Co-reporter:Cai-Feng Wang, Jing Lin Zuo, Jie-Wen Ying, Tong Ren and Xiao-Zeng You
Inorganic Chemistry October 20, 2008 Volume 47(Issue 20) pp:9716-9722
Publication Date(Web):September 24, 2008
DOI:10.1021/ic8011684
Four tetranuclear heterometallic compounds, [(Tp)Fe(CN)3]2[Ru2(DMBA)4] (1), [(MeTp)Fe(CN)3]2[Ru2(DMBA)4] (2), [(iBuTp)Fe(CN)3]2[Ru2(DMBA)4] (3), and [(PhTp)Fe(CN)3]2[Ru2(DMBA)4] (4) [DMBA = N,N′-dimethylbenzamidinate, Tp = (hydrotris(pyrazolyl)borate, MeTp = (methyltris(pyrazolyl)borate, iBuTp = (2-methylpropyltris(pyrazolyl)borate, and PhTp = (tris(pyrazolyl)phenylborate)] were prepared from the combination of Ru2(DMBA)4(NO3)2 and an appropriate [(RTp)Fe(CN)3]−. Molecular structures of compounds 1−4 were established using single-crystal X-ray diffraction, and all feature a linear Fe−C≡N−Ru−Ru−N≡C−Fe array. The magnetic study revealed that the temperature dependence of χMT is mostly attributed to the zero-field splitting of the Ru2 center, indicating the absence of strong spin coupling among three metallic centers. The electronic independence was further confirmed by the vis−NIR spectroscopic studies. Also described are the voltammetric properties of these compounds.
Co-reporter:Jing-Yuan Ge, Long Cui, Jing Li, Fei Yu, You Song, Yi-Quan Zhang, Jing-Lin ZuoMohamedally Kurmoo
Inorganic Chemistry 2017 Volume 56(Issue 1) pp:336-343
Publication Date(Web):December 15, 2016
DOI:10.1021/acs.inorgchem.6b02243
Co-reporter:Hai-Ying Wang;Jing-Yuan Ge;Carol Hua;Cheng-Qi Jiao;Yue Wu;Chanel F. Leong; Dr. Deanna M. D'Alessro; Dr. Tao Liu; Dr. Jing-Lin Zuo
Angewandte Chemie 2017 Volume 129(Issue 20) pp:5557-5562
Publication Date(Web):2017/05/08
DOI:10.1002/ange.201611824
AbstractA major challenge is the development of multifunctional metal–organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4-pyridyl)tetrathiafulvalene (TTF(py)4) and spin-crossover FeII centers. The materials exhibit redox activity, in addition to thermally and photo-induced spin crossover (SCO). A crystal-to-crystal transformation induced by I2 doping has also been observed and the resulting intercalated structure determined. The conductivity could be significantly enhanced (up to 3 orders of magnitude) by modulating the electronic state of the framework via oxidative doping; SCO behavior was also modified and the photo-magnetic behavior was switched off. This work provides a new strategy to tune the spin state and conductivity of framework materials through guest-induced redox-state switching.
Co-reporter:Hai-Ying Wang;Jing-Yuan Ge;Carol Hua;Cheng-Qi Jiao;Yue Wu;Chanel F. Leong; Dr. Deanna M. D'Alessro; Dr. Tao Liu; Dr. Jing-Lin Zuo
Angewandte Chemie International Edition 2017 Volume 56(Issue 20) pp:5465-5470
Publication Date(Web):2017/05/08
DOI:10.1002/anie.201611824
AbstractA major challenge is the development of multifunctional metal–organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4-pyridyl)tetrathiafulvalene (TTF(py)4) and spin-crossover FeII centers. The materials exhibit redox activity, in addition to thermally and photo-induced spin crossover (SCO). A crystal-to-crystal transformation induced by I2 doping has also been observed and the resulting intercalated structure determined. The conductivity could be significantly enhanced (up to 3 orders of magnitude) by modulating the electronic state of the framework via oxidative doping; SCO behavior was also modified and the photo-magnetic behavior was switched off. This work provides a new strategy to tune the spin state and conductivity of framework materials through guest-induced redox-state switching.
Co-reporter:Hai-Ying Wang, Long Cui, Jia-Ze Xie, Chanel F. Leong, Deanna M. D’Alessandro, Jing-Lin Zuo
Coordination Chemistry Reviews 2017 Volume 345(Volume 345) pp:
Publication Date(Web):15 August 2017
DOI:10.1016/j.ccr.2016.10.011
•Coordination polymers based on tetrathiafulvalenes showing redox-active properties.•Charge transfer and electron transport are studied in TTF coordination polymers.•Some coordination polymers based on tetrathiafulvalenes showing porosity and multifunctions.This review article focuses on the development of coordination polymers based on tetrathiafulvalene and its derivatives. We aim to demonstrate novel opportunities for these coordination polymers in terms of their architectures and potential applications. The review is presented in five general sections according to the type of coordinating functional group in the organic linkers. Synthetic approaches, structural analyses, as well as physical and chemical properties are presented for each example. Valuable potential applications and perspectives for these novel materials are also discussed.
Co-reporter:Zhong-Peng Lv;Tao Wang;Jing-Yuan Ge;Zhong-Zhi Luan;Di Wu;Shouheng Sun
Journal of Materials Chemistry C 2017 vol. 5(Issue 29) pp:7200-7206
Publication Date(Web):2017/07/27
DOI:10.1039/C7TC01021D
We report a solution phase based assembly method to tune the transport mechanism and magnetoresistance (MR) of Fe3O4 nanoparticles (NPs). The NP topological arrangement is altered by the NP coating of tetrathiafulvalene carboxylic acid (TTFCOOH) or its dicarboxylic analogue (TTF(COOH)2). Consequently, the transport mechanism of the assembly switches from tunneling to Mott hopping. The MR ratios of the Fe3O4 NP assemblies can be further tuned by the polarity of the solvent used in the ligand exchange process. The TTF(COO)2-coated Fe3O4 NP assembly has a 5% room temperature MR ratio, which is the highest value among all TTF-COO-Fe3O4 NP assemblies reported so far.
Co-reporter:Jing Li;Rong-Min Wei;Tian-Cheng Pu;Fan Cao;Li Yang;Yuan Han;Yi-Quan Zhang;You Song
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 1) pp:114-122
Publication Date(Web):2017/01/13
DOI:10.1039/C6QI00407E
The magnetic relaxation and magnetization blocking barriers of butterfly complexes, [Dy2Zn2(L)4(NO3)2(CH3OH)2] (1), [Dy2Mn2(L)4(NO3)2(DMF)2] (2) and [Dy2Co2(L)4(NO3)2(DMF)2]·2DMF (3) (H2L = (E)-2-ethoxy-6-(((2-hydroxyphenyl)imino)methyl)phenol), were systematically investigated. The change of SMM behavior originating from the purposeful replacement of two ZnII sites in 1 with MnII and CoII was elucidated by a combined experimental and theoretical study. The quantum tunnelling of magnetization (QTM) was observed in 1. Contrarily, it was quenched in 2 and 3 by spin–spin exchange. A detailed comparative study on these closely-related model complexes reveals the remarkable changes of the ligand field splitting, anisotropy of the Dy-coordinated moiety and the total exchange spectrum due to the replacement of ZnII with CoII and MnII.
Co-reporter:Long Cui;Jing-yuan Ge;Chanel F. Leong;Deanna M. D'Alessandro
Dalton Transactions 2017 vol. 46(Issue 12) pp:3980-3988
Publication Date(Web):2017/03/21
DOI:10.1039/C6DT04903F
An oxamato unit has been introduced into a tetrathiafulvalene (TTF) system for the first time via direct condensation, generating a new π-extended TTF ligand, TTF-Et2H2opba (opba = ortho-phenylenebis-oxamato). On the basis of this ligand, the Cu(II) complex [(n-Bu)4N]2[Cu(TTF-opba)] (1) has been obtained. By employing this complex as a “metalloligand”, we have successfully prepared an interesting heterometallic one-dimensional complex {[Cu(TTF-opba)][Mn(CH3OH)2]}n (2), via coordination of the free carbonyl-oxygen atoms of the two oxamato groups with Mn(II) ions. The new compounds have been structurally characterized, and their electrochemical and magnetic properties probed. Complex 2 shows a ferrimagnetic behavior with g = 1.96 and J = −22.36 cm−1.
Co-reporter:Fei Yu;Zi-Heng Cao;Jing-Yuan Ge;Yi-Chen Sun;Zhong-Wen Ouyang;Zhenxing Wang;Mohamedally Kurmoo
Dalton Transactions 2017 vol. 46(Issue 13) pp:4317-4324
Publication Date(Web):2017/03/27
DOI:10.1039/C7DT00110J
Three Fe(III) dimers, [Fe2(L-H)2]·2CH3CN (1), [Fe2(L-OCH3)2] (2) and [Fe2(L-OC2H5)2]·2CH3CN (3), containing the pentadentate O,N,N,O,O-donor Schiff-base ligands with variable size pendants, were synthesized and structurally characterized. The three ligands were generated in situ from 2-(iminomethyl)phenol, 2-methoxy-6-(iminomethyl)phenol and 2-ethoxy-6-(iminomethyl)phenol, respectively. All three crystal structures contain centrosymmetric dimers of edge-sharing octahedra of Fe(III) ions through a pair of μ2-phenoxido bridges. The exchange coupling is ferromagnetic for 1 (J = +0.47(1) cm−1, ∠Fe–O–Fe = 98.02°) and 2 (J = +0.86(1) cm−1, ∠Fe–O–Fe = 97.17°), but antiferromagnetic for 3 (J = −0.72(1) cm−1, ∠Fe–O–Fe = 98.53°), which are correlated by high-field electron paramagnetic resonance revealing moderate magneto-anisotropy of D = −0.24(3) cm−1, E = 0.08(1) cm−1 for 1, D = −0.38(1) cm−1, E = 0.11(1) cm−1 for 2, and D = 0.30(3) cm−1, E = 0.02(1) cm−1 for 3. The exchange couplings were further estimated by DFT calculations, which gave the finest Fe–O–Fe angle of 97.83° for the ferromagnetic–antiferromagnetic crossover.
Co-reporter:Jing-Yuan Ge;Hai-Ying Wang;Jing Li;Jia-Ze Xie;You Song
Dalton Transactions 2017 vol. 46(Issue 10) pp:3353-3362
Publication Date(Web):2017/03/07
DOI:10.1039/C7DT00298J
Three dinuclear lanthanide complexes, [Ln2(thd)4Pc]·2C6H6 (Hthd = 2,2,6,6-tetramethylheptanedione, Ln = Sm (1), Tb (2), Dy (3)), have been synthesized based on phthalocyanine (Pc). They can be reversibly transformed into [Ln2(thd)4Pc] (Ln = Sm (1′), Tb (2′), Dy (3′)) via desolvation and resolvation of the lattice benzene molecules. This change generates dramatic influences on the structural and magnetic properties of the dysprosium analogue. In complex 3, one crystallographically independent metal center is observed, and it exhibits a single relaxation process of magnetization with an energy barrier of 55.7 K. Upon desolvation, the resulting complex 3′ contains two types of metal centers, and shows the field-induced single-molecule magnetic behavior with two thermally activated magnetic relaxation processes. The anisotropy barriers for 3′ are as high as 63.3 K and 109.6 K, respectively. This work confirms that the solvated molecules can finely tune the magnetic relaxation mechanisms.
Co-reporter:Bin Chen, Zhong-Peng Lv, Carol Hua, Chanel F. Leong, Floriana Tuna, Deanna M. D’Alessandro, David Collison, and Jing-Lin Zuo
Inorganic Chemistry 2016 Volume 55(Issue 9) pp:4606-4615
Publication Date(Web):April 12, 2016
DOI:10.1021/acs.inorgchem.6b00437
The synthesis of a π-extended bridging ligand with both redox-active tetrathiafulvalene (TTF) and 1,10-phenanthroline (phen) units, namely, bis(1,10-phenanthro[5,6-b])tetrathiafulvalene (BPTTF), was realized via a self-coupling reaction. Using this ligand and Ru(tbbpy)2Cl2 (tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine), the dinuclear ruthenium(II) compound [{Ru(tbbpy)2}2(BPTTF)](PF6)4 (1) has been obtained by microwave-assisted synthesis. Structural characterization of 1 revealed a crossed arrangement of the TTF moieties on adjacent dimers within the crystal structure. The optical and redox properties of 1 were investigated using electrochemical, spectroelectrochemical, electron paramagnetic resonance (EPR), and absorption spectroscopic studies combined with theoretical calculations. One exhibits a rich electrochemical behavior owing to the multiple redox-active centers. Interestingly, both the ligand BPTTF and the ruthenium compound 1 are EPR-active in the solid state owing to intramolecular charge-transfer processes. The results demonstrate that the TTF-annulated bis(phen) ligand is a promising bridging ligand to construct oligomeric or polymeric metal complexes with multiple redox-active centers.
Co-reporter:Jin-Feng Mei, Zhong-Peng Lv, Jian-Cheng Lai, Xiao-Yong Jia, Cheng-Hui Li, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2016 vol. 45(Issue 13) pp:5451-5454
Publication Date(Web):02 Mar 2016
DOI:10.1039/C6DT00346J
A novel europium(III) complex simultaneously exhibiting photocolorimetric and photofluorometric behavior was obtained. Multiple distinguishable identities can be obtained and reversibly modulated using light as external stimuli. With this novel photo-responsive complex, double encryption and advanced anti-counterfeiting were realized.
Co-reporter:Jing-Yuan Ge, Jia-Ze Xie, Zhuang-Yu Zhao, Jing Ru, You Song and Jing-Lin Zuo
RSC Advances 2016 vol. 6(Issue 2) pp:1143-1150
Publication Date(Web):17 Dec 2015
DOI:10.1039/C5RA23697E
Three heterodinuclear complexes, [(NiL1)Ln(L2)(CH3OH)]·acetone (Ln = Gd (1), Tb (2), Dy (3); H3L1 = 1,1,1-tris[(salicylideneamino)methyl]ethane), were stepwise synthesized based on a thiacalix[4]arene ligand (H2L2 = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-dihydroxy-26,28-dimethoxy thiacalix[4]arene). In 1–3, NiII and LnIII ions are doubly bridged by two phenoxo O atoms of L1. The NiII ion, only coordinated by the L1 ligand, features a {NiN3O3} coordination sphere; and the LnIII ion adopts a seven-coordinated {LnO7} environment, capped by one thiacalix[4]arene ligand in a bowl-shaped conformation. Magnetic studies on all complexes reveal that ferromagnetic couplings are operative between the NiII and LnIII ions. The dysprosium analogue (3) exhibits field-induced single-molecule magnet (SMM) behavior under a dc-applied field of 800 Oe. Moreover, the Dy:Y (1:10) magnetically diluted sample (3′) shows slow magnetic relaxation at zero dc field. The results demonstrate that the stepwise synthetic method is more useful and effective than self-assembly for designing new 3d–4f heterodinuclear complexes with the thiacalix[4]arene ligand or other derivatives. The introduction of this type of thiacalix[4]arene ligand into the heterodinuclear complexes renders them promising candidates for new SMMs.
Co-reporter:Xian-He Bu
Science China Chemistry 2016 Volume 59( Issue 8) pp:927-928
Publication Date(Web):2016 August
DOI:10.1007/s11426-016-5603-2
Co-reporter:Hai-Ying Wang; Yue Wu; Chanel F. Leong; Deanna M. D’Alessandro
Inorganic Chemistry 2015 Volume 54(Issue 22) pp:10766-10775
Publication Date(Web):October 29, 2015
DOI:10.1021/acs.inorgchem.5b01803
Seven new coordination polymers based on the redox-active tetra(4-pyridyl)-tetrathiafulvalene ligand (TTF(py)4) and different transition-metal ions, namely, {[Cu(hfac)2][TTF(py)4]·2(CH2Cl2)}n (1), {[Co(acac)2][TTF(py)4]0.5·(CHCl3)}n (2), {[Mn(hfac)2][TTF(py)4]0.5}n (3), {[Cu2(OAc)4][TTF(py)4]0.5·1.5(CHCl3)·0.5(H2O)·(CH3CN)}n (4), {[Mn(SCN)2][TTF(py)4]·6(CH2Cl2)}n (5), {[Mn(SeCN)Cl][TTF(py)4]}n (6), and {Cu2[TTF(py)4]2·(ClO4)2·2.5(CH2Cl2)·1.5(CH3CN)}n (7), were synthesized and characterized. The tetrapyridyl ligand coordinates to metal ions in a bidentate or tetradentate fashion, forming complexes 1–7 with different structures. Complex 1 exhibits a one-dimensional chain structure. Complexes 2, 3, and 4 possess similar (4,2)-connected binodal two-dimensional networks, while complexes 5 and 6 have similar (4,4)-connected binodal two-dimensional networks with two different rings. Complex 7 shows a 2-fold interpenetrated (4,4)-connected binodal PtS-type three-dimensional framework. Meanwhile, these complexes feature diverse nonclassical hydrogen bonding interactions. In addition, magnetic and solid-state electrochemical properties for typical complexes have been studied.
