720A
Five new cadmium(II) tetrazole-based compounds, {[Cd4(3-tzba)4(H2O)2]·2H2O (1), [Cd(3-tzba)(2,2′-bipy)2] (2), [Cd(3-tzba)(1,10-phen)] (3), [Cd3(3-tzba)2(NA)2(H2O)] (4) and [Cd(3-tzba)(BIO)] (5), where 3-tzba = 3-(1H-tetrazol-5-yl)benzoate, 2,2′-bipy = 2,2′-bipyridine, 1,10-phen = 1,10-phenanthroline, NA = nicotinic acid, BIO = benzo-biimidazolediones}, were successfully synthesized involving the in situ generation of ligand under hydrothermal conditions. The compounds were thoroughly characterized by elemental analyses, Fourier transform infrared spectroscopy, thermal studies, and single crystal and powder X-ray diffraction. Compound 1 represents a three-dimensional (3D) coordination framework built up by the assembly of two-dimensional (2D) Cd-3-tzba wheel layers and 3-tzba linkers, exhibiting a pcu (412·63) topological net. Compound 2 displays a one-dimensional (1D) zigzag chain formed by the linkage of Cd(II) centers and 3-tzba ligands. Compound 3 shows a 1D pearl-necklace-like chain built by the interconnection of Cd(II) centers and 3-tzba ligands. Compound 4 is a 3D coordination framework which is constructed by 1D [Cd3] chains with 3-tzba and NA ligands linkers displaying a hxl (36) type net. Compound 5 exhibits a 3D sql (44) topological network, with 1D Cd chains linking the adjacent 3-tzba and BIO ligands. It is noted that the 3-tzba and BIO ligands are generated in situ from the precursor 3-cyanobenzoic acid and 1,2,4,5-benzenetetracarboxylic acid (H4bta), respectively. In addition, the luminescent properties of these compounds were investigated.
Co-reporter:Li Ma, Naiqian Yu, Susu Chen and Hong Deng
CrystEngComm 2013 vol. 15(Issue 7) pp:1352-1364
Publication Date(Web):27 Nov 2012
DOI:10.1039/C2CE26323H
By variation of reaction parameters such as metal salts and secondary ligands, a series of new coordination polymers, [Cd(QTZ)2] (1), [Cd(QTZ)N3·H2O] (2), [Zn(QTZ)Cl] (3), [Cd2(QTZ)2(INA)2]·0.25H2O (4), [Cd2(QTZ)(btrc)·2(H2O)]·1.67H2O (5), 2[Cd3(QTZ)2(btec)·H2O]·H2O (6) (QTZ = 5-(quinolyl)tetrazole; HINA = isonicotinic acid; H3btrc = 1,3,5-benzenetricarboxylic acid; H4btec = 1,2,4,5-benzenetetracarboxylic acid) were successfully synthesized under hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction. The QTZ ligands in these compounds are in situ generated from a [2 + 3] cycloaddition reaction of 3-quinolinecarbonitrile and NaN3 in water with the acid of CdII/ZnII salt. Compound 1 displays a three-dimensional (3D) 2-fold interpenetrating diamond network with Schläfli symbol 66. Compound 2 represents a two-dimensional (2D) coordination framework constructed of infinite Cd–N3− chains and QTZ ligands. Compound 3 exhibits a 4-connected 2D (4,4) net built up by interconnection of Zn2(QTZ)2Cl2 subunits. Compound 4 is a 2D framework constructed by interconnection of Cd2(QTZ)2(INA)2 subunit and Cd2(QTZ)2 subunit. Compound 5 exhibits a 2D layered structure with the Cd2–QTZ chain extended by btrc ligands. In compound 6, trinuclear CdII clusters link each other by pairs of QTZ ligands to form an infinite zigzag Cd3–QTZ chain; furthermore the adjacent Cd3–QTZ chains are extended by the btec ligands to form a 3D network. These results indicate that QTZ is a powerful functional ligand and the nature of secondary ligands and transition metal ions also play significant roles in dominating molecular self-assembled structure. In addition, the luminescent properties of all compounds have been investigated in the solid state at room temperature.
Co-reporter:Guo Peng, Li Ma, Li Liang, Yingzhao Ma, Chengfeng Yang and Hong Deng
CrystEngComm 2013 vol. 15(Issue 5) pp:922-930
Publication Date(Web):13 Nov 2012
DOI:10.1039/C2CE26277K
Four novel 3d–4f heterometallic coordination polymers [Dy4Mn(PDA)6(SO4)2 (H2O)4]·13H2O (1) and [Ln4M(PDA)4(SO4)2(INA)2(H2O)8]·5H2O [Ln = Gd, M = Mn (2); Ln = Eu, M = Zn (3); Ln = Tb, M = Zn (4); PDA = pyridine-2,6-dicarboxylate; INA = isonicotinate] have been hydrothermally synthesized and structurally characterized. Compound 1 possesses a 1D chainlike structure with the tetranuclear [Dy4(PDA)6(SO4)2(H2O)2] “metalloligand” linking the adjacent Mn atoms. Compounds 2–4 are isostructural and possess a 2D heterometallic layer network with a (4,4) connected topology. Furthermore, the magnetic and luminescent properties of compounds 1–4 were investigated.
Co-reporter:Limin Zhang, Naiqian Yu, Kaihong Zhang, Ruishuo Qiu, Yixuan Zhao, Wencong Rong, Hong Deng
Inorganica Chimica Acta 2013 400() pp: 67-73
Publication Date(Web):
DOI:10.1016/j.ica.2013.02.016
Co-reporter:Li Liang, Guo Peng, Li Ma, Lin Sun, Hong Deng, Hong Li, and Weishan Li
Crystal Growth & Design 2012 Volume 12(Issue 3) pp:1151-1158
Publication Date(Web):January 3, 2012
DOI:10.1021/cg200856e
A series of novel three-dimensional (3D) Ln(III)–Cu(I) heterometallic tetrazole-based coordination frameworks, namely, [LnCu(3-tzba)2(H2O)4] [Ln = Eu (1), Gd (2), Tb (3), Dy (4); 3-tzba = 3-(1H-tetrazol-5-yl)benzoate], were successfully synthesized through in situ [2 + 3] cycloaddition reaction under hydrothermal conditions. Compounds 1–4 are isostructural 3D coordination frameworks with 1D anionic chains [Ln(3-tzba)2(H2O)4]− linking the adjacent Cu(I) ions possessing a uninodal 10-connected topology with the short (Schläfli) vertex symbol of (312.424.59). To the best of our knowledge, they are the first lanthanide–transition heterometal–organic coordination frameworks obtained through in situ tetrazole synthesis. In addition, the luminescence properties of 1 and 3 and the magnetic properties of 2 and 4 were also investigated.
Co-reporter:Lin Sun, Li Ma, Jin-Biao Cai, Li Liang and Hong Deng
CrystEngComm 2012 vol. 14(Issue 3) pp:890-898
Publication Date(Web):15 Nov 2011
DOI:10.1039/C1CE05829K
By control of the in situtetrazole ligand reaction and by the addition of different secondary ligands such as 2,2′-bipy, 4,4′-bipy or INA, five interesting frameworks, namely, Cd(tza)(2,2′-bipy)·H2O (1), [Cd2(btm)2(2,2′-bipy)2]·2.24H2O (2a), [Zn2(btm)2(2,2′-bipy)2]·3H2O (2b), Cd(btm)(4,4′-bipy)1/2 (3), [Zn(5MT)(INA)]2·2H2O (4) and Mn2(btm)2(2,2′-bipy)2 (5) (H2tza = 1H-tetrazolate-5-carboxylate; bipy = bipyridine; H2btm = bis(tetrazole) methane; 5MT = 5-methyl-tetrazole; HINA = isonicotinic acid), were synthesized and structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a two-dimensional (2D) framework constructed of the dinuclear [Cd2O2] clusters and μ3-κN4:κN6,O1:κO1 bridging tza. Compounds 2a and 2b display 2D frameworks built up by the linkage of infinite one-dimensional (1D) helical zigzag -M-btm-M- chains (M = Cd, Zn, respectively) with dinuclear units [MN2]2.. Compounds 1, 2a and 2b all exhibit a 2D four-connected (4,4) topological network. Compound 3 represents a three-dimensional (3D) framework constructed of 2D layers formed by the linkage of [Cd2N4] cluster units and μ4-κN2:κN4:κN8:κN1, N5 tetrazolate groups as "double-bridges", which are pillared through 4,4-bipy, finally giving a pcu (412 63) topology. Compound 4 exhibits a 3D two-fold interpenetrating diamond-like network constructed by infinite -5MT-Zn-5MT- chains and INA as bridging coligands. Compound 5 is a 2D framework which is built up by Mn1-tetrazole helical chains, [Mn2N2]2 clusters and μ3-κN11:κN14, N15:κN17 and μ3-κN3, N7:κN4:κN10 tetrazole groups. It is noted that both H2tza and H2btm ligands are in situ generated from the same precursor, malononitrile. These results show the influence of the reactant ratio, the nature of the secondary ligands and the metal ions in the construction of metal frameworks based on tetrazole. The photoluminescent properties of 1, 2a, 2b, 3, 4 and thermal stabilities of 1, 3, 4, 5 are investigated in the solid state at room temperature.
Co-reporter:Li Liang, Guo Peng, Guizhu Li, Yanhua Lan, Annie K. Powell and Hong Deng
Dalton Transactions 2012 vol. 41(Issue 19) pp:5816-5823
Publication Date(Web):21 Feb 2012
DOI:10.1039/C2DT30175J
A family of six dinuclear lanthanide complexes have been obtained via in situ hydrothermal synthesis with lanthanide ions as catalyst. These six complexes are formulated as [Ln2(3-Htzba)2(3-tzba)2(H2O)8]·4H2O [Ln = Gd, 1; Dy, 2; Eu, 3; Tb, 4; Sm, 5; Er, 6; 3-H2tzba = 3-(1H-tetrazol-5-yl)benzoic acid]. The magnetic investigations show that complex 2 behaves as a single-molecule magnet (SMM) with a quantum relaxation time of ∼10−2 s.
Co-reporter:Guo Peng, Zhihui Liu, Li Ma, Li Liang, Limin Zhang, George. E Kostakis and Hong Deng
CrystEngComm 2012 vol. 14(Issue 18) pp:5974-5984
Publication Date(Web):14 Jun 2012
DOI:10.1039/C2CE25214G
A series of three-dimensional (3D) lanthanide–copper coordination polymers, namely [Ln2(NA)6Cu6Br6(H2O)4]·3.5H2O] [Ln = Sm (1), Eu (2), Tb (3), NA− = nicotinate], [Ln(NA)2Cu2Br2(C2O4)0.5(H2O)2]·2H2O [Ln = Gd (4), Er (5), C2O4 = oxalate], [Ln(NA)2Cu3Br3(OAc)(H2O)] [Ln = Sm (6), Eu (7), Tb (8), OAc = acetate], [Er2(NA)6Cu7Br7(H2O)4]·2H2O (9) and [Gd(NA)3Cu3Cl3(H2O)2]·H2O (10) have been hydrothermally synthesized and structurally characterized. Compounds 1–3 are constructed from Ln–organic chains and two distinct Cu4Br4 clusters possessing a (411.64)2(414.67)2(418.610)(49.6)2 topology. Compounds 4 and 5 are composed of two-dimensional (2D) Ln–organic layers and cubane-like Cu4Br4 clusters possessing a (43.66.8)(43)(46.66.83) topology. Compounds 6–8 can be viewed as the connection between Ln–organic chains and prism-like Cu6Br6 clusters with 4,6T50 topology. Compound 9 is constructed by Er–organic chains and dicubane-like Cu8Br7 clusters possessing a fluorite (flu) topology. Compound 10 consists of Gd–organic chains and inorganic Cu3Cl3 chains with tcj/hc topology. The diversity of the products demonstrates that the auxiliary ligand, pH value, reaction temperature and anion have significant effect on the construction of the structures. Moreover, the photoluminescence of 1–3 and 6–8, and the magnetism of 9 and 10 were investigated.