Co-reporter:Zhongguo Li, Feng Gao, Zhengguo Xiao, Guanghong Ao, Xingzhi Wu, Yu Fang, Zhongquan Nie, Tai-Huei Wei, Junyi Yang, Yuxiao Wang, Xueru Zhang, Jinglin Zuo, Yinglin Song
Dyes and Pigments 2015 Volume 119() pp:70-74
Publication Date(Web):August 2015
DOI:10.1016/j.dyepig.2015.03.025
•First investigation on nonlinear optical properties of mixed sandwich-type complexes.•Nonlinearity parameters were evaluated from experimental data.•Large nonlinear optical susceptibility.A novel sandwich-type erbium triple-decker complexes with mixed phthalocyanine and Schiff-base ligands was synthesized and characterized by optical absorption spectroscopy. The third-order nonlinear optical properties of the sandwich-type complexes in dichloromethane were investigated using Z-scan measurement at 532 nm with 20 ps pulses. The Z-scan results reveal that the sandwich-type complexes exhibit strong reverse saturable absorption and self-focusing effect. The third-order nonlinear susceptibility and second-order hyperpolarizability of the complexes are estimated to be 7.31 × 10−13 esu and 0.94 × 10−30 esu, respectively. Our results indicate that the sandwich-type mixed (phthalocyaninato)(Schiff-base) complexes are promising candidate materials for future nonlinear optical applications such as wavelength conversion and optical switching.
Co-reporter:Bin Chen, Zhong-Peng Lv, Chanel F. Leong, Yue Zhao, Deanna M. D’Alessandro, and Jing-Lin Zuo
Crystal Growth & Design 2015 Volume 15(Issue 4) pp:1861-1870
Publication Date(Web):February 11, 2015
DOI:10.1021/acs.cgd.5b00014
Four new polymeric metal compounds based on the redox-active tetrathiafulvalene-tetrabenzoate ligand and different divalent cations (Co(II), Cd(II), Ba(II)), including {[Co2(TTFTB)(2,2′-Bpy)2(H2O)2]·DMF·2H2O}n (1), {[Co2(TTFTB)(4,4′-Bpy)(H2O)6]·DMF}n (2), {[Cd(H2TTFTB)(Bpea)(H2O)2]·DMF·3H2O}n (3), and {[Ba(H2TTFTB)(H2O)2]·DMF·C2H5OH}n (4) (2,2′-Bpy = 2,2′-bipyridine, 4,4′-Bpy = 4,4′-bipyridine, Bpea = 1,2-bis(4-pyridyl)ethane), were synthesized and characterized. The versatile redox-active tetracarboxylate ligand was coordinated to divalent metal ions in a multidentate fashion, forming different structures for complexes 1–4. Complex 1 exhibits a one-dimensional chain structure, whereas the 3-fold interpenetrating 3,4L13 net was observed in complex 2. Importantly, complex 3 displays a (3,8)-connected tfz-d net and complex 4 features a new (4,8)-connected three-dimensional topological network with a point symbol of (44.62)2(48.64.816). The solid-state electrochemical properties and gas adsorption behaviors of 3 and 4 were subsequently investigated. Due to the incorporation of π-electron conjugated TTF rings into porous metal–organic frameworks, complexes 3 and 4 exhibit two reversible oxidation processes and adsorption selectivity for CO2 over N2. These compounds enrich the study of redox-active porous materials.
Co-reporter:Jing-Yuan Ge, Jing Ru, Feng Gao, You Song, Xin-Hui Zhou and Jing-Lin Zuo
Dalton Transactions 2015 vol. 44(Issue 35) pp:15481-15490
Publication Date(Web):20 Jul 2015
DOI:10.1039/C5DT02062J
A series of pentanuclear LnIII clusters, [Ln5(μ4-OH)(μ3-OH)4(L1)(acac)6] (H4L1 = p-tert-butylthiacalix[4]arene; acac = acetylacetonate; Ln = Dy, Ho, Er) and [Ln5(μ5-OH)(μ3-OH)4(L1)(L2)2(acac)2(CH3OH)2] (H3L2 = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26,27-trihydroxy-28-methoxy thiacalix[4]arene; Ln = Dy, Ho, Er), have been synthesized based on the thiacalix[4]arene ligand. All of these complexes feature a square-based pyramid with four triangular Ln3 structural motifs. One μ4-OH group bridges four LnIII ions in the basal plane of 1–3, while the OH group in complexes 4–6 adopts the μ5-coordination mode. Our results illuminate the coordination modes of the versatile thiacalix[4]arene ligands and their application to new cluster compounds. The structural and magnetic studies confirm that the molecular symmetries and coordination geometries for lanthanide metal cores have a significant effect on some parameters as single-molecule magnets. Among them, two Dy5 pyramids exhibit distinct slow magnetic relaxation.
Co-reporter:Jing Ru, Tian-Xiang Zong, Jing-Yuan Ge, Min-Xia Yao and Jing-Lin Zuo
RSC Advances 2015 vol. 5(Issue 113) pp:93470-93479
Publication Date(Web):23 Oct 2015
DOI:10.1039/C5RA15752H
A new ruthenium(III)-based building block, trans-(Ph4P)[RuIII(L)2(CN)2] (L = 2′-hydroxyacetophenone imine), has been synthesized and characterized. Reactions of this building block with different MnIII Schiff base (SB) complexes, [Mn(SB)(H2O)2]ClO4, result in 1-D zigzag chain complexes, [RuIII(L)2(CN)2MnIII(SB)]n (SB = salen, 1; salcy, 2; nappa, 4; napcy, 5), respectively. X-ray crystallographic studies reveal that each of the MnIII centers has a distorted octahedral environment, while complex 3 possesses a single cationic chain structure consisting of [Cu(chxn)2][Ru(L)2(CN)2]n units and their corresponding [Ru(L)2(CN)2]− anions. Compounds 1–3 exhibit antiferromagnetic coupling between the RuIII and MnIII/CuII centers, whereas 4 and 5 reveal ferromagnetic coupling between the RuIII and MnIII centers through the cyano bridges. Furthermore, magneto-structural correlation for some typical cyano-bridged heterobimetallic RuIII–MnIII/CuII compounds is discussed.
Co-reporter:Long Cui;Feifei Zhu;Chanel F. Leong;Jing Ru;Feng Gao
Science China Chemistry 2015 Volume 58( Issue 4) pp:650-657
Publication Date(Web):2015 April
DOI:10.1007/s11426-014-5177-9
Reaction of [Mn(TTF-salphen)][OAc] (TTF-salphen2−=2,2′-((2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3-benzodithiole-5,6-diyl)bis(nitrilomethylidyne)bis(phenolate)dianion) and the cyanometalate building blocks [n-Bu4N][(Tp)Fe(CN)3] (Tp−=Tris(pyrazolyl)hydroborate) or [n-Bu4N][Ru(salen)(CN)2] (salen2−=N,N′-ethylenebis(salicylideneimine)dianion) resulted in the formation of two redox-active complexes, the dinuclear heterometallic complex [(Tp)Fe(CN)3Mn(TTF-salphen)·CH3OH] (1) and the one dimensional complex [Ru(salen)(CN)2Mn(TTF-salphen)]n (2). Both complexes were characterized by X-ray crystallography and solid state electrochemistry, in addition to static and dynamic magnetic measurements. Antiferromagnetic couplings are found to be operative between metal ion centers bridged by cyanide in both complexes. Complex 1 exhibited field-induced SMM behavior with an energy barrier of 13.8 K. The introduction of the redox-active TTF unit into cyanide-bridged complexes with interesting magnetic properties renders them promising candidates for the construction of new hybrid inorganic-organic materials.
Co-reporter:Zhong-Peng Lv, Zhong-Zhi Luan, Hai-Ying Wang, Sheng Liu, Cheng-Hui Li, Di Wu, Jing-Lin Zuo, and Shouheng Sun
ACS Nano 2015 Volume 9(Issue 12) pp:12205
Publication Date(Web):November 13, 2015
DOI:10.1021/acsnano.5b05444
We report a strategy to coat Fe3O4 nanoparticles (NPs) with tetrathiafulvalene-fused carboxylic ligands (TTF-COO−) and to control electron conduction and magnetoresistance (MR) within the NP assemblies. The TTF-COO-Fe3O4 NPs were prepared by replacing oleylamine (OA) from OA-coated 5.7 nm Fe3O4 NPs. In the TTF-COO-Fe3O4 NPs, the ligand binding density was controlled by the ligand size, and spin polarization on the Fe3O4 NPs was greatly improved. As a result, the interparticle spacing within the TTF-COO-Fe3O4 NP assemblies are readily controlled by the geometric length of TTF-based ligand. The shorter the distance and the better the conjugation between the TTF’s HOMO and LUMO, the higher the conductivity and MR of the assembly. The TTF-coating further stabilized the Fe3O4 NPs against deep oxidation and allowed I2-doping to increase electron conduction, making it possible to measure MR of the NP assembly at low temperature (<100 K). The TTF-COO-coating provides a viable way for producing stable magnetic Fe3O4 NP assemblies with controlled electron transport and MR for spintronics applications.Keywords: electron-conduction; Fe3O4 nanoparticles; magnetoresistance; spin transport; TTF;
Co-reporter:Feng Gao, Fei-Fei Zhu, Xing-Yong Wang, Yan Xu, Xin-Ping Wang, and Jing-Lin Zuo
Inorganic Chemistry 2014 Volume 53(Issue 10) pp:5321-5327
Publication Date(Web):May 2, 2014
DOI:10.1021/ic5006117
After the chemical oxidation of the neutral tetrakis(methylthio)tetrathiafulvalene (TMT-TTF, 1) by specific oxidation agents with weakly coordinating anion, [Al(ORF)4]− [ORF = OC(CF3)3], the radical cation TMT-TTF•+ (1•+) and dication TMT-TTF2+ (12+) were successfully stabilized and isolated. All the compounds are well-soluble in some solvents and have been systematically investigated by absorption spectra, 1H NMR, electron paramagnetic resonance (EPR) measurements. Their crystal structures and electronic properties have been studied in conjunction with theoretical calculation. The synthetic approach for chemical oxidation by specific salts of weakly coordinating anions is useful for stable radical cations of tetrathiafulvalene (TTF) and its derivatives in both solution and solid state, which will extend the further research, including structure–property relations on stable radicals for TTF derivatives and new functional materials based on them.
Co-reporter:Feng Gao ; Long Cui ; You Song ; Yi-Zhi Li
Inorganic Chemistry 2014 Volume 53(Issue 1) pp:562-567
Publication Date(Web):December 19, 2013
DOI:10.1021/ic4026624
Three new single paramagnetic lanthanide-based complexes, [Ln(L)(LOEt)] (Ln3+ = Dy3+, Tb3+, and Ho3+), are synthesized with the multidentate calix[4]arene ligand H2L (H2L = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-dihydroxy-26,28-dimethoxycalix[4]arene) and Kläui’s tripodal ligand LOEt– (LOEt– = (η5-cyclopentadienyl)tris(diethylphosphito-p)cobaltate(III)). All of the complexes have been characterized by single crystal X-ray diffraction analysis, thermal stability, absorption spectra, and magnetization measurements. The magnetic properties and magnetostructural correlation in this seven-coordinated system are investigated. The dysprosium complex 1 shows typical single-molecule magnetic behavior with characteristic magnetic hysteresis loops and the slow relaxation of magnetization.
Co-reporter:Jing Ru, Feng Gao, Min-Xia Yao, Tao Wu and Jing-Lin Zuo
Dalton Transactions 2014 vol. 43(Issue 48) pp:18047-18055
Publication Date(Web):03 Oct 2014
DOI:10.1039/C4DT02518K
By the reaction of chiral MnIII Schiff-base complexes with the dicyanoruthenate building block, [Ru(salen)(CN)2]− (salen2− = N,N′-ethylenebis(salicylideneimine) dianion), two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes, [Mn((R,R)-salcy)Ru(salen)(CN)2]n (1-(RR)) and [Mn((S,S)-salcy)Ru(salen)(CN)2]n (1-(SS)) (Salcy = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [Mn((R,R)-salphen)Ru(salen)(CN)2]n (2-(RR)) and [Mn((S,S)-salphen)Ru(salen)(CN)2]n (2-(SS)) (salphen = N,N′-(1,2-diphenylethylene)bis(salicylideneiminato) dianion), were synthesized and structurally characterized. Circular dichroism (CD) and vibrational circular dichroism (VCD) spectra confirm the enantiomeric nature of the optically active complexes. Structural analyses reveal the formation of neutral cyano-bridged zigzag single chains in 1-(RR) and 1-(SS), and double chains in 2-(RR) and 2-(SS). Magnetic studies show that antiferromagnetic coupling is operative between RuIII and MnIII centers bridged by cyanide. Compounds 1-(RR) and 1-(SS) show metamagnetic behavior with a critical field of about 7.2 kOe at 1.9 K resulting from the intermolecular π⋯π interactions. Additionally, magnetostructural correlation for some typical cyano-bridged heterobimetallic RuIII–MnIII compounds is discussed.
Co-reporter:Yu-Yang Li, Feng Gao, Jonathon E. Beves, Yi-Zhi Li and Jing-Lin Zuo
Chemical Communications 2013 vol. 49(Issue 35) pp:3658-3660
Publication Date(Web):15 Mar 2013
DOI:10.1039/C3CC41237G
A giant metallo-supramolecular cage encapsulating a single-molecule magnet, [Ag42{Ho(W5O18)2}(t-BuCC)28Cl4]OH, is prepared and structurally characterized. It shows an interesting “peanut-like” structure and remains intact in solution as demonstrated by NMR studies.
Co-reporter:Feng Gao, Min-Xia Yao, Yu-Yang Li, Yi-Zhi Li, You Song, and Jing-Lin Zuo
Inorganic Chemistry 2013 Volume 52(Issue 11) pp:6407-6416
Publication Date(Web):May 21, 2013
DOI:10.1021/ic400245n
A series of seven-coordinate mononuclear lanthanide(III) complexes of the general formula [(TPP)Ln(LOEt)]·0.25H2O and [(Pc)Ln(LOEt)] (Ln3+ = Dy3+, Tb3+, Ho3+, and Gd3+; TPP = 5,10,15,20-tetraphenylporphyrinate; Pc = phthalocyaninate; LOEt– = [(η5-C5H5)Co(P(=O)(OEt)2)3]−) are synthesized on the basis of the tripodal ligand LOEt– and either porphyrin or phthalocyanine ligands. All of the complexes are characterized by X-ray crystallography and by static and dynamic magnetic measurements. The Dy and Tb complexes show the field-induced slow relaxation of magnetization, and they are interesting seven-coordinate single-lanthanide-based SMMs. The magnetic relaxation properties of these double-decker sandwich complexes are influenced by the local molecular symmetry and are sensitive to subtle distortions of the coordination geometry of the paramagnetic lanthanide ions, such as metal-to-plane distances, plane center distances, and bending angles.
Co-reporter:Feng Gao, Long Cui, Wei Liu, Liang Hu, Yu-Wu Zhong, Yi-Zhi Li, and Jing-Lin Zuo
Inorganic Chemistry 2013 Volume 52(Issue 19) pp:11164-11172
Publication Date(Web):September 24, 2013
DOI:10.1021/ic401421h
Three seven-coordinate lanthanide(III) sandwich-type mononuclear complexes with π-conjugated TTF-Schiff base ligand H2L (L2– = 2,2′-((2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3-benzodithiole-5,6-diyl)bis(nitrilomethylidyne)bis(4-chlorophenolate)) and the tripodal ligand LOEt– (LOEt– = [(η5-C5H5)Co(P(═O)(OEt)2)3]−), [(LOEt)Ln(L)]·0.25H2O (Ln3+ = Dy3+, 1; Tb3+, 2; Ho3+, 3), have been synthesized and structurally characterized. All of the complexes are also characterized by absorption spectra and electrochemical, spectroelectrochemical, and magnetic studies. The Dy complex exhibits the field-induced slow relaxation of magnetization with an energy barrier of 41.6 K, indicating it shows single lanthanide-based SMM behavior. Introduction of the redox-active TTF unit into the sandwich-type lanthanide(III) complexes with interesting magnetic properties renders them promising for elaboration of new hybrid inorganic–organic materials.
Co-reporter:Feng Gao, Yu-Yang Li, Cai-Ming Liu, Yi-Zhi Li and Jing-Lin Zuo
Dalton Transactions 2013 vol. 42(Issue 31) pp:11043-11046
Publication Date(Web):02 Jul 2013
DOI:10.1039/C3DT51051D
A new triple-decker dinuclear sandwich-type dysprosium complex based on both the phthalocyanine ligand and the tetradentate Schiff base ligand was synthesized, which is of interest for synthetic chemistry and also shows single-molecule magnetic behaviour.
Co-reporter:Xinhui Zhou, Honghui Li, Hongping Xiao, Liang Li, Qiang Zhao, Tao Yang, Jinglin Zuo and Wei Huang
Dalton Transactions 2013 vol. 42(Issue 16) pp:5718-5723
Publication Date(Web):04 Feb 2013
DOI:10.1039/C3DT00055A
A microporous metal–organic framework (MOF) Eu3(MFDA)4(NO3)(DMF)3 (1, H2MFDA = 9,9-dimethylfluorene-2,7-dicarboxylic acid) has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is a three-dimensional coordination polymer with pcu type rod-packing structure, through which 1D rhombic channels penetrate. The solvent-free form 1a could be obtained by direct heating of 1. Both 1 and 1a exhibit high intensity red light emissions with high quantum yields and long luminescence lifetimes when excited at 336 nm at ambient temperature. The potential of 1a for nitro explosive sensing is studied through luminescence quenching experiments, which show that 1a is a potential luminescent sensory material for nitro explosives.