Co-reporter:Li-Min Zhang, Da-Yi Deng, Guo Peng, Lin Sun, Li Liang, Guo-Qiang Lan and Hong Deng
CrystEngComm 2012 vol. 14(Issue 23) pp:8083-8089
Publication Date(Web):04 Sep 2012
DOI:10.1039/C2CE26028J
A series of homochiral lanthanide coordination polymers, [Ln(IDA)(HIDA)]n [Ln = Eu (1), Gd (2), Tb (3), Dy (4); IDA = iminodiacetate; HIDA = N-protonated iminodiacetate] have been hydrothermally synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. Compounds 1–4 are isostructural three-dimensional (3D) coordination polymers. Spontaneous resolution occurs during crystal growth in the absence of a chiral source, as the enantiomers are obtained and confirmed by single-crystal X-ray diffraction and solid-state circular dichroism (CD) measurements. Furthermore, photoluminescence measurements indicate europium compound (1) and terbium compound (3) are red and green emitters, respectively, in the solid state at room temperature.
Co-reporter:Lin Sun;Gui-Zhu Li;Mei-Hua Xu;Xiao-Jian Li;Jian-Rong Li
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 11) pp:1764-1772
Publication Date(Web):
DOI:10.1002/ejic.201101289
Abstract
Three series of novel lanthanide-based 1D, 2D, and 3D metallic coordination frameworks involving the 2-pyridin-4-yl-4,5-imidazoledicarboxylic acid (H3PIDC) ligand have been characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The compound [Tb(PIDC)(H2O)4]·H3PIDC·4H2O (1) upon slow evaporation at room temperature gave a 1D coordination chain framework constructed of [Tb2O2] dimers bridged through the carboxylate groups of PIDC3– ligands; a 3D supramolecular structure is generated through hydrogen bonding and π–π interactions. The second kind of lanthanide-based coordination framework, namely [Ln(H2PIDC)(ox)H2O]·3H2O [Ln = Sm (2), Gd (3), Dy (4), and Ho (5), ox = oxalic acid], synthesized under hydrothermal conditions, self-assemble through Ln2[H2PIDC]2 building blocks and bridging oxalate ligands to give a 2D coordination layer structure. The adjacent layers stack to form a 3D supramolecular framework through weak interactions such as hydrogen bonding and π–π interactions. The third series of lanthanide-based coordination compounds with chemical formula [Ln(HPIDC)(ox)1/2H2O]·3H2O [Ln = Gd (6), Dy (7), Tb (8) and Ho (9)] were also synthesized by hydrothermal reaction. These isostructural compounds contain an infinite –Ln–O–C–O–Ln– zigzag chain, which connect to each other through the oxygen atoms of the HPIDC2– ligands to form a wave-like layer. The layers are bridged by oxalate ligands to generate a 3D coordination framework.
Co-reporter:Lin Sun, Xiaojian Li, Naiqian Yu, Susu Chen, Shuqin Yao, Hong Deng
Inorganic Chemistry Communications 2012 Volume 24() pp:241-246
Publication Date(Web):October 2012
DOI:10.1016/j.inoche.2012.07.029
The synthesis of three new zinc coordination polymers, [Zn(3-pttz)2(4,4'-bipy)] (1), [Zn(3-pttz)(TPA)(H2O)2] (2) and [Zn(3-pttz)(PMA)0.5] (3) (3-pttz = 5-(3-pyridyl)tetrazolate, TPA = terephthalic acid and PMA = 1,2,4,5-Benzenetetracarboxylic acid), with sodium azide and 3-cyanopyridine via in situ hydrothermal method have been investigated. These three coordination polymers were successfully synthesized, and characterized by elemental analysis, Fourier transform infrared (FTIR) spectroscopy, thermal studies and single-crystal X-ray diffraction. The results indicate that in compound 1, the 3-pttz ligands adopt monodentate coordination mode while the 4,4'-bipy ligands bridge the Zn(II) ions to generate infinite − Zn − 4,4'-bipy − Zn − chains, which furthermore through weak C-H···N hydrogen bonds to form a three-dimensional (3D) supermolecular structure. For compound 2, the Zn(II) ions are connected by 3-pttz ligands to form one-dimension (1D) − 3-pttz − Zn − 3-pttz − helical chains, and the secondary ligands TPA adopt the terminal mode; the chains are assembled into a 3D supermolecular framework via hydrogen bonds. Compound 3 is a two-dimensional (2D) network constructed from self-assembly of Zn (II) ions and PMA ligands with the 3-pttz ligands by assuming the monodentate coordination mode, resulting in the formation of a 3D supermolecular framework via weak C-H···O hydrogen bonds. Furthermore, thermal behaviors and luminescence properties for these crystalline materials have been investigated.Three new zinc coordination polymers, [Zn(3-pttz)2(4,4'-bipy)] (1), [Zn(3-pttz)(TPA)(H2O)2] (2) and [Zn(3-pttz)(PMA)0.5] (3) (3-pttz = 5-(3-pyridyl)tetrazolate, TPA = terephthalic acid and PMA = 1,2,4,5-Benzenetetracarboxylic acid), were successfully synthesized through in situ hydrothermal reaction.Highlights► Three new zinc tetrazole-based coordination polymers have been successfully synthesized. ► 5-(3-pyridyl)tetrazolate ligand is in situ generated from the [2 + 3] cycloaddition reaction. ► Compounds 1–3 are potential candidates for applications as photoactive materials.
Co-reporter:Guoqiang Lan, Ruoting Dong, Naiqian Yu, Limin Zhang, Yingzhao Ma, Chengfeng Yang, Hong Deng
Inorganic Chemistry Communications 2012 Volume 24() pp:190-194
Publication Date(Web):October 2012
DOI:10.1016/j.inoche.2012.07.007
By the addition of different secondary ligands, three new d10 metal coordination polymers, [M2(ET)(pzdc)(μ3-OH)] [M = Cd(1), Zn(2)] and [Zn(Et)(Hbic)] (3) (ET = 5-ethyltetrazole; H2pzdc = Pyrazine-2,3-dicarboxylic acid; Hbic = 1H-benzimidazole-5-carboxylic acid), have been successfully prepared under hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction analysis. The ET ligand in compounds 1–3 is in situ generated from the [2 + 3] cycloaddition reaction of the precursor propionitrile and NaN3 in water with the aid of zinc/cadmium salt. Compounds 1 and 2 present three-dimensional (3D) (4,4,4,4)-connected net based on O-centered M3 isosceles triangle. Compound 3 exhibits a 3D diamond framework constructed by infinite –ET–Zn–ET– 1D zigzag chains and Hbic as bridging coligand. Furthermore, the thermal stabilities of compounds 1–3 and the luminescence properties of compounds 1 and 2 have been investigated.Three new d10 metal coordination polymers, [M2(ET)(pzdc)(μ3-OH)] [M = Cd(1), Zn (2)] and [Zn(ET)(Hbic)] (3) (ET = 5-ethyltetrazole; H2pzdc = Pyrazine-2,3-dicarboxylic acid; Hbic = 1 H-benzimidazole-5- carboxylic acid), have been successfully prepared under hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction.Highlights► Zinc/cadmium tetrazole-based coordination polymers have been synthesized. ► 5-ethyltetrazole ligand is in situ generated from the [2 + 3] cycloaddition reaction. ► Studies of luminescence properties of 1 and 2 indicate that they may be good blue-light emitting candidate materials.
Co-reporter:Li Liang, Guizhu Li, Lin Sun, Guoqiang Lan, Limin Zhang, Chengfeng Yang, Yingzhao Ma, Hong Deng
Inorganic Chemistry Communications 2012 20() pp: 295-298
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.032
Co-reporter:Limin Jin, Yongcai Qiu, Hong Deng, Weishan Li, Hong Li, Shihe Yang
Electrochimica Acta 2011 Volume 56(Issue 25) pp:9127-9132
Publication Date(Web):30 October 2011
DOI:10.1016/j.electacta.2011.07.097
We report here a polymer-templated hydrothermal growth method and subsequent calcination to achieve carbon coated hollow CuFe2O4 spheres (H–CuFe2O4@C). This material, when used as anode for Li-ion battery, retains a high specific capacity of 550 mAh g−1 even after the 70th cycle, which is much higher than those of both CuFe2O4@C (∼300 mAh g−1) and H–CuFe2O4 (∼120 mAh g−1). And galvanostatic cycling at different current densities reveals that a capacity of 480 mAh g−1, 91% recovery of the specific capacity cycling at 100 mA g−1, can be obtained even after 50 cycles running from 100 to 1600 mA g−1. The significantly enhanced electrochemical performances of H–CuFe2O4@C with regard to Li-ion storage are ascribed to the following factors: (1) the hollow void, which could mitigate the pulverization of electrode and facilitate the lithium-ion, electron and electrolyte transport; (2) the conductive carbon coating, which could enhance the conductivity, alleviate the agglomeration problem, prevent the formation of an overly thick SEI film and buffer the electrode. Such a structural motif of H–CuFe2O4@C is promising, for electrode materials of LIBs, and points out a general strategy for creating other hollow-shell electrode materials with improved electrochemical performances.
Co-reporter:Guo Peng, Li Ma, Jinbiao Cai, Li Liang, Hong Deng, and George E. Kostakis
Crystal Growth & Design 2011 Volume 11(Issue 6) pp:2485-2492
Publication Date(Web):April 26, 2011
DOI:10.1021/cg200255r
A series of chiral and achiral lanthanide-alkali coordination polymers, [LnM(INA)3(OAc)] where [M = Li, Ln = Eu (1); M = Li, Ln = Tb (2); M = Na, Ln = Eu (3); M = Na, Ln = Tb (4); INA = isonicotinate; OAc = acetate] and [TbK(INA)2(OAc)2] (5), have been solvothermally synthesized and structurally characterized. The acetate groups were in situ obtained from oxidation of CH3CN during the reaction. Structures with remarkably different connectivities are formed when Li(I), Na(I), and K(I) were introduced into the system. Compounds 1–4 are isostructural three-dimensional (3D) coordination polymers and built up by right-/left-handed Ln-O-M chiral helicals and INA linkers possessing a 3,3,4,7T2 topology. Compound 5 is a 3D pillared coordination polymer constructed from two-dimensional (2D) Tb–O–K layers with INA as connectivities possessing an alb-4,8-P21/c topology. Circular dichroism (CD) measurements confirmed that the resulting crystals of 1, 3, and 4 were racemic mixtures. The photoluminescent properties of compounds 1–5 were investigated, exhibiting intense characteristic emission spectra of lanthanide ions.
Co-reporter:Li Ma;Yong-Cai Qiu;Guo Peng;Jin-Biao Cai
European Journal of Inorganic Chemistry 2011 Volume 2011( Issue 23) pp:3446-3453
Publication Date(Web):
DOI:10.1002/ejic.201100213
Abstract
Four d10 metal directed coordination frameworks, [Zn2(MT)3(IN)] (1; MT = 5-methyltetrazole, IN = isonicotinic acid), [Zn(ET)(IN)] (2; ET = 5-ethyltetrazole), [Zn(PT)2] (3; PT = 5-propyltetrazole), and [Zn(IPT)2] (4; IPT = 5-isopropyltetrazole), have been obtained by in situ tetrazole synthesis and structurally characterized by elemental analyses, FTIR spectroscopy, and thermal studies, as well as by single-crystal and powder X-ray diffraction analyses. Compound 1 exhibits a two-fold diamondoid network constructed of two-dimensional (2D) Zn–MT wheel layers and IN linkers. Compound 2 displays a similar two-fold diamondoid network constructed by interconnection of Zn–ET–IN honeycomb layers and IN ligands. Compound 3 represents a 3D coordination polymer constructed from numerous Zn6(PT)6 wheels with a diamondoid net. Compound 4 is a 2D network constructed by the self-assembly of Zn ions and IPT ligands with an sql net. Furthermore, the solid-state properties of these crystalline materials, such as their thermal behavior and photoluminescence properties, have also been investigated.