Co-reporter:Liang Hu;Wei Liu;Cheng-Hui Li;Xin-Hui Zhou
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 35) pp:6037-6048
Publication Date(Web):
DOI:10.1002/ejic.201301151
Abstract
Two tetrathiafulvalene (TTF) functionalized 2,2′:6′,2″-terpyridine derivatives, 4′-tetrathiafulvalene-2,2′:6′,2″-terpyridine (L1) and 6,6″-dimethyl-4′-tetrathiafulvalene-2,2′:6′,2″-terpyridine (L2), were synthesized and characterized. Based on L1 and L2, four electrochemically active TTF-containing iron(II) complexes, [FeII(L1)2][ClO4]2 (1), [FeII(L1·+)2][ClO4]4 (2), [FeII(L1)2][CF3SO3]2 (3) and [FeII(L2)2][ClO4]2 (4), were successfully obtained. The preparation, spectroscopic and electrochemical properties of these new compounds as well as the crystal structures of complexes 1, 3 and 4 are described. Magnetic studies on 4 (with the ligand L2) suggest that the FeII ion is in the high-spin state. Complex 2 was isolated as an interesting and stable open-shell substance, and the free spin is mainly associated with the TTF radicals, as indicated by EPR, UV/Vis spectra, electrochemical analysis, spectroelectrochemical measurements and XPS spectra. After the oxidation and the formation of the radical cation, the electrical conductivity of 2 is almost 3 orders of magnitude higher than that of 1. DFT and TDDFT calculations provided insight into interpreting the electronic properties of complex 1 and its oxidized states.
Co-reporter:Jing Xiong, Long Cui, Wei Liu, Jonathon E. Beves, Yu-Yang Li, Jing-Lin Zuo
Tetrahedron Letters 2013 Volume 54(Issue 15) pp:1998-2000
Publication Date(Web):10 April 2013
DOI:10.1016/j.tetlet.2013.02.005
A new dual electro-optical fluoride sensor based on tetrathiafulvalene (TTF) generates the largest known electrochemical response to fluoride ions, a ΔE1/2 of almost 400 mV. The sensor is highly selective for fluoride over other anions, and displays ‘naked eye’ optical detection.A new dual electro-optical fluoride sensor based on tetrathiafulvalene (TTF) generates the largest known electrochemical response to fluoride ions, a ΔE1/2 of almost 400 mV. The sensor is highly selective for fluoride over other anions, and displays ‘naked eye’ optical detection.
Co-reporter:Rong-Mei Zhu, Liang Hu, Yi-Zhi Li, You Song, Jing-Lin Zuo
Inorganic Chemistry Communications 2013 Volume 35() pp:79-82
Publication Date(Web):September 2013
DOI:10.1016/j.inoche.2013.05.021
•New complexes with the dimerized quinoxaline-2,3-dithiolate ligand are synthesized.•The dinuclear complexes show the new κ2(S, N)-coordination mode.•The magnetic properties of the complexes are studied.New dinuclear complexes with the bridging S―S coupled and dimerized quinoxaline-2,3-dithiolate (dsqdt) ligand, [TpPh2M(dsqdt)MTpPh2] (TpPh2 = hydro-tris(3,5-diphenylpyrazol-1-yl)borate; M = Co, 1; M = Ni, 2; M = Mn, 3), were prepared. X-ray crystal structure studies for complexes 1–3 indicate that the dsqdt ligand forms the unique κ2-coordinated mode through S and N atoms from the same qdt unit. The absorption spectra, redox behavior and magnetic properties of the compounds are reported.Three dinuclear complexes with the bridging S―S coupled and dimerized quinoxaline-2,3-dithiolate ligand (dsqdt) have been synthesized and structurally characterized. The dsqdt ligand shows the new κ2(S, N)-coordination mode. The absorption spectra, electrochemical and magnetic properties for all complexes are studied.
Co-reporter:Dr. Min-Xia Yao;Qi Zheng;Kang Qian;Dr. You Song;Dr. Song Gao;Dr. Jing-Lin Zuo
Chemistry - A European Journal 2013 Volume 19( Issue 1) pp:294-303
Publication Date(Web):
DOI:10.1002/chem.201203361
Abstract
By using the node-and-spacer approach in suitable solvents, four new heterotrimetallic 1D chain-like compounds (that is, containing 3d–3d′–4f metal ions), {[Ni(L)Ln(NO3)2(H2O)Fe(Tp*)(CN)3]⋅2 CH3CN⋅CH3OH}n (H2L=N,N′-bis(3-methoxysalicylidene)-1,3-diaminopropane, Tp*=hydridotris(3,5-dimethylpyrazol-1-yl)borate; Ln=Gd (1), Dy (2), Tb (3), Nd (4)), have been synthesized and structurally characterized. All of these compounds are made up of a neutral cyanide- and phenolate-bridged heterotrimetallic chain, with a {FeCNNi(OLn)NC}n repeat unit. Within these chains, each [(Tp*)Fe(CN)3]− entity binds to the NiII ion of the [Ni(L)Ln(NO3)2(H2O)]+ motif through two of its three cyanide groups in a cis mode, whereas each [Ni(L)Ln(NO3)2(H2O)]+ unit is linked to two [(Tp*)Fe(CN)3]− ions through the NiII ion in a trans mode. In the [Ni(L)Ln(NO3)2(H2O)]+ unit, the NiII and LnIII ions are bridged to one other through two phenolic oxygen atoms of the ligand (L). Compounds 1–4 are rare examples of 1D cyanide- and phenolate-bridged 3d–3d′–4f helical chain compounds. As expected, strong ferromagnetic interactions are observed between neighboring FeIII and NiII ions through a cyanide bridge and between neighboring NiII and LnIII (except for NdIII) ions through two phenolate bridges. Further magnetic studies show that all of these compounds exhibit single-chain magnetic behavior. Compound 2 exhibits the highest effective energy barrier (58.2 K) for the reversal of magnetization in 3d/4d/5d–4f heterotrimetallic single-chain magnets.
Co-reporter:Min-Xia Yao ; Qi Zheng ; Xu-Min Cai ; Yi-Zhi Li ; You Song
Inorganic Chemistry 2012 Volume 51(Issue 4) pp:2140-2149
Publication Date(Web):February 3, 2012
DOI:10.1021/ic201982d
By the reactions of MnIII Schiff-base complexes with the tricyanometalate building block, [(Tp)Cr(CN)3]− (Tp = Tris(pyrazolyl) hydroborate), two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes, [Mn((R,R)-Salcy)Cr(Tp)(CN)3·1/4H2O·1/2CH2Cl2]n (1) and [Mn((S,S)-Salcy)Cr(Tp)(CN)3·1/4H2O·1/2CH2Cl2]n (2) (Salcy = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [Mn((R,R)-Salphen)Cr(Tp)(CN)3]n (3) and [Mn((S,S)-Salphen)Cr(Tp)(CN)3]n (4) (Salphen = N,N′-1,2-diphenylethylene-bis(salicylideneiminato) dianion), have been successfully synthesized. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Structural analyses reveal the formation of neutral cyano-bridged zigzag single chains in 1 and 2, and neutral cyano-bridged zigzag double chains in 3 and 4. Magnetic studies show that antiferromagnetic couplings are operative between CrIII and MnIII centers bridged by cyanide. Complexes 1 and 2 are the rare examples of chiral ferrimagnets; while complexes 3 and 4 exhibit a coexistence of chirality and spin-glass behavior in a 1D chain.
Co-reporter:Liang Hu, Jie Qin, Nan Zhou, Yi-Fei Meng, Yan Xu, Jing-Lin Zuo, Xiao-Zeng You
Dyes and Pigments 2012 Volume 92(Issue 3) pp:1223-1230
Publication Date(Web):March 2012
DOI:10.1016/j.dyepig.2011.08.003
Metal complexes containing a new multi-sulfur atom containing 1,2-dithiolene ligand, [4′,5′:5,6] [1,4] dithiino[2,3-b] quinoxaline-1′,3′-dithiolate, have been synthesized and characterized by electrochemical measurements, IR, UV–NIR and ESR spectroscopies. X-ray structure analysis reveals that the anions of the Ni-complex derived from the new ligand form a zig-zag chain along the b axis, and the anions of Au complex of the ligand stack along the a axis while the cations occupy the holes. The Ni-complex exhibits remarkable absorption at 1082 nm (ɛ = 15 000 dm3 mol−1 cm−1) and good solubility that render this complex as a promising near-IR dye for Q-switching neodymium lasers. The third-order non-linear optical properties of the complexes are measured by the Z-scan technique with a 6.5 ns pulsed laser at 532 nm. The Au complexes exhibit non-linear optical absorptive abilities, while the non-linear absorption of the nickel complex is negligible. All of the complexes show effective self-defocusing performance. The third-order non-linear optical susceptibilities for the Au complexes have been determined to be of the order of 10−13 esu.Metal complexes containing the multi-sulfur dithiolene ligand, [n-Bu4N]n[Ni(L)2] (n = 1, 1; n = 0, 2), [R4N][Au(L)2] (R = n-Bu, 3; R = Et, 4) (L = [4′,5′:5,6] [1,4] dithiino[2,3-b] quinoxaline-1′,3′-dithiolate), have been synthesized and characterized. Complex 1 exhibits a remarkable absorption at 1082 nm (ɛ = 15 000 dm3 mol−1 cm−1) and good solubility that makes it a promising near-IR dye for Q-switching neodymium lasers. Gold complexes 3 and 4 exhibit third-order non-linear optical absorptive abilities. All complexes show effective self-defocusing performance.Highlights► A new multi-sulfur containing 1,2-dithiolene type ligand and four metal complexes are synthesized. ► The nickel complex 1 exhibits remarkable absorption at 1082 nm and is a promising near-IR dye. ► The third-order non-linear optical properties of complexes 1, 3 and 4 are studied.
Co-reporter:Min-Xia Yao, Qi Zheng, Feng Gao, Yi-Zhi Li, You Song and Jing-Lin Zuo
Dalton Transactions 2012 vol. 41(Issue 44) pp:13682-13690
Publication Date(Web):02 Aug 2012
DOI:10.1039/C2DT31203D
Four couples of enantiomerically pure chiral seven-coordinated mononuclear lanthanide complexes, [(LOEt)Dy((R,R)-Salphen)]2·3H2O (1, LOEt = [(Cp)Co(P(O)(OEt)2)3], Cp = cyclopentadiene, Salphen = N,N′-1,2-diphenylethylenebis(salicylideneiminato) dianion), [(LOEt)Dy((S,S)-Salphen)]2·3H2O (2), [(LOEt)Dy((R,R)-5-Cl-Salcy)]·CH3OH·1/8H2O (3, Salcy = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [(LOEt)Dy((S,S)-5-Cl-Salcy)]·CH3OH·1/8H2O (4), [(LOEt)Tb((R,R)-5-Cl-Salcy)]·CH3OH·1/8H2O (5), [(LOEt)Tb((S,S)-5-Cl-Salcy)]·CH3OH·1/8H2O (6), [(LOEt)Ho((R,R)-5-Cl-Salcy)]·CH3OH·1/8H2O (7) and [(LOEt)Ho((S,S)-5-Cl-Salcy)]·CH3OH·1/8H2O (8), have been successfully synthesized by using tetradentate chiral salen-type ligands and the Kläui's tripodal ligand of LOEt. Structural analyses reveal that all compounds have a typical double-decker sandwich structure, and the Ln(III) ions exhibit a rare seven-coordinated mode, situating in a distorted monocapped triangular prism polyhedron. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes and demonstrate that the chirality is successfully transferred from the ligand to the coordination environment of the Ln(III) ions. Field-induced slow relaxation of the magnetization is observed for complexes 1–4, suggesting that they can be rare chiral single-ion magnets (SIMs) based on the seven-coordinated lanthanide ions.
Co-reporter:Xi-Li Li, Yu-Liang Gao, Xiang-Li Feng, You-Xuan Zheng, Chun-Lai Chen, Jing-Lin Zuo and Shao-Ming Fang
Dalton Transactions 2012 vol. 41(Issue 38) pp:11829-11835
Publication Date(Web):01 Aug 2012
DOI:10.1039/C2DT31007D
Using the enantiomeric bis-bidentate bridging ligands (+)/(−)-2,5-bis(4,5-pinene-2-pyridyl)pyrazine (LS/LR) and depending on the ratio control of reactants, two mono- and dinuclear Eu(III)-based enantiomeric pairs with the formulae Eu(dbm)3LR/S·2H2O (LR in R-1, LS in S-1 and dbm = dibenzoylmethanato) and Eu2(dbm)6LR/S·H2O (LR in R-2 and LS in S-2) have been stereoselectively synthesized and structurally characterized. The circular dichroic (CD) spectra confirmed their chiroptical activities and enantiomeric natures. The homochiral dinuclear species represents the first example of a polynuclear lanthanide β-diketonate complexes with circular dichroic and crystallographic evidences. The photoluminescent properties studies revealed that both mono- and dinuclear Eu(III) complexes exhibited the characteristic red emissions of Eu(III) ions in the solid state (at 77 K and 300 K) and CH2Cl2 solution. Notably, the photophysical properties of the mononuclear enantiomers were superior to the dinuclear species. Interestingly, R-2 displayed a ferroelectric property at room temperature, which was not observed for R-1 due to the lack of crystalline polarity. R/S-2 are the first examples of homochiral polynuclear lanthanide complexes with luminescence and ferroelectric properties, being potential multifunctional materials.
Co-reporter:Liang Hu;Jie Qin;Rong-Mei Zhu;Yi-Zhi Li, ;Xiao-Zeng You
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 15) pp:2494-2501
Publication Date(Web):
DOI:10.1002/ejic.201200047
Abstract
New π-extended tetrathiafulvalenes (exTTF) 4a, 4b, 5a, and 5b have been synthesized by direct phosphite-mediated cross-couplings of anthraquinone with 1,3-dithiole-2-thione derivatives. Further coordination reactions of the exTTF ligands including the phenanthroline unit (5a and 5b) with [Re(CO)5Cl] afford interesting tricarbonylrhenium(I) complexes 6a and 6b, respectively. The X-ray crystal structures of compounds 4a and 4b show a saddlelike conformation of the exTTF framework. The electrochemical and spectroscopic properties of compounds 4a–6a and 4b–6b have been studied. The results suggest that the oxidation of the exTTF derivatives shows the typical quasi-reversible two-electron oxidation wave of the exTTF core at potentials that vary depending on the substituents.
Co-reporter:Jie Qin;Chen-Xi Qian;Nan Zhou;Rong-Mei Zhu;Yi-Zhi Li, ;Xiao-Zeng You
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 2) pp:234-245
Publication Date(Web):
DOI:10.1002/ejic.201101022
Abstract
π-Conjugated tetrathiafulvalene (TTF)-based donors with a monoamine moiety, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3-benzodithiol-5-amine (La) and 2-(5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-benzodithiol-5-amine (Lb), have been synthesized. Condensation of the TTF amines with different pyridinecarbaldehydes afforded new TTF-fused π-extended Schiff base ligands, La-imine-4-pyridyl (L1), La-imine-3-pyridyl (L2), and Lb-imine-2-pyridyl (L3). Four metal complexes based on these Schiff base pyridine ligands, M(hfac)2(L)2 (M = CuII, L = L1, 4; M = MnII, L = L1, 5; M = CuII, L = L2, 6; hfac = hexafluoroacetylacetonate) and [Re(CO)4(L3)][Re2(CO)6Cl3] (7), have been synthesized and structurally characterized. The ligands in all of the complexes show a near planar structure, and the different coordination modes of the metal ions and relative orientation of the terminal N donors result in a different crystalline organization in the solid state. The absorption spectra and redox behavior of these new compounds have been studied. These paramagnetic complexes are promising building blocks for the construction of multifunctional materials due to their planar structures and inherent redox properties.
Co-reporter:Ya Liao, Nan Zhou, Jie Qin, Yi-Zhi Li, You-Xuan Zheng, Jing-Lin Zuo
Inorganic Chemistry Communications 2012 Volume 21() pp:104-108
Publication Date(Web):July 2012
DOI:10.1016/j.inoche.2012.04.024
New amide functional tetrathiafulvalene ligands containing naphthyridine moiety (L1–L3) were synthesized. Further coordination reactions of these ligands with Re(CO)5Cl afford three interesting rhenium tricarbonyl complexes, ClRe(CO)3(L). Crystal structures of ClRe(CO)3(L1) (1) and ClRe(CO)3(L2) (2) have been determined. Electrochemical and spectroscopic properties of all compounds are investigated.New amide functional tetrathiafulvalene ligands containing naphthyridine ligands and two rhenium tricarbonyl complexes based on them have been prepared. Electrochemical and spectroscopic behaviors of these compounds have been studied. The results suggest that the redox-active amide functional tetrathiafulvalene ligands are useful for new metal complexes.Highlights► Three amide functional tetrathiafulvalene-based naphthyridine ligands are synthesized. ► Rhenium(I) tricarbonyl complexes based on the ligands are synthesized and characterized. ► The redox-active amide functional tetrathiafulvalene ligands are useful for new metal complexes.