Co-reporter:Guo Peng, Yong-Cai Qiu, Zhi-Hui Liu, Biao Liu and Hong Deng
Crystal Growth & Design 2010 Volume 10(Issue 1) pp:114
Publication Date(Web):December 11, 2009
DOI:10.1021/cg900571v
A series of new d−f heterometallic coordination frameworks, namely, [LnM(Hbic)2(ox)H2O]·2H2O [Ln = Nd, M = Cu (1); Ln = Eu, M = Ag (2); Ln = Tb, M = Ag (3); H2bic = 1H-benzimidazole-5-carboxylic acid; ox = oxalate] for type I, [LnCu(Hbic)3(ox)0.5]·H2O [Ln = Sm (4), Ln = Dy (5)] for type II, and [LnAg(Hbic)(ox)1.5] [Ln = Eu (6)] for type III, were successfully synthesized by using different metal salts and rationally controlling reaction temperature. Complexes 1−3 represent 1D polymeric chain architectures that are constructed from the connections between lanthanide-oxalate chains and M(Hbic)2 subunits. Complexes 4 and 5 are 2D layered structures which are assembled by lanthanide-oxalate and Cu(Hbic)3 units. Complex 6 exhibits another 2D layered coordination framework that is built up by tetranuclear Eu2Ag2 clusters and mixed ox and Hbic linkers. The polymeric coordination frameworks of complexes 1−6 are sustained by both hydrogen bonding and π−π stacking interactions, and they are self-assembled to form the 3D supramolecular frameworks.
Co-reporter:Yongcai Qiu, Yinghua Li, Guo Peng, Jinbiao Cai, Limin Jin, Li Ma, Hong Deng, Matthias Zeller and Stuart R. Batten
Crystal Growth & Design 2010 Volume 10(Issue 3) pp:1332-1340
Publication Date(Web):February 15, 2010
DOI:10.1021/cg9013619
Seven three-dimensional (3D) cadmium coordination frameworks, {[Cd(5MT)2] (1a); [Cd5(N3)(5MT)9·0.12H2O] (1b); [Cd3(OH)Cl1.39(N3)0.61(5MT)3] (1c), 5MT = 5-methyl-tetrazole}; {[Cd3(OH)Cl(N3)(5AT)3 (2a); Cd2(OH)Br(5AT)2 (2b), 5AT = 5-amino-tetrazole]}; {[Cd7Cl2(5BT)12(H2O)2 (3a); and [Cd7Br2(5BT)12(H2O)2 (3b), 5BT = 5-butyl-tetrazole], were obtained through in situ tetrazole synthesis and have been structurally characterized by elemental analyses, Fourier transform infrared spectroscopy, thermal studies, and single crystal and powder X-ray diffraction. Compounds 1a and 1b were constructed by the interconnection of 5MT and cadmium metal ions, and both exhibited distinct topological nets: 1a has a diamond-like framework, while 1b has the acs topological net. Compounds 1c and 2a represented similar structural network motifs; both were intricate coordination polymers constructed from interconnected {ClCd3O} subnets through tetrazole anions. Compound 2b was constructed from two-dimensional (2D) wavelike {BrCd3O} layers bridged by 5AT anions. Compounds 3a and 3b were structural isomorphs, constructed from 2D Cd-5BT wheel layers and halogen linkers. Furthermore, the luminescent properties of these complexes were investigated.
Co-reporter:Biao Liu, Yong-Cai Qiu, Guo Peng and Hong Deng
CrystEngComm 2010 vol. 12(Issue 1) pp:270-276
Publication Date(Web):07 Sep 2009
DOI:10.1039/B910418F
Three novel heteronuclear coordination complexes, namely, [Cu2K(Mtta)I2] (1), [Cu3K(Mtta)3I] (2) and [Cu2Na(Mtta)2(CH3CN)I] (3) (HMtta = 5-methyl-1H-tetrazole) have been solvothermal synthesized by CuI, MCl [M = K (1) and (2); M = Na (3)], sodium azide and acetonitrile generated via a [3 + 2] cycloaddition reaction of acetonitrile and sodium azide. Single crystal X-ray diffraction reveals that all complexes are three-dimensional (3D) frameworks, where complex 1 is constructed by connecting rare µ5-N bridging Mtta ligands to Cu–I–K layers, complex 2 is built up by connecting inorganic cationic [Cu6I2]4+ clusters with numerous Mtta ligands, while complex 3 is constructed from open Cu(Mtta) subnets and Na+ centers. Furthermore, the luminescence properties of all complexes have been investigated. This work further supplements the mechanism of the Demko-Sharpless reaction in heteronuclear tetrazole-based coordination polymers.
Co-reporter:Guo Peng, Li Ma, Biao Liu, Jin-Biao Cai, Hong Deng
Inorganic Chemistry Communications 2010 Volume 13(Issue 5) pp:599-602
Publication Date(Web):May 2010
DOI:10.1016/j.inoche.2010.02.012
Three novel Ln(III)–Cu(I) coordination polymers, namely [LnCu(Hbic)3(ox)0.5] [Ln = Sm (1), Dy (2), Hbic = benzimidazole-5-carboxylate, ox = oxalate] and [EuCu(Hbic)2(ox)H2O]·2H2O (3) have been hydrothermally synthesized and stucturally characterized. Both complexes 1 and 2 display the same unusual 2D layer heterometallic coordination frameworks that are built up by dimeric [Ln2(Hbic)6] cores and oxalate ligands by sharing Cu(I) ions. Complex 3 represents 1D polymeric chain architecture constructed from Eu2Cu2 ring units and oxalate ligands. Furthermore, the luminescent property of complex 3 has also been investigated.Three novel Ln(III)–Cu(I) coordination polymers, namely [LnCu(Hbic)3(ox)0.5] [Ln = Sm (1), Dy (2), Hbic = benzimidazole-5-carboxylate, ox = oxalate] and [EuCu(Hbic)2(ox)H2O]·2H2O (3) have been hydrothermally synthesized and stucturally characterized.
Co-reporter:Yongcai Qiu, Biao Liu, Guo Peng, Jinbiao Cai, Hong Deng, Matthias Zeller
Inorganic Chemistry Communications 2010 Volume 13(Issue 6) pp:749-752
Publication Date(Web):June 2010
DOI:10.1016/j.inoche.2010.03.038
Two novel mercury(II)-organic polymeric complexes [HgCl(pzta)]n (1) and [Hg3Cl2(pzta)4(H2O)2]n (2) [pzta = pyrazinyl tetrazolate] were obtained by in situ synthesis of pyrazinyl tetrazolate from the reaction of pyrazinecarbonitrile with sodium azide in the presence of mercury(II) salts. Complex 1 is a 3D coordination polymer with a 3,5-connected hms [(63)(69 · 8)] net consisting of mildly undulate (6, 3) sheets and bridging chlorine ligands; while complex 2 is also a 3D supramolecular network built from 2D layers with the 4-connected sql {44 · 62} net that are assembled via hydrogen bonds and π⋯π stacking interactions. Last but not least, photofluorescent properties of the two complexes have also been investigated.Two novel mercury(II)-organic polymeric complexes [HgCl(pzta)]n (1) and [Hg3Cl2(pzta)4(H2O)2]n (2) [pzta = pyrazinyl tetrazolate] were obtained by in situ synthesis of pyrazinyl tetrazolate from the reaction of pyrazinecarbonitrile with sodium azide in the presence of mercury(II) salts.
Co-reporter:Zhi-Hui Liu, Yong-Cai Qiu, Ying-Hua Li, Guo Peng, Biao Liu, Hong Deng
Inorganic Chemistry Communications 2009 Volume 12(Issue 3) pp:204-207
Publication Date(Web):March 2009
DOI:10.1016/j.inoche.2008.12.011
By control of mixed organic ligands with different geometries, three unusual 4d–4f heterometallic coordination polymers, [AgLn(nic)2(ox)] · 2H2O [Ln = Eu (1); Dy (2); Ho (3)] [nic = nicotinate; ox = oxalate] have been synthesized under hydrothermal reaction. Three structures represent 3D open heterometallic coordination frameworks that are constructed from rare zigzag lanthanide-ox-silver chains and nic linkers. Furthermore, the luminescent property of complex 1 was discussed.Three unusual 3D 4d–4f coordination polymer, [AgLn(nic)2(ox)] · 2H2O [Ln = Eu (1); Dy (2); Ho (3)] [nic = nicotinate; ox = oxalate] were successfully synthesized. All three structures exhibit same 3D open heterometallic coordination frameworks that are constructed from rare zigzag lanthanide-ox-silver chains and nic linkers.
Co-reporter:Biao Liu, Yong-Cai Qiu, Guo Peng, Li Ma, Li-Ming Jin, Jin-Biao Cai, Hong Deng
Inorganic Chemistry Communications 2009 Volume 12(Issue 12) pp:1200-1203
Publication Date(Web):December 2009
DOI:10.1016/j.inoche.2009.09.018
Two new d10 coordination polymers, Zn(Beta)2 (1) and Cd2(Beta)3Cl(H2O) (2) (Hbeta = 5-benzyl-tetrazole) have been synthesized by the in situ [3 + 2] cycloaddition reaction of 5-benzylacetonitrile, sodium azide and MCl2 [M = Zn (1); M = Cd (2)] under hydrothermal condition. Complex 1 is a coordination polymer comprised of numerous mildly undulated two-dimensional (2D) layers with a (4, 4) topological network; while complex 2 is a 3D coordination framework constructed from the interconnection of various helical chains through cadmium–chlorine bridges. Furthermore, the luminescence properties of two complexes have been investigated.Two new d10 coordination polymers, Zn(Beta)2 (1) and Cd2(Beta)3Cl(H2O) (2) (Hbeta = 5-benzyl-tetrazole) have been synthesized by the in situ [3 + 2] cycloaddition reaction of 5-benzylacetonitrile, sodium azide and MCl2 [M = Zn (1); M = Cd (2)] under hydrothermal condition. Complex 1 is a coordination polymer comprised of numerous mildly undulated two-dimensional (2D) layers with a (4, 4) topological network; while complex 2 is a 3D coordination framework constructed from the interconnection of various helical chains through cadmium–chlorine bridges.
Co-reporter:Hong Deng, Yong-Cai Qiu, Ying-Hua Li, Zhi-Hui Liu, Olivier Guillou
Inorganica Chimica Acta 2009 Volume 362(Issue 6) pp:1797-1804
Publication Date(Web):20 April 2009
DOI:10.1016/j.ica.2008.08.020
Six lanthanide coordination polymers La2(1,4-BDOA)2(OX)(H2O) (1), Ln2(1,4-BDOA)2(OX)(H2O) [Ln = La (2); Ln = Pr (3); Ln = Sm (4); Ln = Eu (5); Ln = Tb (6)], [BDOA = benzene-1,4-dioxydiacetate; OX = oxalate] had been prepared under hydrothermal conditions, which were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Compounds 1–6 crystallize in a triclinic system, space group P1¯; compounds 1 and 2 are true structural supramolecular isomers based on BDOA ligands constructed from different acid effects; compounds 2–5 are isostructural and exhibit new 3D 12-connected topological networks, which are the same as the topological structure of 6, while 1 shows another 3D 11-connected topological architecture. Furthermore, the luminescent properties of 5 and 6 were studied.Six lanthanide coordination polymers La2(1,4-BDOA)2(OX)H2O 1, Ln2(1,4-BDOA)2(OX)H2O (Ln = La 2; Ln = Pr 3; Ln = Sm 4; Ln = Eu 5; Ln = Tb 6), (H2BDOA = benzene-1,4-dioxydiacetate; OX = oxalate) have been prepared under hydrothermal conditions. Compounds 1 and 2 are true structural supramolecular isomers based on BDOA ligands constructed from different acid effects.
Co-reporter:Hong Deng, Yong-Cai Qiu, Ying-Hua Li, Zhi-Hui Liu, Rong-Hua Zeng, Matthias Zeller and Stuart R. Batten
Chemical Communications 2008 (Issue 19) pp:2239-2241
Publication Date(Web):13 Mar 2008
DOI:10.1039/B800938D
The metal–organic framework [Cd15(5MT)18(OH)4(SO4)4] (5-MT = 5-methyl-1H-tetrazole) with an unprecedented Cd3(μ3-OH)(μ3-SO4) core and two kinds of tetrazole coordination modes was formed by self-assembly and in situ synthesis of the 5-MT tetrazole ligand; the structure exhibits an unusual 39·412·515 topological network and shows reversible shrinkage and expansion in a crystal-to-crystal dehydration/rehydration process.