Co-reporter:Xu-Min Cai, Xiang-Yi Zhang, Julia Savchenko, Zhi Cao, Tong Ren, and Jing-Lin Zuo
Organometallics 2012 Volume 31(Issue 24) pp:8591-8597
Publication Date(Web):December 4, 2012
DOI:10.1021/om300985z
Under the weak base conditions, diruthenium(III) tetrakis-N,N′-dimethylbenzamidinate (DMBA) nitrate (Ru2(DMBA)4(NO3)2) reacted with electroactive tetrathiafulvalene acetylene ligands, HC≡C–TTF1 (5-ethynyl-2-(4,5-dimethyl-1,3-dithiol-2-ylidene)benzo[d][1,3]dithiole) and HC≡C–TTF2 (2-(5-ethynylbenzo[d][1,3]dithiol-2-ylidene)benzo[d][1,3]dithiole), to afford new compounds trans-Ru2(DMBA)4(C≡C–TTF1)2 (1) and trans-Ru2(DMBA)4(C≡C–TTF2)2 (2), respectively. The trans orientation and the planar nature of the ethynyltetrathiafulvalene ligands around the Ru2(III,III) core were supported by the single-crystal X-ray diffraction study of compound 1. Both compounds 1 and 2 and their TTF ligand precursors were characterized with the spectroscopic and voltammetric techniques, which revealed a minimal electronic interaction between the two TTF moieties within the same compound. The electronic structure of trans-Ru2(DMBA)4(C≡C–TTF)2 was analyzed based on a DFT calculation of a model compound, and the resultant distribution of valence MOs is consistent with the voltammetric results.
Co-reporter:Xiaoyu Chen;Binbin Ma;Dr. Xingyong Wang;Shengxin Yao;Lichen Ni;Zhaoyi Zhou; Yizhi Li; Wei Huang; Jing Ma; Jinglin Zuo; Xinping Wang
Chemistry - A European Journal 2012 Volume 18( Issue 37) pp:11828-11836
Publication Date(Web):
DOI:10.1002/chem.201103972
Abstract
Salts that contain radical cations of benzidine (BZ), 3,3′,5,5′-tetramethylbenzidine (TMB), 2,2′,6,6′-tetraisopropylbenzidine (TPB), and 4,4′-terphenyldiamine (DATP) have been isolated with weakly coordinating anions [Al(ORF)4]− (ORF=OC(CF3)3) or SbF6−. They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of benzidine or its alkyl-substituted derivatives in CH2Cl2. The salts were characterized by UV absorption and EPR spectroscopy as well as by their single-crystal X-ray structures. Variable-temperature UV/Vis absorption spectra of BZ.+[Al(ORF)4]− and TMB.+[Al(ORF)4]− in acetonitrile indicate an equilibrium between monomeric free radical cations and a radical-cation dimer. In contrast, the absorption spectrum of TPB.+SbF6− in acetonitrile indicates that the oxidation of TPB only resulted in a monomeric radical cation. Single-crystal X-ray diffraction studies show that in the solid state BZ and its methylation derivative (TMB) form radical-cation π dimers upon oxidation, whereas that modified with isopropyl groups (TPB) becomes a monomeric free radical cation. By increasing the chain length, π stacks of π dimers are obtained for the radical cation of DATP. The single-crystal conductivity measurements show that monomerized or π-dimerized radicals (BZ.+, TMB.+, and TPB.+) are nonconductive, whereas the π-stacked radical (DATP.+) is conductive. A conduction mechanism between chains through π stacks is proposed.
Co-reporter:Jing Xiong, Wei Liu, Yong Wang, Long Cui, Yi-Zhi Li, and Jing-Lin Zuo
Organometallics 2012 Volume 31(Issue 10) pp:3938-3946
Publication Date(Web):May 7, 2012
DOI:10.1021/om300159r
Two new bis(3,5-dimethylpyrazole)-substituted tetrathiafulvalene ligands, 2,6(7)-bis(methylthio)-3,7(6)-bis(3-sulfanyl-3,5-dimethylpyrazole)tetrathiafulvalene (L1) and 2,3-bis(methylthio)-6,7-bis(3-sulfanyl-3,5-dimethylpyrazole)tetrathiafulvalene (L2), have been prepared and characterized. On the basis of the two ligands, three interesting rhenium(I) tricarbonyl mono- or dinuclear complexes, ClRe(CO)3(cis-L1) (1), [ClRe(CO)3(trans-L1)]2 (2), and [ClRe(CO)3(L2)]2 (3), have been prepared and structurally characterized. Electrochemical studies show sequential oxidation processes of the compounds to the corresponding radical cation and dication states, suggesting that redox events are essentially dependent on the structures of the rhenium(I) complexes. The results have evidenced electronic interactions between the TTF cores in complexes 1 and 2. Geometric and electronic structures as well as the spectroscopic properties for complexes 1–3 have been investigated by using DFT and TDDFT calculations.
Co-reporter:Jie Qin, Ya Liao, Xiao-Yu Chen, Chen-Xi Qian, Jing-Lin Zuo, Xiao-Zeng You
Journal of Organometallic Chemistry 2012 716() pp: 275-280
Publication Date(Web):
DOI:10.1016/j.jorganchem.2012.05.029
Co-reporter:Min-Xia Yao, Zheng-You Wei, Zhi-Guo Gu, Qi Zheng, Yan Xu, and Jing-Lin Zuo
Inorganic Chemistry 2011 Volume 50(Issue 17) pp:8636-8644
Publication Date(Web):August 10, 2011
DOI:10.1021/ic2011875
Using the tricyano precursor (Bu4N)[(Tp)Cr(CN)3] (Bu4N+ = tetrabutylammonium cation; Tp = tris(pyrazolyl)hydroborate), a pentanuclear heterometallic cluster [(Tp)2Cr2(CN)6Cu3(Me3tacn)3][(Tp)Cr(CN)3](ClO4)3·5H2O (1, Me3tacn = N,N′,N′-trimethyl-1,4,7-triazacyclononane), three tetranuclear heterometallic clusters [(Tp)2Cr2(CN)6Cu2(LOEt)2]·2.5CH3CN (2, LOEt = [(Cp)Co(P(O)(OEt)2)3], Cp = cyclopentadiene), [(Tp)2Cr2(CN)6Mn2(LOEt)2]·4H2O (3), and [(Tp)2Cr2(CN)6Mn2(phen)4](ClO4)2 (4, phen = phenanthroline), and a one-dimensional (1D) chain polymer [(Tp)2Cr2(CN)6Mn(bpy)]n (5, bpy = 2,2′-bipyridine) have been synthesized and structurally characterized. Complex 1 shows a trigonal bipyramidal geometry in which [(Tp)Cr(CN)3]− units occupy the apical positions and are linked through cyanide to [Cu(Me3tacn)]2+ units situated in the equatorial plane. Complexes 2–4 show similar square structures, where CrIII and MII (M = CuII or MnII) ions are alternatively located on the rectangle corners. Complex 5 consists of a 4,2-ribbon-like bimetallic chain. Ferromagnetic interactions between CrIII and CuII ions bridged by cyanides are observed in complexes 1 and 2. Antiferromagnetic interactions are presented between CrIII and MnII ions bridged by cyanides in complexes 3–5. Complex 5 shows metamagnetic behavior with a critical field of about 22.5 kOe at 1.8 K.
Co-reporter:Ru Wang, Ling-Chen Kang, Jing Xiong, Xiao-Wei Dou, Xiao-Yu Chen, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2011 vol. 40(Issue 4) pp:919-926
Publication Date(Web):08 Dec 2010
DOI:10.1039/C0DT00739K
The bis(pyridyl)-substituted TTF derivative, 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (TTF(py)2), and an inorganic analogue, [Ni(4-pedt)2] (4-pedt = 1-(pyridin-4-yl)ethylene-1,2-dithiolate), were used as bridging ligands to construct two multinuclear complexes {CoII2(TpPh2)2(OAc)2[TTF(py)2]} (1, TpPh2 = hydridotri(3,5-diphenylpyrazol-1-yl)borate) and {CoII2(TpPh2)2(OAc)2[Ni(4-pedt)2]} (2), and two 1D zigzag chain complexes, {[MII(tta)2][TTF(py)2]}n (M = Cu for 3, and Mn for 4; tta = thenoyltrifluoroacetonate). X-Ray structural studies indicate that complexes 1 and 2 are very similar as a result of the isolobal analogy between TTF(py)2 and [Ni(4-pedt)2], whereas complexes 3 and 4 are isostructural. The absorption spectra, electrochemical and magnetic properties for these new complexes have been studied. The results show that the interactions between the paramagnetic ions are weak owing to the large separation of the bridging ligands of TTFs and the inorganic analogue.
Co-reporter:Ling-Chen Kang, Min-Xia Yao, Xin Chen, Yi-Zhi Li, You Song, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2011 vol. 40(Issue 10) pp:2204-2212
Publication Date(Web):13 Dec 2010
DOI:10.1039/C0DT00954G
With the use of Kläui's tripodal ligand, [(Cp)Co(P(O)(OEt)2)3]− (LCoEt, Cp = cyclopentadiene) as the auxiliary ligand to react with different metal salts and tricyanometalate building blocks, five neutral trimetallic hexanuclear complexes: [(Tp)2Fe2(CN)6Cu2(LCoEt)2]·6H2O (1, Tp = hydridotris(pyrazolyl)borate), [(Tp*)2Fe2(CN)6Cu2(LCoEt)2]·2H2O (2, Tp* = hydridotris(3,5-dimethyl-pyrazolyl)borate), [(pzTp)2Fe2(CN)6Cu2(LCoEt)2]·H2O·3MeOH (3, pzTp = tetra(pyrazolyl)borate), [(Tp)2Fe2(CN)6Ni2(LCoEt)2(MeCN)2]·2MeCN·2H2O (4) and [(Tp)2Fe2(CN)6Mn2(LCoEt)2(MeCN)2]·2MeCN (5), have been obtained and structurally characterized. Magnetic measurements confirm that there are ferromagnetic couplings between the cyano-bridged Fe and Cu/or Ni ions and antiferromagnetic interaction between the cyano-bridged Fe and Mn ions. Slow relaxation of the magnetization is observed in complexes 1 and 4, while complex 3 exhibits metamagnetic behavior with a critical field of 17.5 kOe.
Co-reporter:Jing Xiong;Gao-Nan Li;Lei Sun;Yi-Zhi Li, ;Xiao-Zeng You
European Journal of Inorganic Chemistry 2011 Volume 2011( Issue 33) pp:5173-5181
Publication Date(Web):
DOI:10.1002/ejic.201100627
Abstract
A series of tetrathiafulvalene-substituted acetylacetonate ligands (L1–L4) has been synthesized and characterized. Reaction of the ligands with (Tp)Co(OAc)(Hpz) and (Tp)Ni(OAc) [Tp = hydrotris(3,5-diphenylpyrazol-1-yl)borate; Hpz = 3,5-diphenylpyrazole] afforded eight new mono- or dinuclear complexes 1–8: TpML1 or (TpM)2L (M = Co, Ni; L = L2, L3 and L4). The crystal structures of L4 and 1–3, 5, and 6 were determined by X-ray crystallography. The absorption spectra and redox behavior of these compounds have been studied. The optimized geometry and electron absorption spectrum of 2 were analyzed by DFT and time-dependent (TD)-DFT.
Co-reporter:Jing Xiong, Lei Sun, Ya Liao, Gao-Nan Li, Jing-Lin Zuo, Xiao-Zeng You
Tetrahedron Letters 2011 Volume 52(Issue 46) pp:6157-6161
Publication Date(Web):16 November 2011
DOI:10.1016/j.tetlet.2011.09.042
A new tetrathiafulvalene (TTF) derivative with the boron–dipyrromethene (BODIPY) moiety shows selectively optical and electrochemical sensing for fluoride ion. The mechanism of anion recognition has been investigated by 1H NMR titration and DFT calculations. The results show that the receptor with redox active TTF moiety and fluorescent BODIPY subunits may be useful as sensors for detecting and sensing fluoride ion.A new tetrathiafulvalene(TTF)-substituted boron–dipyrromethene (BODIPY) compound has been prepared, which exhibits selectively optical and electrochemical sensing for fluorion. Titration 1H NMR and DFT calculations have been carried out to study the mechanism of anion recognition.
Co-reporter:Tao Jin, Gao-Nan Li, Xin-Hui Zhou, Jing-Lin Zuo
Inorganic Chemistry Communications 2011 Volume 14(Issue 12) pp:1944-1947
Publication Date(Web):December 2011
DOI:10.1016/j.inoche.2011.09.017
Using the deprotection–realkylation methodology, a new electroactive tetrathiafulvalene-based bipyridine ligand, 5-[{2-[4,5-Bis(methylthio)-1,3-dithiol-2-ylidene]-5-(methylthio)-1,3-dithiol-4-yl}thio]-methyl-2,2′-bipyridine (L), has been synthesized. Reactions of the above ligand with Re(CO)5Br or Re(CO)5Cl afford the corresponding tricarbonyl rhenium(I) complexes ReL(CO)3X (X = Br, 1; X = Cl, 2), respectively. Crystal structures of 1 and 2 have been described. The absorption properties of these new compounds have been studied. Electrochemical measurements have been performed and TTF/TTF+•/TTF2+ redox processes are observed.Two rhenium(I) tricarbonyl complexes with the new electroactive tetrathiafulvalene-based bipyridine ligand, 5-[{2-[4,5-Bis(methylthio)-1,3-dithiol-2-ylidene]-5-(methylthio)-1,3-dithiol-4-yl}thio]-methyl-2,2′-bipyridine (L), have been prepared and structurally characterized. The absorption and electrochemical properties of these new compounds have been studied.Highlights► A new electroactive tetrathiafulvalene-based bipyridine ligand is synthesized. ► Two rhenium(I) tricarbonyl complexes based on the ligand are structurally characterized. ► The TTF/TTF+•/TTF2+ redox processes are observed for the ligand and the related metal complexes.
Co-reporter:Jing Xiong, Lei Sun, Ling-Chen Kang, Wei Liu, You-Xuan Zheng, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2011 Volume 376(Issue 1) pp:36-43
Publication Date(Web):1 October 2011
DOI:10.1016/j.ica.2011.05.035
A new type of multidentate ligand with both acetylacetonate and bis(2-pyridyl) units on the 1,3-dithiole moiety, 3-[2-(dipyridin-2-yl-methylene)-5-methylsulfanyl-[1,3]dithiol-4-ylsulfanyl]-pentane-2, 4-dione (L), has been prepared. Through reactions of the ligand with Re(CO)5X (X = Cl, Br), new rhenium(I) tricarbonyl complexes ClRe(CO)3(L) (2) and BrRe(CO)3(L) (3), have been obtained. With the use of 2 or 3 as the precursors, the further reactions with (TpPh2)Co(OAc)(HpzPh2) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate); HpzPh2 = 3,5-diphenyl-pyrazole) or M(OAc)2(M = Mn, Zn), afford four new heteronuclear complexes: ClRe(CO)3(L)Co(TpPh2) (4), BrRe(CO)3(L)Co(TpPh2) (5), [ClRe(CO)3(L)]2Mn(CH3OH)2 (6) and [ClRe(CO)3(L)]2Zn(CH3OH)2 (7), respectively. Crystal structures of complexes 2 and 4–7 have been determined by X-ray diffraction. Their absorption spectra, photoluminescence and magnetic properties have been studied.Graphical abstractA new versatile bridging ligand containing both acetylacetonate and bis(2-pyridyl) units on the 1,3-dithiole moiety, 3-[2-(di-pyridin-2-yl-methylene)-5-methylsulfanyl-[1,3]dithiol-4-ylsulfanyl]-pentane-2,4-dione (L), has been prepared. Based on the ligand, two mononuclear rhenium(I) tricarbonyl complexes and four heteronuclear complexes have been prepared and structurally characterized. Their absorption spectra, photoluminescence and magnetic properties have been studied.Highlights► A new bridging ligand containing both acetylacetonate and bis(2-pyridyl) units on the 1,3-dithiole moiety are prepared. ► Heteronuclear coordination complexes are obtained based on the ligand and their crystal structures are studied. ► The photoluminescence and magnetic studies show that the multidentate ligand could be useful for new multifunctional materials.
Co-reporter:Gao-Nan Li, Di Wen, Tao Jin, Ya Liao, Jing-Lin Zuo, Xiao-Zeng You
Tetrahedron Letters 2011 Volume 52(Issue 6) pp:675-678
Publication Date(Web):9 February 2011
DOI:10.1016/j.tetlet.2010.11.129
Three new π-conjugated pyridine ligands with redox-active tetrathiafulvalene (TTF) derivatives, L1–L3, have been synthesized and characterized. The Diels–Alder reaction is the key step for this multistep synthetic strategy. The crystal structures of L1 and L3 have been studied. The electrochemical and spectroscopic properties of these new ligands, as well as the corresponding tricarbonyl rhenium(I) complexes (ReL1(CO)3X, X = Cl, 5; X = Br, 6) have also been investigated.Three new π-conjugated pyridine ligands with redox-active tetrathiafulvalenes (TTF) derivatives, L1–L3, have been synthesized and characterized. The Diels–Alder reaction is the key step for this multistep synthetic strategy. The crystal structures of L1 and L3 have been determined. The electrochemical and spectroscopic properties of these ligands and the corresponding tricarbonyl rhenium(I) complexes (5 and 6) have also been investigated.
Co-reporter:Jie Qin, Liang Hu, Gao-Nan Li, Xi-Sen Wang, Yan Xu, Jing-Lin Zuo, and Xiao-Zeng You
Organometallics 2011 Volume 30(Issue 8) pp:2173-2179
Publication Date(Web):March 31, 2011
DOI:10.1021/om101141h
A series of tetrathiafulvalene-annulated phenanthroline ligands, 4′,5′-dimethyldithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L1), 4′,5′-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L2), and 4′,5′-bis(methyloxycarbonyl)dithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L3), have been prepared by a facile and efficient synthetic procedure under mild conditions. Further coordination reactions of these ligands with Re(CO)5Cl afford new rhenium tricarbonyl complexes, Re(CO)3Cl(L) (L = L1, 3a; L = L2, 3b; L = L3, 3c), respectively. X-ray crystal structure determinations on 3a,c reveal that the ligands are nearly planar and they show a unique packing mode in the solid state. The electrochemical and spectroscopic behavior of these compounds (L1−L3, 3a−c) has been studied. The results suggest that the redox-active tetrathiafulvalene-phenanthroline ligands are useful for new metal complexes.
Co-reporter:Gao-Nan Li, Jing Xiong, Ya Liao, Lei Sun, Yi-Zhi Li, Jing-Lin Zuo
Polyhedron 2011 30(15) pp: 2473-2478
Publication Date(Web):
DOI:10.1016/j.poly.2011.06.039
Co-reporter:Gao-Nan Li, Tao Jin, Lei Sun, Jie Qin, Di Wen, Jing-Lin Zuo, Xiao-Zeng You
Journal of Organometallic Chemistry 2011 696(19) pp: 3076-3085
Publication Date(Web):
DOI:10.1016/j.jorganchem.2011.06.012
Co-reporter:Yan-Hong Peng ; Yi-Fei Meng ; Liang Hu ; Quan-Xiu Li ; Yi-Zhi Li ; Jing-Lin Zuo ;Xiao-Zeng You
Inorganic Chemistry 2010 Volume 49(Issue 4) pp:1905-1912
Publication Date(Web):January 21, 2010
DOI:10.1021/ic9023713
Two new π-conjugated 1,3-dithiol-2-ylidene-containing ligands, 4,5-[1′,4′]dithiino[2′,3′-b]quinoxaline-2-bis(2-pyridyl)methylene-1,3-dithiole (L1) and 4,5-bis(methylthio)-2-bis(2-pyridyl)methylene-1,3-dithiole (L2), have been synthesized and characterized. Using L1, L2, or dimethyl 2-[di(pyridin-2-yl)methylene]-1,3-dithiole-4,5-dicarboxylate (L3) as the auxiliary ligand and [(Tp)Fe(CN)3]− or [(i-BuTp)Fe(CN)3]− [Tp = tris(pyrazolyl)borate; i-BuTp = 2-methylpropyltris(pyrazolyl)borate] as the building block, two rectangular-square Fe2Ni2 clusters [(Tp)Fe(CN)3Ni(L1)2]2·2ClO4·6H2O (1) and [(i-BuTp)Fe(CN)3Ni(L3)2]2·2ClO4·6H2O (2) and two trinuclear clusters [(Tp)2Fe2(CN)6Ni(L2)2]·8H2O (3) and [(Tp)2Fe2(CN)6Co(L3)2]·5H2O (4) have been prepared in parallel and structurally characterized. Complexes 1 and 2 show similar square structures, and weaker intermolecular π−π-stacking interactions through the pyrazolyl groups of the Tp− ligands are observed. 2D sheet structures are formed in complexes 3 and 4 through intermolecular π−π-stacking interactions. In 3, shorter S···S contacts further connect the 2D sheets to 3D supramolecular structures. Magnetic studies show intramolecular ferromagnetic coupling in complexes 1−4. Complexes 1 and 2 show obvious frequency dependencies in the alternating-current magnetic susceptibility data, indicating single-molecule-magnet behavior with effective spin-reversal barriers of 8.7 K for 1 and 13.5 K for 2, respectively.
Co-reporter:Ling-Chen Kang ; Xin Chen ; Hui-Sheng Wang ; Yi-Zhi Li ; You Song ; Jing-Lin Zuo ;Xiao-Zeng You
Inorganic Chemistry 2010 Volume 49(Issue 20) pp:9275-9282
Publication Date(Web):September 23, 2010
DOI:10.1021/ic100861n
The reactions of copper(II) salts, 1,3-bis(dimethylamino)-2-propanol (bdmapH) or 1,3-bis(amino)-2-propanol (bapH) and [(Tp)Fe(CN)3]− (Tp = tris(pyrazolyl)hydroborate) gave four mixed-bridged heterometallic one-dimensional (1D) coordination polymers, {[(Tp)2Fe2(CN)6(OAc)(bdmap)Cu2(H2O)]·2H2O}n (1, HOAc = acetic acid), {[(Tp)2Fe2(CN)6(Pa)(bdmap)Cu2(H2O)]·2MeCN}n (2, HPa = propionic acid), {[(Tp)2Fe2(CN)6(Tfa)(bdmap)Cu2(H2O)]·2MeCN}n (3, HTfa = trifluoroacetic acid), and {[(Tp)2Fe2(CN)6(OAc)(bap)Cu2(MeOH)]·2MeOH·H2O}n (4). Complexes 1−3 show unique branched zigzag chain structures and complex 4 exhibits as a steplike chain. Ferromagnetic interactions between FeIII and CuII ions by bridging cyanides are observed in all complexes. Strong antiferromagnetic interactions are presented between the CuII ions in complexes 1−3, whereas similar antiferromagnetic coupling between CuII ions is obviously weakened in complex 4 because of the distortion of penta-coordinated CuII ions.
Co-reporter:Xiao-Qiang Liang, Dong-Ping Li, Cheng-Hui Li, Xin-Hui Zhou, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You
Crystal Growth & Design 2010 Volume 10(Issue 6) pp:2596
Publication Date(Web):April 27, 2010
DOI:10.1021/cg1000107
A series of new coordination polymers, {[Zn(1,2-bimb)(d-ca)]·2H2O}n (1), [Zn(1,3-bimb)(d-ca)]n (2), [Cd(1,3-bimb)(d-ca)]n (3), [Zn(1,4-bimb)(d-ca)]n (4), and {[Cd2(dpys)(d-ca)2(H2O)2]·H2O}n (5), (d-H2ca = d-camphoric acid, 1,2-bimb =1,2-bis(imidazol-1-ylmethyl)-benzene, 1,3-bimb = 1,3-bis(imidazol-1-ylmethyl) -benzene, 1,4-bimb = 1,4-bis(imidazol-1-ylmethyl)-benzene, dpys = 4,4′-dipyridylsulfide), have been prepared under hydrothermal conditions and characterized by elemental analyses, IR, vibrational circular dichroism, thermogravimetric and X-ray structural analyses. Their structures and properties can be tuned by variable coordination positions and conformations of the auxiliary ligands. Complex 1 features a three-dimensional (3D) supramolecular framework with a one-dimensional (1D)-nanosized channel. Complexes 2 and 3 show acentric 1D double-stranded chains. The chiral two-dimensional sheet with (4,4) topology is found in compound 4. Compound 5 displays a 1D ladderlike chain. Photoluminescent properties of 1 and 5 are studied. Compounds 2−5 display a second-order nonlinear optical effect and ferroelectric behaviors.
Co-reporter:Ling-Chen Kang, Xin Chen, Xiao-Yu Chen, You Song, Jing-Lin Zuo, Xiao-Zeng You
Inorganic Chemistry Communications 2010 Volume 13(Issue 1) pp:109-111
Publication Date(Web):January 2010
DOI:10.1016/j.inoche.2009.10.032
An unusual μ1,1,3-cyanamido bridged trinuclear copper complex, [(2,2′-bpy)6Cu3(NCN)](ClO4)4·H2O (1) (2,2′-bpy = 2,2′-bipyridine), has been synthesized and structurally characterized. Magnetic studies show the existence of large antiferromagnetic coupling between the copper(II) ions.An unusual μ1,1,3-cyanamido bridged trinuclear copper(II) complex, [(2,2′-bipyridine)6Cu3(NCN)](ClO4)4·H2O, has been prepared and structurally characterized. Magnetic studies show the existence of strong antiferromagnetic coupling.
Co-reporter:Yan-Hong Peng, Yu-Jia Li, Cheng-Hui Li, Liang Hu, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2010 Volume 363(Issue 14) pp:3742-3749
Publication Date(Web):25 November 2010
DOI:10.1016/j.ica.2010.05.028
By deprotonation reaction of the rhenium(I) tricarbonyl complex, ClRe(CO)3(H2bpydt) (2, H2dpydt = 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylic acid, our previous work in J. Organomet. Chem. 694 (2009) 763), complex 3, [Bu4N][ClRe(CO)3(Hbpydt)], is synthesized and characterized. Using 3 as the starting material, two trinuclear heterometallic complexes M(MeOH)4[ClRe(CO)3(Hbpydt)]2·2MeOH (M = Cu, 4; M = Mn, 5) are obtained. The crystal structures of 2–5 have been determined by X-ray crystallography. Complexes 4 and 5 are isostructural. Their absorption and emission properties are studied. The magnetic properties of complexes 4 and 5 have also been investigated.By deprotonation reaction of the rhenium(I) tricarbonyl complex ClRe(CO)3(H2bpydt) (2, H2dpydt = 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylic acid), complex 3, [Bu4N][ClRe(CO)3(Hbpydt)], is synthesized. Using 3 as the building block, two interesting trinuclear heterometallic complexes M(MeOH)4[ClRe(CO)3Hbpydt]2·2MeOH (M = Cu, 4; M = Mn, 5) are obtained. These complexes have been characterized by IR, UV and single X-ray crystallography.
Co-reporter:Cai-Feng Wang, Dong-Ping Li, Xin Chen, Xiao-Ming Li, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You
Chemical Communications 2009 (Issue 45) pp:6940-6942
Publication Date(Web):22 Oct 2009
DOI:10.1039/B916637H
The assembly of chirality into magnetic nanowires enables the formation of two new cyano-bridged heterobimetallic 3,2-chain enantiomeric complexes, representing the first example of multiferroic compounds bearing both slow magnetization relaxation and ferroelectricity.
Co-reporter:Zhi-Guo Gu, Yi-Fan Xu, Ling-Chen Kang, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You
Inorganic Chemistry 2009 Volume 48(Issue 12) pp:5073-5080
Publication Date(Web):April 29, 2009
DOI:10.1021/ic8023524
A new family of polynuclear clusters containing the FeIII3MII cores [(Tp4Bo)6Fe6(CN)18M2Na2(H2O)16]·4H2O (M = Cu, Co, Mn; 1−3) and [(Tp4Bo)6Fe6(CN)18M2Na2(H2O)12(DMF)4]·H2O (M = Cu, Co, Mn; 4−6) have been synthesized and structurally characterized. Complexes 1−3 crystallize in the P21/c space group, and 4−6 crystallize in the P21/n space group. All six complexes consist of two symmetry-related T-shaped [(Tp4Bo)3(CN)9Fe3M]− subunits linked by two Na+ cations. Each polynuclear cluster in 1−6 strongly interacts with 12 adjacent such units through π−π interactions, leading to the formation of 3D 12-connected frameworks. Magnetic studies show appreciable magnetic anisotropies in compounds 1, 2, 4, and 5. Antiferromagnetic interactions were observed in complexes 3 and 6.
Co-reporter:Xiao-Ming Li, Cai-Feng Wang, Yong Ji, Ling-Chen Kang, Xin-Hui Zhou, Jing-Lin Zuo and Xiao-Zeng You
Inorganic Chemistry 2009 Volume 48(Issue 19) pp:9166-9173
Publication Date(Web):August 27, 2009
DOI:10.1021/ic900757s
With the use of the tailored tricyanometalate precursors [(L)Fe(CN)3]− (L = Tp, tris(pyrazolyl)hydroborate; L = i-BuTp, 2-methylpropyltris(pyrazolyl)borate) and terephthalate (ta) units as the mixed bridging ligands, a new one-dimensional (1D) chain polymer {[(Tp)2Fe2(CN)6Cu2(ta)(dmbpy)2]·7H2O}n (1), a pentanuclear heterometallic cluster [(Tp)2Fe2(CN)6Cu3(phen)3(ta)2(MeOH)(H2O)2]·8H2O (2), and a tetranuclear heterometallic cluster [(i-BuTp)2Fe2(CN)6Cu2(ta)(phen)2(EtOH)2]·2MeOH·H2O (3) (dmbpy = 4,4′-dimethyl-2,2′-bipyridyl, phen = 1,10-phenanthroline) have been synthesized and structurally characterized. The FeIII and CuII ions are bridged by cyanides, and the CuII ions are further linked by terephthalate to form the 1D chain polymer, the pentanuclear cluster, and the tetranuclear cluster for complexes 1−3, respectively. All complexes show ferromagnetic interactions between the FeIII and CuII ions. Complex 1 shows metamagnetic behavior with the critical field of about 1.2 T at 1.8 K.
Co-reporter:Xin-Hui Zhou, Yan-Hong Peng, Xiao-Di Du, Jing-Lin Zuo and Xiao-Zeng You
CrystEngComm 2009 vol. 11(Issue 9) pp:1964-1970
Publication Date(Web):28 May 2009
DOI:10.1039/B819302A
Three new coordination polymers with 1,2,3-triazolate ligands, [Cd3(ta)3Cl3]n (1), {[Cd3(ta)6]·6H2O}n (2) and [Cu6(ta)3I3]n (3) (Hta = 1,2,3-triazole), have been hydrothermally synthesized and structurally characterized. In complex 1, the Cd2+ and Cl− ions form a 3D [(Cd3Cl3)3+]n inorganic framework with (82.12)(4.8.10) topology while the Cd2+ ions and ta− ligands give a {[Cd3(ta)3]3+}n double helical chain. The two moieties are fused with each other by sharing “hinge” Cd2+ ions leading to a 3D organic–inorganic hybrid structure. The 3D porous metal–organic framework of complex 2 shows the topology of the diamond net with the Cd-centered CdCd4 tetrahedron units as the connecting nodes. The desolvated structure of 2 has 48% solvent accessible space of the total volume. Complex 3 is an undulating 1D organic–inorganic hybrid complex consisting of interesting discrete five-capped [Cu6I5]− triangular prism clusters and arched metallacycle [Cu6(ta)6I]+ moieties.
Co-reporter:Xiao-Qiang Liang, Xin-Hui Zhou, Chao Chen, Hong-Ping Xiao, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You
Crystal Growth & Design 2009 Volume 9(Issue 2) pp:1041
Publication Date(Web):January 2, 2009
DOI:10.1021/cg8008859
Six d10 metal metal-organic coordination polymers, {[Zn2(Htpim)2(tp)2]·2H2O}n (1), {[Cd3(H0.5tpim)4(pa)2(H2O)2]·5H2O}n (2), [Zn(Htpim)2(Htma)]n (3), {[Zn4(Htpim)4(ip)4]·2H2O}n (4), [Cd(Htpim)(ca)]n (5), and {[Cd4(Htpim)2(d-ca)4(H2O)2]·5H2O}n (6) (Htpim = 2,4,5-tri(4-pyridyl)-imidazole, H2tp = terephthalic acid, H2pa = phthalic acid, H3tma = trimesic acid, H2ip = isophthalic acid, H2ca = racemic camphor acid, d-H2ca = d-camphor acid), have been prepared and structurally characterized. In all complexes, the rigid ligand Htpim exhibits different coordination modes and leads to the formation of various architectures. Complex 1 shows a two-dimensional (2D) network with (6,3) topology, where hydrogen-bonding interactions further link these sheets to a three-dimensional (3D) supramolecular structure. Complex 2 exhibits a 2D layer with (53)(54) network topology. Complex 3 is a corrugated 2D layer with (4,4) topology, and the separated layers are connected through weak π−π stacking interactions to generate a 3D supramolecular architecture. Complex 4 is a rhombic 2D layer with (4,4) topology, and the 3D overlapped array is formed by hydrogen-bonding and π−π stacking interactions. A 3D diamondoid framework with 4-fold interpenetration is found in 5. Complex 6 contains a complicated 3D framework, and the vacancy is occupied by the guest water molecules. Their luminescent properties have been investigated in the solid state.
Co-reporter:Xin-Hui Zhou, Yan-Hong Peng, Xiao-Di Du, Cai-Feng Wang, Jing-Lin Zuo and Xiao-Zeng You
Crystal Growth & Design 2009 Volume 9(Issue 2) pp:1028
Publication Date(Web):December 19, 2008
DOI:10.1021/cg800848n
A series of 3d−4f heterometallic coordination polymers {[CuLn2(pdc)2(SO4)(H2O)6]·H2O}n (Ln = Tb (1), Dy (2); H3pdc = 3,5-pyrazoledicarboxylic acid), {[CuLn2(pdc)2(SO4)(H2O)4]·H2O}n (Ln = Sm (3), Eu (4), Gd (5), Tb (6), Dy (7)) have been hydrothermally synthesized and structurally characterized. The sulfate anions were in situ obtained from oxidation of CuSCN during the reaction. Complexes 1−7 are all constructed from pyrazole-bridged CuIILnIII dinuclear units and sulfate anions. Complexes 1 and 2 are isostructural and possess an infinite double-stranded tapelike 1D coordination framework. However, complexes 3−7 are interesting 3d−4f heterometallic coordination polymers with similar 3D framework structures. The magnetic properties of compounds 2, 4−6 have been investigated through the magnetic measurements over the temperature range of 1.8−300 K.