Co-reporter:Yongcai Qiu, Zhihui Liu, Yinghua Li, Hong Deng, Ronghua Zeng and Matthias Zeller
Inorganic Chemistry 2008 Volume 47(Issue 12) pp:5122-5128
Publication Date(Web):May 10, 2008
DOI:10.1021/ic702366t
Two unusual d10 compounds, [Zn2(bipy)3(H2O)8(ClO4)2(paba)2]·2(bipy)·4H2O (1) and [Cd2(bipy)4(H2O)6(ClO4)2(paba)2]·(bipy)·5H2O (2) (bipy = 4,4′-bipyridine, paba = p-aminobenzoate), were obtained from reaction of the metal salts, bipy and paba in an EtOH/H2O mixture. The bipy ligands in the two compounds exhibit two new modes of coordinating to transition metal ions, resulting in the formation of large porous frameworks. Immersion of single crystals of 1 in an aqueous solution of NH4PF6 results in the formation of its hexafluorophosphate derivative 3 as shown by single crystal diffraction. Immersion of crystals of 3 in NaClO4 regenerates 1. Furthermore, compound 1 also shows interesting anion sensing properties in an EtOH/H2O mixture.
Co-reporter:Hong Deng ; Yongcai Qiu ; Carole Daiguebonne ; Nicolas Kerbellec ; Olivier Guillou ; Matthias Zeller ;Stuart R. Batten
Inorganic Chemistry 2008 Volume 47(Issue 13) pp:5866-5872
Publication Date(Web):May 31, 2008
DOI:10.1021/ic800164b
Hydrothermal reaction of diaminomaleonitrile and copper salts under different conditions resulted in copper cyanide coordination polymers {[Cu(H2O)(NH3)4][Cu3(CN)5]·H2O}n (1), {(CH3)4N[Cu(H2O)(NH3)4][Cu4(CN)7]}n (2), and {(CH3OH2)2[Cu2(CN)3]}n (3). 1 and 2 are new mixed-valence Cu(I,II), two 3D organic−inorganic molecular framework complexes that exhibit ionic inclusion. 3 is an open copper cyanide framework hosting a guest molecule. Cyanides in 1, 2, and 3 are produced by in situ C−C bond cleavage of diaminomaleonitrile, and then the remaining product is oxidized to form an oxalate group. The potential porosity of the hydrated coordination polymer 3 was estimated using a computational method based on Connolly’s algorithm.
Co-reporter:Guo Peng, Yong-Cai Qiu, Zhi-Hui Liu, Ying-Hua Li, Biao Liu, Hong Deng
Inorganic Chemistry Communications 2008 Volume 11(Issue 11) pp:1409-1411
Publication Date(Web):November 2008
DOI:10.1016/j.inoche.2008.09.017
The self-assembly of nicotinic acid and sodium oxalate with mixed 3d–4f metal salts under hydrothermal conditions gave three isostructural 3D 3d–4f coordination polymers, [LnCu(nic)2(ox)] · xH2O [Ln = La, x = 1 (1); Ln = Eu, x = 2 (2); Ln = Gd, x = 2 (3)] [ox = oxalate, nic = nicotinate]. All three structures exhibit same unusual 3D microporous heterometallic coordination frameworks that are built up by rare tetranuclear Ln2Cu2 clusters and mixed ox and nic linkers. Furthermore, the luminescent property of complex 2 has also been investigated.Three unusual 3D 3d–4f coordination polymer, [LnCu(nic)2(ox)] · xH2O [Ln = La, x = 1 (1); Ln = Eu, x = 2 (2); Ln = Gd, x = 2 (3)] [ox = oxalate, nic = nicotinate] have been successfully synthesized. All three structures exhibit same unusual 3D microporous heterometallic coordination frameworks that are built up by rare tetranuclear Ln2Cu2 clusters and mixed ox and nic linkers. Furthermore, the fluorescent property of complex 2 has been investigated.
Co-reporter:Hong Deng, Ying-Hua Li, Yong-Cai Qiu, Zhi-Hui Liu, Matthias Zeller
Inorganic Chemistry Communications 2008 Volume 11(Issue 10) pp:1151-1154
Publication Date(Web):October 2008
DOI:10.1016/j.inoche.2008.06.024
The self-assembly of pyrazine-2-carboxylate and oxalate with mixed-metal salts under hydrothermal conditions gave three isostructural 3D 4d-4f coordination polymers, LnAg(ox)(2-pzc)2 · H2O [Ln = Eu (1); Tb (2); Dy (3)] [ox = oxalate, 2-pzc = pyrazine-2-carboxylate]. All three structures exhibit same unusual 3D nanoporous heterometallic coordination frameworks constructed by zigzag lanthanide–oxalate chains and Ag(2-pzc)2 units. Furthermore, the luminescent properties of complexes 1 and 2 are discussed.Three unusual 3D 4d–4f coordination polymer, LnAg(ox)(2-pzc)2·H2O [Ln = Eu (1); Tb (2); Dy (3)] [ox = oxalate, 2-pzc = pyrazine-2-carboxylate] has been hydrothermal synthesized and characterized. All three structures exhibit same unusual 3D nanoporous heterometallic coordination frameworks constructed by helical lanthanide–oxalate chains and Ag(2-pzc)2 units. They represent the first examples of 3D 4d–4f heterometallic open coordination frameworks by spontaneous assembly.
Co-reporter:Hong Deng, Zhihui Liu, Yongcai Qiu, YingHua Li, Matthias Zeller
Inorganic Chemistry Communications 2008 Volume 11(Issue 9) pp:978-981
Publication Date(Web):September 2008
DOI:10.1016/j.inoche.2008.04.041
A 3d–4f heterometallic coordination polymer, {[Cu10Er4(IN)14ClBr7(H2O)10] · 2H2O}n (1) [IN = isonicotinate], has been synthesized by hydrothermal reaction of the ligand with CuBr2, NaCl and Er2O3. Complex 1 represents a rare 3D heterometallic coordination framework constructed from Er-carboxylate subunits and unique Cu-halide (Br/Cl) chains that are bridged by a single type of linear ligand. Furthermore, the luminescent properties of complex 1 have also been investigated.A 3D 3d–4f coordination polymer, {[Cu10Er4(IN)14ClBr7(H2O)10] · 2H2O}n (1) [IN = isonicotinic acid], has been hydrothermal synthesized and characterized. Complex 1 shows a rare 3D heterometallic coordination framework. Furthermore, the luminescent properties of complex 1 have also been investigated.
Co-reporter:Yongcai Qiu, Kunnan Wang, Yan Liu, Hong Deng, Feng Sun, Yuepeng Cai
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:1819-1824
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.09.027
Two novel complexes [Cu(DBA)2(1,10-phen)]n (1) and [Cd(DBA)2(1,10-phen)2] (2) [HDBA = benzilic acid: (C6H5)2C(OH)COOH] have been synthesized and characterized by element analysis and fluorescence spectroscopy. The crystal structures of compounds 1, 2 and HDBA (3) were also determined. Complex 1 is a one-dimensional (1D) helical infinite chain, in which [(1,10)-phen]Cu(II) units were bridged by benzilic acid. Complex 2 is a mononuclear structure, and is self-assembled through π–π stacking interactions to form a 1D helical chain. Compound 3 is self-assembled to form a 1D helical chain through hydrogen bonds interactions. Thermal analyses indicate that complexes 1 and 2 are stable under 200 and 254 °C in solid state, respectively.A novel helical copper(II) complex polymer [Cu(L)2(1,10-phen)]n and a distorbed octahedron cadmium(II) complex Cd(L)2(1,10-phen)2 [L = benzilic acid: (C6H5)2C(OH)COOH] have been synthesized. The copper(II) polymer is like a 1D infinite nanostructure chain was derived from a hydroxy and a carboxyl groups bridging [(1,10)-phen]CuII units. The rutile framework cadmium(II) complex forms a 1D chain through π–π stacking interactions between Phens.
Co-reporter:Hong Deng, Hongyu Chen, He Li
Materials Chemistry and Physics 2007 Volume 101(2–3) pp:509-513
Publication Date(Web):15 February 2007
DOI:10.1016/j.matchemphys.2006.10.002
A low-temperature solvothermal synthetic method was developed for the large-scale synthesis of uniform-sized ferrite MFe2O4 (M = Mg, Cu, Ni) microspheres. The size of the as-prepared ferrite MFe2O4 microspheres could be controlled to be diameters 300–800 nm in diameter by adjusting some growth parameters, such as reaction time and concentration. The structures of the as-prepared ferrite MFe2O4 microspheres were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDAX). The magnetic properties of the ferrite MFe2O4 microspheres were also investigated.
Co-reporter:Yongcai Qiu, Carole Daiguebonne, Jianqiang Liu, Ronghua Zeng, Nicolas Kerbellec, Hong Deng, Olivier Guillou
Inorganica Chimica Acta 2007 Volume 360(Issue 10) pp:3265-3271
Publication Date(Web):2 July 2007
DOI:10.1016/j.ica.2007.03.063
Four crystalline lanthanide(III) three-dimensional (3D) coordination polymers {[La(BDOA)1.5(H2O)] · H2O}n (1), {[Nd(BDOA)1.5(H2O)] · H2O}n (2), [Tm(BDOA)1.5(H2O)]n (3), [Yb(BDOA)1.5(H2O)]n (4) were obtained under hydrothermal conditions and characterized by elemental analysis, IR, as well as single-crystal X-ray diffraction. Compounds 1 and 2 crystallize in the monoclinic system, space group P21/c, they are isostructural and exhibit the same 321.457.513 topological network constructed from different coordination modes of two BDOA ligands, whereas isostructural 3 and 4 crystallizes in the triclinic system, space group P1¯, it holds 39.420.57 topological architecture based on another two different coordination modes BDOA ligands. Moreover, a computational method is applied to evaluate the potential porosity of complex 1.Four crystalline lanthanide(III) three-dimensional (3D) coordination polymers {[La(BDOA)1.5(H2O)] · H2O}n (1), {[Nd(BDOA)1.5(H2O)] · H2O}n (2), [Tm(BDOA)1.5(H2O)]n (3), [Yb(BDOA)1.5(H2O)]n (4) were obtained under hydrothermal conditions.
Co-reporter:Guizhu Li, Yongcai Qiu, Yuan Hou, Hongfei Li, Lisha Zhou, Hong Deng and Yuegang Zhang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 3) pp:NaN1109-1109
Publication Date(Web):2014/11/12
DOI:10.1039/C4TA04864D
A facile solvothermal method was used to synthesize V2O5 nanosheet hierarchical structures. Using different solvent systems, we obtained the hierarchical structures with different nanosheet thicknesses of <10 nm, 50–100 nm and 100–200 nm, respectively. A systematic investigation of their electrochemical properties showed that both the reversible lithium storage capacity and the cycling stability increased with the reduced thickness of nanosheets. In order to prevent the serious structural damage of the V2O5 electrodes during cycling, we employed a voltage-regulation charge/discharge scheme which led to a long cycle-life with an average capacity decay of 0.04% (2.0 to 3.0 V) and 0.10% per cycle (2.8 to 4.0 V) over 500 cycles.
Co-reporter:Li Liang, Guo Peng, Guizhu Li, Yanhua Lan, Annie K. Powell and Hong Deng
Dalton Transactions 2012 - vol. 41(Issue 19) pp:NaN5823-5823
Publication Date(Web):2012/02/21
DOI:10.1039/C2DT30175J
A family of six dinuclear lanthanide complexes have been obtained via in situ hydrothermal synthesis with lanthanide ions as catalyst. These six complexes are formulated as [Ln2(3-Htzba)2(3-tzba)2(H2O)8]·4H2O [Ln = Gd, 1; Dy, 2; Eu, 3; Tb, 4; Sm, 5; Er, 6; 3-H2tzba = 3-(1H-tetrazol-5-yl)benzoic acid]. The magnetic investigations show that complex 2 behaves as a single-molecule magnet (SMM) with a quantum relaxation time of ∼10−2 s.
Co-reporter:Hong Deng, Yong-Cai Qiu, Ying-Hua Li, Zhi-Hui Liu, Rong-Hua Zeng, Matthias Zeller and Stuart R. Batten
Chemical Communications 2008(Issue 19) pp:NaN2241-2241
Publication Date(Web):2008/03/13
DOI:10.1039/B800938D
The metal–organic framework [Cd15(5MT)18(OH)4(SO4)4] (5-MT = 5-methyl-1H-tetrazole) with an unprecedented Cd3(μ3-OH)(μ3-SO4) core and two kinds of tetrazole coordination modes was formed by self-assembly and in situ synthesis of the 5-MT tetrazole ligand; the structure exhibits an unusual 39·412·515 topological network and shows reversible shrinkage and expansion in a crystal-to-crystal dehydration/rehydration process.