Co-reporter:Xiao-Qiang Liang, Dong-Ping Li, Xin-Hui Zhou, Yan Sui, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You
Crystal Growth & Design 2009 Volume 9(Issue 11) pp:4872
Publication Date(Web):September 15, 2009
DOI:10.1021/cg900676x
A new family of coordination polymers, [{Cd(d-ca)(bte)}·H2O]n (1, d-H2ca = d-camphor acid, bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), [Cd4(d-ca)4(btp)2(H2O)4]n (2, btp = 1,3-bis(1,2,4-triazol-1-yl)propane), [{Cd(d-ca)(btb)1.5}·3H2O]n (3, btb = 1,4-bis(1,2,4-triazol-1-yl)butane), [{Cd4(d-ca)4(bth)4}·2H2O]n (4, bth = 1,6-bis(1,2,4-triazol-1-yl)hexane), and [{Cd(d-Hca)2(bth)(H2O)}·H2O]n (5), have been prepared under hydrothermal conditions and characterized by elemental analyses, IR, thermogravimetric and X-ray structural analyses. The bis(triazole) ligands with different spacer lengths exhibit conformational flexibility and lead to the generation of diversified architectures. Complex 1 shows a two-dimensional (2D) rectangular network with (4,4) topology. Complex 2 displays the chiral three-dimensional (3D) framework with (32·4) (3·84·12) (83) (4·8·10) topology. The 2D honeycomb motif with one-dimensional (1D) nanosized channels is found in compound 3. Compound 4 is a 2D parallelogram sheet with (4,4) topology. Compound 5 shows a chiral 1D fish-bone chain, and the chains are further connected through hydrogen-bonding interactions to form a 3D supramolecular framework. Their luminescent, second-order nonlinear optical and ferroelectric properties have been investigated in the solid state.
Co-reporter:Xin-Hui Zhou, Xiao-Di Du, Gao-Nan Li, Jing-Lin Zuo, and Xiao-Zeng You
Crystal Growth & Design 2009 Volume 9(Issue 10) pp:4487
Publication Date(Web):August 10, 2009
DOI:10.1021/cg900509r
Seven coordination polymers with 3,5-pyrazoledicarboxylic acid (H3pdc) and bridging triazolyl ligands, [Ni3(pdc)2(btb)2(H2O)6]n (1), [Zn2(Hpdc)2(btb)(H2O)2]n (2), {[Ni3(pdc)2(bth)(H2O)8]·2DMF}n (3), [Ni(Hpdc)(bth)]n (4), [Ni3(pdc)2(bth)3(H2O)4]n (5), [Ni(Hpdc)(bth)(H2O)]n (6), and {[Zn(Hpdc)(bth)(H2O)]·2H2O}n (7) (btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bth = 1,6-bis(1,2,4-triazol-1-yl)hexane), have been hydrothermally or solvothermally synthesized and structurally characterized. Complexes 1, 3, and 4 are all one-dimensional chain coordination polymers. The structure of 2 comprises herringbone-like two-dimensional 63 nets. 5 possesses a six-connected self-penetrated three-dimensional (3D) architecture with 44.610.8 topological symbol. Complexes 6 and 7 have a similar 3D framework and can be simplified as a four-connected 66 topological network. However, because of the flexibility of the bth ligands in conformations, homochiral helical and meso-helical chains are formed by metal ions and bth ligands in 6 and 7, respectively. The magnetic properties of compounds 1, 3, 5, and 6 are investigated over the temperature range of 1.8−300 K.
Co-reporter:Yan Zhou, Hong-Ping Xiao, Ling-Chen Kang, Jing-Lin Zuo, Cheng-Hui Li and Xiao-Zeng You
Dalton Transactions 2009 (Issue 46) pp:10256-10262
Publication Date(Web):16 Oct 2009
DOI:10.1039/B914262B
By reacting metal cyanide complexes with NaBPh4 in the presence of acid at room temperature, a new class of neutral isocyanotriphenylborate-containing complexes trans-Ru(L)4(CNBPh3)2 (L = pyridine, 1; 4-methylpyridine, 2; 4-tert-butylpyridine, 3), cis-Ru(bipy)2(CNBPh3)2 (4, bipy = 2,2′-bipyridine) and cis-M(phen)2(CNBPh3)2 (M = Ru, 5; M = Fe, 6; phen = 1,10-phenanthroline) have been synthesized. These new complexes are characterized by IR, UV spectroscopy and single-crystal X-ray diffractions. The electron withdrawing triphenylborate group on the isocyanide ligands has a pronounced effect on the photophysical properties of complexes 1–6 in comparison with other ruthenium(II) and iron(II) isocyanide complexes. The excitation energies corresponding to metal-to-ligand charge transfer (MLCT) shift to higher energies while the 3MLCT emissions are quenched at room temperature.
Co-reporter:Ru Wang, Wei Liu, Ya Chen, Jing-Lin Zuo, Xiao-Zeng You
Dyes and Pigments 2009 Volume 81(Issue 1) pp:40-44
Publication Date(Web):April 2009
DOI:10.1016/j.dyepig.2008.09.001
A novel, metal-free, crown-ether-tetrathiafulvalene annulated phthalocyanine was synthesized by tetramerization of the corresponding phthalonitrile derivative; both compounds were characterized by elemental analysis, IR, UV–vis, DPV or CV and MS spectra. The crystal structure of the precursor was determined by X-ray crystallography. The charge transfer absorption bands of the two compounds lay ∼400 nm after addition of 7,7,8,8-tetracyanoquinodimethane. Electrochemical studies revealed that both compounds displayed good complexation selectivity for Na+ ion with large positive redox shifts, indicating that they may be a new redox-active sensor.
Co-reporter:Xiu-Ju Yin, Xin-Hui Zhou, Zhi-Guo Gu, Jing-Lin Zuo, Xiao-Zeng You
Inorganic Chemistry Communications 2009 Volume 12(Issue 6) pp:548-551
Publication Date(Web):June 2009
DOI:10.1016/j.inoche.2009.04.012
Two 3D organic–inorganic hybrid coordination polymers, [M2(ttmb)2(SO4)2(H2O)2] · 7H2O (M = Cd, 1; M = Mn, 2; ttmb = 1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene), have been synthesized and structurally characterized. They are isostructural and possess a 3D architecture fused from 2D (4,4) M(ttmb) networks and MSO4 chains by sharing “hinge” metal atoms. The thermal properties of 1 and 2, luminescent property of 1 as well as magnetic property of 2 have been investigated.Two 3D coordination polymers with the flexible tripodal ligand ttmb (1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene), [M2(ttmb)2(SO4)2(H2O)2] · 7H2O (M = Cd or Mn), have been synthesized and structurally characterized. They are isostructural and possess a 3D architecture fused from 2D (4,4) M(ttmb) networks and MSO4 chains by sharing “hinge” metal atoms. The thermal, luminescent and magnetic properties have been studied.
Co-reporter:Ling-Chen Kang, Xin Chen, Cai-Feng Wang, Xin-Hui Zhou, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2009 Volume 362(Issue 15) pp:5195-5202
Publication Date(Web):1 December 2009
DOI:10.1016/j.ica.2009.09.027
Co-reporter:Xin-Hui Zhou, Yan-Hong Peng, Zhi-Guo Gu, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2009 Volume 362(Issue 10) pp:3447-3453
Publication Date(Web):1 August 2009
DOI:10.1016/j.ica.2009.03.025
A series of pyrazole-bridged heterometallic 3d–4f complexes, [CuDy(ipdc)2(H2O)4] · (2H2O)(H3O+) (1) and [CuLn(pdc)(ipdc)(H2O)4] · H3O+ (Ln = Ho (2), Er (3), Yb (4); H3ipdc = 4-iodo-3,5-pyrazoledicarboxylic acid; H3pdc = 3,5-pyrazoledicarboxylic acid), {[Cu3Ln4(ipdc)6(H2O)16] · xH2O}n (Ln = Sm (5), x = 8.5; Ln = Eu (6), x = 7; Ln = Gd (7), Tb (8), x = 9), have been synthesized and structurally characterized. Ligand H3ipdc was in situ obtained by iodination of ligand H3pdc. Complexes 1–4 are pyrazole-bridged heterometallic dinuclear complexes, and 2–4 are isostructural. Complexes 5–8 are isostructural and comprised of an unusual infinite one-dimensional tape-like chain based on pyrazole-bridged heterometallic dinuclear units. The magnetic properties of compounds 1–4, 7 and 8 have been investigated through the magnetic measurement over the temperature range of 1.8–300 K.Under hydrothermal or solvothermal conditions, eight pyrazole-bridged heterometallic 3d–4f complexes have been synthesized and structurally characterized. Complexes 1–4 are pyrazole-bridged heterometallic dinuclear complexes, while 5–8 are isostructural and comprised of an unusual infinite one-dimensional tape-like chain. The magnetic properties of compounds 1–4, 7 and 8 have been investigated.
Co-reporter:Wei Liu, Zhi-Guo Gu, Ru Wang, Xin-Hui Zhou, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2009 Volume 362(Issue 8) pp:2556-2564
Publication Date(Web):1 June 2009
DOI:10.1016/j.ica.2008.11.025
Two new mononuclear spin-crossover iron(II) complexes, [FeL2(NCS)2] · H2O (1) and [FeL2(NCSe)2] (2), have been synthesized from the reaction of the versatile ligand 4,5-bis(2-cyanoethylthio)-2-bis(2-pyridyl)methylene-1,3-dithiole (L), Fe(ClO4)2, and KNCX (X = S/Se). Reactions of L with CuII or CoII salts afford one mononuclear complex [CuL(hfac)2] · CH3OH (hfac = hexafluoroacetylacetonate) (3), one dinuclear complex [(CuLCl)2(μ-Cl)2] · CH3OH (4), and two 1D chain species, [CuL2]n(BF4)2n (5) and [CoL2]n(ClO4)2n · 2nCH2Cl2 (6). The crystal structures of complexes 1 and 3–6 have been determined by X-ray crystallography. Short intermolecular S⋯S contacts between neighboring 1D arrays are observed in 5 and 6, which lead to the formation of the 2D structure. The magnetic properties are studied, and antiferromagnetic couplings between the CuII centers across the chloride bridges have been found in 4 (J = 2.04 cm–1). Spin-crossover behaviors between high and low spin states are observed at T1/2 = 80 K for 1 and T1/2 = 300 K for 2, respectively.Two mononuclear spin-crossover iron(II) complexes, [FeL2(NCS)2] · H2O (1) and [FeL2(NCSe)2] (2) (L = 4,5-bis(2-cyanoethylthio)-2-bis(2-pyridyl)methylene-1,3-dithiole), have been synthesized. Reactions of L with CuII or CoII salts afford the mononuclear complex [CuL(hfac)2] · CH3OH (3), dinuclear complex [(CuLCl)2(μ-Cl)2] · CH3OH (4), and two 1D chain species, [CuL2]n(BF4)2n (5) and [CoL2]n (ClO4)2n · 2nCH2Cl2 (6). Their magnetic properties have been studied and spin-crossover behaviors between high and low spin state are observed at T1/2 = 80 K for 1 and T1/2 = 300 K for 2, respectively.
Co-reporter:He-Rui Wen, Cai-Feng Wang, You Song, Yi-Zhi Li, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2009 Volume 362(Issue 5) pp:1485-1490
Publication Date(Web):1 April 2009
DOI:10.1016/j.ica.2008.07.014
Using the tetracyanometalate precursor [Fe(4,4′-dmbipy)(CN)4]- (4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine) as the building block, two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [M(CH3OH)2Fe2(4,4′-dmbipy)2(CN)8]n (M = Cu, 1; Mn, 2), have been synthesized and structurally characterized. X-ray crystallography reveals that complexes 1 and 2 consist of heterobimetallic chains of squares, and the central MII ion is six-coordinated as an elongated distorted octahedral geometry. Magnetic studies show ferromagnetic coupling between FeIII and CuII ions in complex 1. Complex 2 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (SMn = 5/2 and SFe = 1/2), which interact antiferromagnetically through bridging cyanide groups. magpack program has been employed to investigate the magnetic nature of squares chain structure.Using the tetracyanometalate precursor [Fe(4,4′-dmbipy)(CN)4] (4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine) as the building block, two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [M(CH3OH)2Fe2(4,4′-dmbipy)2(CN)8]n (M = Cu, 1; Mn, 2), have been synthesized. X-ray crystallography reveals that complexes 1 and 2 consist of one-dimensional heterobimetallic chains of squares. Magnetic studies show ferromagnetic coupling between FeIII and CuII ions in complex 1. Complex 2 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (SMn = 5/2 and SFe = 1/2) which interact antiferromagnetically through bridging cyanide groups.
Co-reporter:Ya Chen, Wei Liu, Bin Liu, Xin-Hui Zhou, Zhi-Gang Zou, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2009 Volume 362(Issue 1) pp:143-148
Publication Date(Web):1 January 2009
DOI:10.1016/j.ica.2008.03.053
Two new ruthenium (II) complexes containing coupled di(2-pyridyl) and 1,3-dithiole units, cis-[Ru(Medpydt)2(NCS)2] (2, Medpydt = dimethyl 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate) and cis-[Ru(H2dpydt)2(NCS)2] (3, H2dpydt = 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate), have been synthesized and characterized. The structure of complex 2 has been determined by X-ray crystallography. There exist intermolecular H-bonding interactions between carbomethoxy groups on neighboring pyridine rings giving rise to 2D H-bonded arrays. The metal-to-ligand charge-transfer (MLCT) absorptions were observed around 480 nm. Redox properties of ruthenium complexes have been investigated by cyclic voltammetry. Solar cells involving thin films of anatase TiO2 impregnated with cis-[Ru(H2dpydt)2(NCS)2] were prepared, and the photovoltaic performance was preliminarily investigated.Two new ruthenium (II) complexes containing coupled di(2-pyridyl) and 1,3-dithiole units, cis-[Ru(Medpydt)2(NCS)2] (2, Medpydt = dimethyl 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate) and cis-[Ru(H2dpydt)2(NCS)2] (3, H2dpydt = 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate), have been synthesized and characterized. The structure of complex 2 has been determined by X-ray crystallography. The photovoltaic performance for 3 was preliminarily investigated.
Co-reporter:Ya Chen;ChengHui Li;CaiFeng Wang;Di Wu
Science China Chemistry 2009 Volume 52( Issue 10) pp:1596-1601
Publication Date(Web):2009 October
DOI:10.1007/s11426-009-0237-2
A new Co(II) coordination polymer bearing TTF carboxylate group, [{Co2(trioTTF)2(H2O)6}·5H2O]n (1) (trioTTF = 2-(5,6,8,9,11,12,14,15-octahydro-[1,3]dithiolo[4,5-h][1,4,13,7,10]trioxadithiacyclopentadecin-2-ylidene)-1,3-dithiole-4,5-dicarboxylate), has been prepared and characterized. In the structure of 1, shorter intermolecular S····S contacts (3.565 Å) are found between the trioTTF groups from neighboring chains. The electric conductivity of 1 is poor due to the bulky crown-ether group, but it exhibits ferromagnetic interaction at low temperature.
Co-reporter:Ya Chen, Wei Liu, Jian-Shi Jin, Bin Liu, Zhi-Gang Zou, Jing-Lin Zuo, Xiao-Zeng You
Journal of Organometallic Chemistry 2009 694(5) pp: 763-770
Publication Date(Web):
DOI:10.1016/j.jorganchem.2008.12.018
Co-reporter:Xiao-Qiang Liang, Chao Chen, Xin-Hui Zhou, Hong-Ping Xiao, Yi-Zhi Li, Jing-Lin Zuo, Xiao-Zeng You
Polyhedron 2009 28(5) pp: 947-953
Publication Date(Web):
DOI:10.1016/j.poly.2008.12.059
Co-reporter:Wei Liu, Jing Xiong, Yong Wang, Xin-Hui Zhou, Ru Wang, Jing-Lin Zuo and Xiao-Zeng You
Organometallics 2009 Volume 28(Issue 3) pp:755-762
Publication Date(Web):January 6, 2009
DOI:10.1021/om800919u
A series of new tetrathiafulvalene-substituted 3,5-dimethylpyrazole ligands, 4-[{2,6,7-tris(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (MTSPz*, Pz* = 3,5-dimethylpyrazole, 4a), 4-[{6,7-benzo-2-(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (BTSPz*, 4b), 4-[{6,7-(ethylenedithio)-2-(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (ETSPz*, 4c) and 4-[{6,7-(propylenedithio)-2-(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (PTSPz*, 4d), have been prepared by an efficient synthetic route. Further coordination reactions of the respective ligands with Re(CO)5Cl afford new rhenium(I) tricarbonyl chloro complexes, ClRe(CO)3(MTSPz*)2 (5a), ClRe(CO)3(BTSPz*)2 (5b), ClRe(CO)3(ETSPz*)2 (5c) and ClRe(CO)3(PTSPz*)2 (5d). The crystal structures of the ligand 4d and complexes 5b−d have been determined by X-ray crystallography, showing nearly planar TTF units in these compounds, and the distorted octahedral geometry in all complexes. The absorption spectra and multiredox behaviors of these new compounds (4a−d, 5a−d) have been studied, and are rationalized based on density functional theory. The results suggest that the novel redox-active tetrathiafulvalene-pyrazole ligands are useful for the syntheses of new metal complexes.
Co-reporter:Cai-Feng Wang ; Zhi-Guo Gu ; Xiao-Mei Lu ; Jing-Lin Zuo ;Xiao-Zeng You
Inorganic Chemistry 2008 Volume 47(Issue 18) pp:7957-7959
Publication Date(Web):August 19, 2008
DOI:10.1021/ic801049e
Two homochiral trinuclear clusters, {(MeTp)2Fe2(CN)6Ni[(1R,2R)-chxn]2} (1) and {(MeTp)2Fe2(CN)6Ni[(1S,2S)-chxn]2} (2) [chxn = 1,2-diaminocyclohexane; MeTp = methyltris(pyrazolyl)borate], have been synthesized and structurally characterized. Ferroelectric and magnetic measurements reveal that they are rare examples of metal−organic compounds bearing ferroelectricity and intramolecular ferromagnetic interactions.
Co-reporter:Yong Ji, Rui Zhang, Xiao-Bo Du, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2008 (Issue 19) pp:2578-2582
Publication Date(Web):25 Mar 2008
DOI:10.1039/B719997J
Two new platinum(II) complexes containing both 4,4′-di-tert-butyl-2,2′-bipyridine (dbbpy) and crown ether annelated dithiolate ligands, [Pt(dbbpy)(3O-C2S4)] (1, 3O-C2S42− = 1,4,7-trioxa-10,13-dithiacyclopentadec-11-ene-11,12-dithiolate) and [Pt(dbbpy)(4O-C2S4)] (2, 4O-C2S42− = 1,4,7,10-tetraoxa-13,16-dithiacyclooctadec-14-ene-14,15-dithiolate), have been prepared and characterized. These two complexes show intense electronic absorption bands in the UV-vis region due to the intramolecular mixed metal/ligand-to-ligand charge transfer transition, and they display solvatochromic behavior. The redox properties of these compounds have been investigated by cyclic voltammetry and complex 2 shows a significant response for Na+ ions with a large positive shift of ca. 125 mV. Moreover, complex 2 is very sensitive in detecting Na+ cations with an obvious change in color which can be conveniently observed with the naked eye.
Co-reporter:Zhi-Guo Gu, Yi-Fan Xu, Xiu-Ju Yin, Xin-Hui Zhou, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2008 (Issue 41) pp:5593-5602
Publication Date(Web):26 Aug 2008
DOI:10.1039/B806619A
Three homochiral layered complexes, [Cu3(R-chea)2(N3)6]n (1), [Cu3(S-chea)2(N3)6]n (2) (chea = 1-cyclohexylethylamine) and [Cu3(S-phpa)2(N3)6]n (3) (phpa = 1-phenylpropylamine), and three novel cluster-based coordination polymers, [Cu6(1,2-pn)4(N3)12]n (4) (1,2-pn = 1,2-diaminopropane), {[Cu8(en)4(N3)16]·H2O}n (5) (en = ethylenediamine) and [Cu6(N-Ipren)2(N3)12]n (6) (N-Ipren = N-isopropylethylenediamine), have been synthesized by the self-assembly reactions of Cu(NO3)2·3H2O, NaN3 and small organic amine ligands. Their crystal structures are determined by single-crystal X-ray diffraction. Complexes 1–3 are composed of neutral 2D brick wall networks with only end-on azido bridges. Complexes 4 and 5 are 3D coordination polymers featuring copper–azido clusters and [Cu(diamine)2]2+ units which are linked by the azido bridges. Complex 6 is a 3D coordination framework based on the hexanuclear copper(II) clusters [Cu6(N3)12(N-Ipren)2]. Magnetic studies show that complexes 1–3 are interesting chiral ferromagnets with the magnetic transition temperature at ca. 5.0 K. Complexes 4 and 5 show ferromagnetic coupling in the copper–azido cluster units and antiferromagnetic interaction between neighboring units, while complex 6 shows ferromagnetic ordering at 3.2 K.
Co-reporter:Zhi-Guo Gu, Yi-Fan Xu, Xin-Hui Zhou, Jing-Lin Zuo and Xiao-Zeng You
Crystal Growth & Design 2008 Volume 8(Issue 4) pp:1306
Publication Date(Web):March 4, 2008
DOI:10.1021/cg7010666
By the reactions of FeX2 with α,ω-bis(1,2,4-triazol-1-yl)alkane ligands (X = ClO4−, BF4−, NCS−, and NCSe−), a series of novel iron(II) coordination polymers have been synthesized and characterized. Complexes [Fe(btp)3](ClO4)2 (1a), [Fe(btp)3](BF4)2 (1b), and [Fe(btp)2(NCS)2] (2) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane) are infinite 1D-linear chains. [Fe(btb)3](ClO4)2 (3a) and [Fe(btb)3](BF4)2 (3b) (btb = 1,4-bis(1,2,4-triazol-1-yl)butane) are 3-fold interpenetrated α-polonium cubic frameworks. The two sorts of btb ligands with different conformations alternately link to the Fe(II) centers in [Fe(btb)2(NCS)2]·H2O (4) to form a 3D interpenetrating architecture of CdSO4-like topology. When NCSe− instead of NCS− was used as the framework-regulator, a 2D grid layer [Fe(btb)2(NCSe)2]·2H2O (5) was obtained. The counteranions, spacer length, and conformation of the α,ω-bis(1,2,4-triazol-1-yl)alkane ligands are responsible for the assembled topological architectures. Magnetic studies indicate that all of these iron(II) polymers retain a high-spin ground state upon cooling from 300 to 4 K.
Co-reporter:Cai-Feng Wang;Wei Liu;You Song;Xin-Hui Zhou, ;Xiao-Zeng You
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 5) pp:717-727
Publication Date(Web):
DOI:10.1002/ejic.200701104
Abstract
Three tricyanometalate precursors, (Bu4N)[(PhTp)Fe(CN)3]·H2O (1), (Bu4N)[(MeTp)Fe(CN)3] (2), and (Bu4N)[(iBuTp)Fe(CN)3] (3) [Bu4N+ = tetrabutylammonium cation; PhTp = tris(pyrazolyl)phenylborate; MeTp = methyltris(pyrazolyl)borate; iBuTp = 2-methylpropyltris(pyrazolyl)borate], were successfully synthesized. By using 1–3 as building blocks, four rectangular clusters, [(PhTp)Fe(CN)3Cu(bpy)(H2O)(ClO4)]2·2H2O (4; bpy = 2,2′-bipyridine), [(PhTp)Fe(CN)3Ni(tren)]2(ClO4)2 [5; tren = tris(2-amino)ethylamine], [(MeTp)Fe(CN)3Ni(tren)]2(ClO4)2·2H2O (6), and [(iBuTp)Fe(CN)3Ni(tren)]2(ClO4)2·2H2O·2CH3OH (7), were prepared in parallel and structurally characterized. All clusters show similar square structures, where FeIII and MII (M = CuII or NiII) ions are alternatively located on the rectangle corners. The cyclic voltammograms of FeIII2NiII2 clusters 5–7 reveal two quasireversible iron-centered reduction processes and two quasireversible nickel-centered oxidation processes. Magnetic studies show intramolecular ferromagnetic coupling and appreciable magnetic anisotropy in clusters 4–7. Complexes 5–7 show obvious frequency dependence in the alternating current magnetic susceptibility data, which indicates single-molecule magnet behavior with preexponential factors of τ0 = 4.5 × 10–8 s (5), 6.1 × 10–8 s (6), and 5.0 × 10–8 s (7) and the effective spin-reversal barriers of Ueff = 17.5 K (5), 20.6 K (6), and 20.8 K (7).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:Yu-Jia Li, Wei Liu, Yi-Zhi Li, Jing-Lin Zuo, Xiao-Zeng You
Inorganic Chemistry Communications 2008 Volume 11(Issue 12) pp:1466-1469
Publication Date(Web):December 2008
DOI:10.1016/j.inoche.2008.10.010
Deprotection of the cyanoethyl groups with 2 equivalents of the strong base (CsOH) and subsequent reaction with the electrophilic 3-chloro-2,4-pentanedione afford the bis(acetylacetone)tetrathiafulvalenes, trans- and cis-acac2. The formation of the dinuclear rectangle-shaped complex [Cu2(cis-acac2)2 ⋅ 2DMF ⋅ 2H2O] (1), demonstrates the chelating ability of the interesting TTF-acetylacetonate ligand. Cyclic voltammetry experiments have evidenced the two one-electron steps to the radical cation and dication species of the new ligand, and the two quasi-reversible two-electron oxidation processes of complex 1.A dinuclear copper(II) complex with cis-bis(acetylacetonate)tetrathiafulvalene ligand, [Cu2(cis-acac2)2 ⋅ 2DMF ⋅ 2H2O] (1), was prepared and structurally characterized. The redox properties of both the interesting ligand and the metal complex were investigated by cyclic voltammetry.
Co-reporter:He-Rui Wen, Cai-Feng Wang, Zi-Yi Du, Jing-Lin Zuo
Inorganica Chimica Acta 2008 Volume 361(9–10) pp:2901-2908
Publication Date(Web):27 June 2008
DOI:10.1016/j.ica.2008.02.036
Two tetracyanometalate building blocks, [Fe(5,5′-dmbipy)(CN)4]− (2) and [Fe(4,4′-dmbipy)(CN)4]− (3) (5,5′-dmbipy = 5,5′-dimethyl-2,2′-bipyridine; 4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine), and two cyano-bridged heterobimetallic complexes, [Cu2(bpca)2(H2O)2Fe2(5,5′-dmbipy)2(CN)8] · 2[Cu(bpca)Fe(5,5′-dmbipy)(CN)4] · 4H2O (4) and [Cu(bpca)Fe(4,4′-dmbipy)(CN)4]n (5) (bpca = bis(2-pyridylcarbonyl)amidate), have been synthesized and structurally characterized. Complex 4 contains two dinuclear and one tetranuclear heterobimetallic clusters in an asymmetric unit whereas the structure of complex 5 features a one-dimensional heterobimetallic zigzag chain. The Cu(II) ion is penta-coordinated in the form of a distorted square-based pyramid. Magnetic studies show ferromagnetic coupling between Cu(II) and Fe(III) ions with g = 2.28, J1 = 2.64 cm−1, J2 = 5.40 cm−1 and TIP = −2.36 × 10−3 for complex 4, and g = 2.17, J = 4.82 cm−1 and zJ′ = 0.029 cm−1 for complex 5.Two cyano-bridged heterobimetallic complexes, [Cu2(bpca)2(H2O)2Fe2(5,5′-dmbipy)2(CN)8] · 2[Cu(bpca)Fe(5,5′-dmbipy)(CN)4] · 4H2O (4) and [Cu(bpca)Fe(4,4′-dmbipy)(CN)4]n (5) (bpca = bis(2-pyridylcarbonyl)amidate; 5,5′-dmbipy = 5,5′-dimethyl-2,2′-bipyridine; 4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine), have been synthesized with the use of [Fe(5,5′-dmbipy)(CN)4]− (2) or [Fe(4,4′-dmbipy)(CN)4]− (3) as building blocks. Complex 4 contains two dinuclear and one tetranuclear clusters in an asymmetric unit whereas complex 5 features a one-dimensional zigzag chain. Magnetic studies show ferromagnetic coupling between Cu(II) and Fe(III) ions for both 4 and 5.
Co-reporter:Peng Zheng;Yun-Jun Guo;Wei Liu;Yi-Zhi Li
Transition Metal Chemistry 2008 Volume 33( Issue 6) pp:767-773
Publication Date(Web):2008 September
DOI:10.1007/s11243-008-9109-4
Two new tetrathiafulvalene (TTF) derivatives of acetylacetone, namely, 3-[{6,7-benzo-2-(methylthio)-TTF-3-yl}-thio]-2,4-pentanedione (L1) and 3-[{6,7-(ethylenedithio)-2-(methylthio)-TTF-3-yl}-thio]-2,4-pentanedione (L2), have been synthesized. Four transition metal(II) complexes of these ligands, of general formulae [Zn(L1)2(THF)2] and [M(L2)2(THF)2] (M = Zn, Mn, and Ni), have been prepared and structurally characterized. The redox properties of both the ligands and their complexes were investigated by cyclic voltammetry.
Co-reporter:Wei Liu;Yun-Jun Guo;Yu-Jia Li;Yan-Yan Mao
Research on Chemical Intermediates 2008 Volume 34( Issue 2-3) pp:257-266
Publication Date(Web):2008 February
DOI:10.1163/156856708783623546
Two new fluorescent crown ether derivatives of tetrathiafulvalene (TTF) (2a and 2b) were synthesized and characterized; their electrochemical response to Na+ ions and fluorescence properties were investigated. The mechanism of the strong fluorescence has also been explored.
Co-reporter:Wei Liu, Ru Wang, Xin-Hui Zhou, Jing-Lin Zuo and Xiao-Zeng You
Organometallics 2008 Volume 27(Issue 1) pp:126-134
Publication Date(Web):December 19, 2007
DOI:10.1021/om700776s
A new type of polypyridine ligand containing coupled bis(2-pyridyl) and cyanoethylthio-protected dithiolene, 4,5-bis(2-cyanoethylthio)-2-bis(2-pyridyl)methylene-1,3-dithiole (BPyDT(SCH2CH2CN)2, 3), two mononuclear complexes, BrRe(CO)3(BPyDT(SCH2CH2CN)2) (4) and BPyDTS2Pt(dbbpy) (7), and one homodinuclear complex, BPyDT(SAuPPh3)2 (5), have been synthesized and characterized. With the deprotected polypyridine ligand BPyDTS22− as the bridging unit, one tricarbonyl rhenium(I) heterotrinuclear complex, ClRe(CO)3(BPyDT(SAuPPh3)2) (6), and one heterodinuclear complex, ClRe(CO)3(BPyDTS2Pt(dbbpy)) (8, dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine), have been studied. The structures of all these compounds have been determined by X-ray crystallography. UV–vis studies have been carried out for them, showing distinct electronic absorptions. Compounds 3–6 exhibit blue to red luminescence in CH2Cl2 solution at room temperature. Ground-state electronic structures for 3–8 have been analyzed by the B3LYP calculations.
Co-reporter:Wei Liu ; Ya Chen ; Ru Wang ; Xin-Hui Zhou ; Jing-Lin Zuo ;Xiao-Zeng You
Organometallics 2008 Volume 27(Issue 13) pp:2990-2997
Publication Date(Web):May 23, 2008
DOI:10.1021/om800178k
Two bispyridine ligands containing crown ether-annelated or anthryl-substituted 1,3-dithiole-2-ylidene, 4,5-dithia-(3′,6′,9′,12′-tetraoxatetradecyl)-2-bis(2-pyridyl)methylene-1,3-dithiole (BPyDT(O4S2), 3) and 4-methylthio-5-[{2-(9′-anthryloxy)-ethyl}thio]-2-bis(2-pyridyl)methylene-1,3-dithiole (BPyDT(SMe)(SEA), 7), have been synthesized and characterized. The rhenium(I) tricarbonyl complexes ClRe(CO)3(BPyDT(O4S2)) (4) and BrRe(CO)3(BPyDT(SMe)(SEA)) (8) have been prepared based on them. The crystal structures of compounds 3, 4, and 8 have been determined. Complexes 4 and 8 exhibit greenish-yellow emission, while ligands 3 and 7 show blue luminescence in fluid solutions at room temperature. Redox properties of 3, 4, 7, and 8 have been investigated by cyclic voltammetry, and the crown ether-annelated compounds 3 and 4 show significant Na+-binding properties with large positive redox shifts.
Co-reporter:Zhi-Guo Gu, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2007 (Issue 36) pp:4067-4072
Publication Date(Web):21 Aug 2007
DOI:10.1039/B708789F
Two novel three-dimensional coordination polymers [Cu6(N3)12(N-Eten)2]n (1) (N-Eten = N-ethylethylenediamine) and {[Cu9(N3)18(1,2-pn)4]·H2O}n (2) (1,2-pn = 1,2-diaminopropane) have been synthesized by the self-assembly reactions of Cu(NO3)2·3H2O, NaN3 and small diamine ligands. Their molecular structures were determined by single-crystal X-ray diffraction. Complex 1 is composed of a neutral 3D coordination framework based on unprecedented hexanuclear copper(II) clusters which features three types of bridging modes for azide (µ-1,1, µ-1,3 and µ-1,1,3). Complex 2 is a novel 3D coordination polymer featuring octanuclear copper–azido clusters and [Cu(diamine)2]2+ units which are linked by azido bridges. Magnetic studies for complex 1 show ferromagnetic ordering at 3.5 K, where the azido bridges mediate ferromagnetic coupling between adjacent Cu(II) ions. The magnetic data for 1 were fitted to a uniform hexanuclear copper model which yielded g = 2.21, J = 6.26 cm−1, zJ′ = 0.39 cm−1. Complex 2 shows ferromagnetic coupling in the octanuclear unit and antiferromagnetic interaction between neighboring units.
Co-reporter:Qiao-Fang Yang, Zhi-Guo Gu, Cheng-Hui Li, Jian-Qing Tao, Jing-Lin Zuo, Xiao-Zeng You
Inorganica Chimica Acta 2007 Volume 360(Issue 9) pp:2875-2880
Publication Date(Web):10 June 2007
DOI:10.1016/j.ica.2007.01.017
Two new one-dimensional azido-bridged chiral copper(II) coordination polymers, [(μ-1,1,3-N3)2{Cu2(R-L)2(N3)2}]n (1) (R-L = R-2-(N-(2-hydroxybutyl)carbaldimino) pyridine) and [(μ-1,1,3-N3)2{Cu2(S-L)2(N3)2}]n (2) (S-L = S-2-(N-(2-hydroxybutyl)carbaldimino)pyridine) have been synthesized and structurally characterized. Complexes 1 and 2 crystallize in the monoclinic chiral space group P21. For 1, with a = 6.9565(17) Å, b = 20.675(5) Å, c = 9.859(2) Å, β = 105.944(5)° and Z = 2. In the case of compound 2, a = 6.9650(17) Å, b = 20.705(5) Å, c = 9.878(2) Å, β = 105.941(4)° and Z = 2. Both complexes consist of one-dimensional chiral structures in which the copper(II) ions with a distorted octahedral geometry are interlinked by the unusual μ-1,1,3 azido ligands. Circular dichroism spectra demonstrate that 1 and 2 are a pair of enantiomers. Their magnetic properties have been studied. Fitting of the susceptibility data for 1 and 2 using the Bleany–Bowers expression derived from the isotropic spin-exchange Hamiltonian H = −2JS1S2 leads to the parameters g = 2.21, J = −2.06 cm−1, zJ′ = −0.0309 cm−1 and R = 4.0 × 10−4.Two new one-dimensional azido-bridged chiral copper(II) coordination polymers, [(μ-1,1,3-N3)2{Cu2(R-L)2(N3)2}]n (1) and [(μ-1,1,3-N3)2{Cu2(S-L)2(N3)2}]n (2) (L = 2-(N-(2-hydroxybutyl)carbaldimino)pyridine), have been synthesized and structurally characterized. Both crystal structures and circular dichroism spectra demonstrate that 1 and 2 are a pair of enantiomers. The magnetic studies on them reveal that there exist antiferromagnetic interactions between the copper(II) ions through μ-1,1,3-N3 azide bridges.
Co-reporter:Wei Liu;Xiao-Zeng You;Xi-Rui Zeng;Yun-Jun Guo
Journal of Heterocyclic Chemistry 2007 Volume 44(Issue 4) pp:831-836
Publication Date(Web):13 MAR 2009
DOI:10.1002/jhet.5570440413
A series of new unsymmetrical tetrathiafulvalene carboxylate derivatives (7-11) were synthesized and characterized by NMR, MS, electrochemical studies and X-ray crystal structural determination. Compound 8 showed obvious changes in redox peak potentials as the concentration of p-toluenesulfonic acid changes.
Co-reporter:Rui Zhang;Xiao-Zeng You;Yong Ji;Ming Xu
Journal of Heterocyclic Chemistry 2006 Volume 43(Issue 5) pp:1361-1365
Publication Date(Web):13 MAR 2009
DOI:10.1002/jhet.5570430534
A series of new crown-ether annelated TTF derivatives 2a, 2b, 2c, 3 and 5 have been synthesized and characterized by melting points, NMR, IR and ESI-MS. The crystal structure of compound 3, 2, 3-dithia-(5′,8′-dioxaoctyl)-6,7-ethylenedithiatetrathiafulvalene, has been determined by X-ray crystallography. Redox properties of all these compounds have been investigated by cyclic voltammetry and each compound shows two reversible single-electron redox couples. The results indicate that 3 is responsive for Li+, but not to other alkali metal cations, such as Na+ and K+. Although with the same cavity, compounds 2c and 5 show marked changes upon the addition of sodium perchlorate, while there is no significant response for 2a and 2b at the same condition.
Co-reporter:Sheng-Gui Liu, Jing-Lin Zuo, Yue Wang, Yi-Zhi Li, Xiao-Zeng You
Journal of Physics and Chemistry of Solids 2005 Volume 66(Issue 5) pp:735-740
Publication Date(Web):May 2005
DOI:10.1016/j.jpcs.2004.10.004
A very stable and blue luminescent complex Zn(bbp)Cl2 (bbp: 2,6-bis(benzimidazolyl)pyridine) was synthesized. X-ray crystal structural analysis for the complex revealed that there are intermolecular π⋯π interactions in the solid state. The fluorescence properties for this complex were studied. The similar devices with the structure of [ITO/CuPc(31 nm)/NPB(80 nm)/[Zn(bbp)Cl2] (or L) (85 nm)/LiF15/Al] were constructed to investigate their electroluminescent performance. Both the complex and the ligand can be fabricated as blue-emitting materials. The complex shows emission peak at 555 nm, electroluminescent efficiency 0.017 cd A−1 and turn-on voltage 7 V, compared to 470 nm, 0.036 cd A−1 and 9 V for the ligand.
Co-reporter:Yong Ji, Jing-Lin Zuo, Lixue Chen, Yun-Qi Tian, Yinglin Song, Yi-Zhi Li, Xiao-Zeng You
Journal of Physics and Chemistry of Solids 2005 Volume 66(Issue 1) pp:207-212
Publication Date(Web):January 2005
DOI:10.1016/j.jpcs.2004.09.015
Three nickel complexes with a new multi-sulfur 1,2-dithiolene ligand, (n-Bu4N)[Ni(cddt)2] 1, (Ph4P)[Ni(cddt)2] 2 and [Ni(cddt)2] 3 (cddt=4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3-dithiolate), have been synthesized and characterized by electrochemical measurements, IR, EPR and UV–Vis-NIR spectroscopies. The crystal structure of complex 2 is determined. Their optical nonlinearities are measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm and all exhibit NLO absorptive abilities. Complexes 1 and 2 both exhibit effective self-defocusing performance (n2=−5.81×10−10 esu for 1 and −4.51×10−10 esu for 2). The optical limiting (OL) effects were observed with nanosecond and picosecond laser pulses. The OL capability of complex 3 is superior to C60 at the same experimental condition in ns measurements.
Co-reporter:He-Rui Wen, Jing-Lin Zuo, Wei Liu, You Song, Xiao-Zeng You
Inorganica Chimica Acta 2005 Volume 358(Issue 8) pp:2565-2570
Publication Date(Web):2 May 2005
DOI:10.1016/j.ica.2005.02.003
A novel one-dimensional chiral copper(II) complex with single end-on (EO) azide bridge and chiral 2,2-bipyridine ligand, [Cu(N3)2(L)]n (1), and a mononuclear chiral copper(II) complex, [Cu(N3)2(L)] (2) (L = (1R)-6,6-dimethyl-5,7-methano-2-(2-pyridinyl)-4,5,6,7-tetrahydroquinoline), have been synthesized and characterized. The crystal structure determination shows that complex 1 is a one-dimensional chiral coordination polymer with non-equivalent Cu–N(azide) bonds, in which the central Cu(II) ion is penta-coordinated in the form of a slightly distorted square-based pyramid. Compound 2 is a four-coordinated mononuclear complex where the Cu(II) ion has a highly distorted tetrahedronal environment. Both complexes 1 and 2 crystallize in the chiral space group: P212121 and P1, respectively. The magnetic studies show that there exists antiferromagnetic interaction between the copper(II) ions in complex 1.A novel one-dimensional chiral copper(II) complex with single end-on (EO) azide bridge and chiral 2,2-bipyridine ligand, [Cu(N3)2(L)]n (1), and a mononuclear chiral copper(II) complex [Cu(N3)2(L)] (2) (L = (1R)-6,6-dimethyl-5,7-methano-2-(2-pyridinyl)-4,5,6,7-tetrahydroquinoline), have been synthesized. Both complexes 1 and 2 crystallize in the chiral space group: P212121 and P1, respectively. The magnetic studies show that there exists antiferromagnetic interaction between the copper(II) ions in complex 1.
Co-reporter:Shi Wang, Jing-Lin Zuo, Hong-Cai Zhou, You Song, Xiao-Zeng You
Inorganica Chimica Acta 2005 Volume 358(Issue 6) pp:2101-2106
Publication Date(Web):30 March 2005
DOI:10.1016/j.ica.2004.12.034
Using an anionic precursor [(Tp)FeIII(CN)3]− (1) as a building block, two cyano-bridged centrosymmetric heterotrinuclear complexes, [(Tp)2Fe2III(CN)6MnII(C2H5OH)4]·2C2H5OH (2) and [(Tp)2Fe2III(CN)6Ni(en)2] (3) (en = ethylenediamine), have been synthesized and structurally characterized. In each complex, [TpFe(CN)3]− acts as a monodentate ligand toward a central [Mn(C2H5OH)4]2+ or [Ni(en)2]2+ core through one of its three cyanide groups, the other two cyanides remaining terminal. The intramolecular Fe–Mn and Fe–Ni distances are 5.2354(4) and 5.0669(11) Å, respectively. The magnetic properties of complexes 2 and 3 have been investigated in the temperature range of 2.0–300 K. A weak antiferromagnetic interaction between the Mn(II) and Fe(III) ions has been found in complex 2. The magnetic data of 2 can be fitted with the isotropic Hamiltonian:Hˆ=-2J(Sˆ1·Sˆ2+Sˆ2·Sˆ3)-2J′Sˆ1·Sˆ3 where J and J′ are the intramolecular exchange coupling parameters between adjacent and peripheral spin carriers, respectively. This leads to values of J = −1.37 cm−1 and g = 2.05. The same fitting method is applied to complex 3 to give values of J = 1.2 cm−1 and g = 2.25, showing that there is a ferromagnetic interaction between the Fe(III) and Ni(II) ions.Two cyano-bridged centrosymmetric heterotrinuclear complexes, [(Tp)2Fe2III(CN)6MnII(C2H5OH)4]·2C2H5OH (2) and [(Tp)2Fe2III(CN)6Ni(en)2] (3) (en = ethylenediamine), have been synthesized and structurally characterized. A weak antiferromagnetic interaction between the Mn(II) and Fe(III) ions has been found in complex 2. The magnetic data of 2 can be fitted with the isotropic Hamiltonian: Hˆ=-2J(Sˆ1·Sˆ2+Sˆ2·Sˆ3)-2J′Sˆ1·Sˆ3, where J and J′ are the intramolecular exchange coupling parameters between adjacent and peripheral spin carriers, respectively. This leads to values of J = −1.37 cm−1 and g = 2.05. The same fitting method is applied to complex 3 to give values of J = 1.2 cm−1 and g = 2.25, showing that there is a ferromagnetic interaction between the Fe(III) and Ni(II) ions.
Co-reporter:Shi Wang Dr. Dr.;Hong-Cai Zhou Dr.;Hye Jin Choi Dr.;Yanxiong Ke Dr.;Jeffrey R. Long Dr.;Xiao-Zeng You
Angewandte Chemie 2004 Volume 116(Issue 44) pp:
Publication Date(Web):10 NOV 2004
DOI:10.1002/ange.200461515
Eine magnetische Trickkiste: Die Titelverbindung, ein flächenzentrierter kubischer Cluster, wurde ausgehend von der anionischen Vorstufe [(Tp)Fe(CN)3]− (Tp−=Hydrotris(pyrazolyl)borat) synthetisiert (siehe Struktur; Fe rot, Cu türkis, B orange, C grau, N blau, O dunkelrot). Magnetismusuntersuchungen bescheinigen dem Einzelmolekülmagneten eine beträchtliche axiale magnetische Anisotropie (D=−0.16 cm−1).
Co-reporter:Shi Wang Dr. Dr.;Hong-Cai Zhou Dr.;Hye Jin Choi Dr.;Yanxiong Ke Dr.;Jeffrey R. Long Dr.;Xiao-Zeng You
Angewandte Chemie International Edition 2004 Volume 43(Issue 44) pp:
Publication Date(Web):10 NOV 2004
DOI:10.1002/anie.200461515
A box of magnetic tricks: By using the anionic precursor [(Tp)Fe(CN)3]− (Tp−=hydrotris(pyrazolyl)borate), the title compound, which is a new face-centered-cubic cluster, has been synthesized (see structure; red Fe, turquoise Cu, orange B, gray C, blue N, dark red O). Magnetic studies show that it exhibits single-molecule-magnet behavior with substantial axial magnetic anisotropy (D=−0.16 cm−1).
Co-reporter:Cai-Feng Wang ; Jing Lin Zuo ; Jie-Wen Ying ; Tong Ren ;Xiao-Zeng You
Inorganic Chemistry () pp:
Publication Date(Web):September 24, 2008
DOI:10.1021/ic8011684
Four tetranuclear heterometallic compounds, [(Tp)Fe(CN)3]2[Ru2(DMBA)4] (1), [(MeTp)Fe(CN)3]2[Ru2(DMBA)4] (2), [(iBuTp)Fe(CN)3]2[Ru2(DMBA)4] (3), and [(PhTp)Fe(CN)3]2[Ru2(DMBA)4] (4) [DMBA = N,N′-dimethylbenzamidinate, Tp = (hydrotris(pyrazolyl)borate, MeTp = (methyltris(pyrazolyl)borate, iBuTp = (2-methylpropyltris(pyrazolyl)borate, and PhTp = (tris(pyrazolyl)phenylborate)] were prepared from the combination of Ru2(DMBA)4(NO3)2 and an appropriate [(RTp)Fe(CN)3]−. Molecular structures of compounds 1−4 were established using single-crystal X-ray diffraction, and all feature a linear Fe−C≡N−Ru−Ru−N≡C−Fe array. The magnetic study revealed that the temperature dependence of χMT is mostly attributed to the zero-field splitting of the Ru2 center, indicating the absence of strong spin coupling among three metallic centers. The electronic independence was further confirmed by the vis−NIR spectroscopic studies. Also described are the voltammetric properties of these compounds.
Co-reporter:Jin-Feng Mei, Zhong-Peng Lv, Jian-Cheng Lai, Xiao-Yong Jia, Cheng-Hui Li, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2016 - vol. 45(Issue 13) pp:NaN5454-5454
Publication Date(Web):2016/03/02
DOI:10.1039/C6DT00346J
A novel europium(III) complex simultaneously exhibiting photocolorimetric and photofluorometric behavior was obtained. Multiple distinguishable identities can be obtained and reversibly modulated using light as external stimuli. With this novel photo-responsive complex, double encryption and advanced anti-counterfeiting were realized.
Co-reporter:Jing-Yuan Ge, Jing Ru, Feng Gao, You Song, Xin-Hui Zhou and Jing-Lin Zuo
Dalton Transactions 2015 - vol. 44(Issue 35) pp:NaN15490-15490
Publication Date(Web):2015/07/20
DOI:10.1039/C5DT02062J
A series of pentanuclear LnIII clusters, [Ln5(μ4-OH)(μ3-OH)4(L1)(acac)6] (H4L1 = p-tert-butylthiacalix[4]arene; acac = acetylacetonate; Ln = Dy, Ho, Er) and [Ln5(μ5-OH)(μ3-OH)4(L1)(L2)2(acac)2(CH3OH)2] (H3L2 = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26,27-trihydroxy-28-methoxy thiacalix[4]arene; Ln = Dy, Ho, Er), have been synthesized based on the thiacalix[4]arene ligand. All of these complexes feature a square-based pyramid with four triangular Ln3 structural motifs. One μ4-OH group bridges four LnIII ions in the basal plane of 1–3, while the OH group in complexes 4–6 adopts the μ5-coordination mode. Our results illuminate the coordination modes of the versatile thiacalix[4]arene ligands and their application to new cluster compounds. The structural and magnetic studies confirm that the molecular symmetries and coordination geometries for lanthanide metal cores have a significant effect on some parameters as single-molecule magnets. Among them, two Dy5 pyramids exhibit distinct slow magnetic relaxation.
Co-reporter:Jing Ru, Feng Gao, Min-Xia Yao, Tao Wu and Jing-Lin Zuo
Dalton Transactions 2014 - vol. 43(Issue 48) pp:NaN18055-18055
Publication Date(Web):2014/10/03
DOI:10.1039/C4DT02518K
By the reaction of chiral MnIII Schiff-base complexes with the dicyanoruthenate building block, [Ru(salen)(CN)2]− (salen2− = N,N′-ethylenebis(salicylideneimine) dianion), two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes, [Mn((R,R)-salcy)Ru(salen)(CN)2]n (1-(RR)) and [Mn((S,S)-salcy)Ru(salen)(CN)2]n (1-(SS)) (Salcy = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [Mn((R,R)-salphen)Ru(salen)(CN)2]n (2-(RR)) and [Mn((S,S)-salphen)Ru(salen)(CN)2]n (2-(SS)) (salphen = N,N′-(1,2-diphenylethylene)bis(salicylideneiminato) dianion), were synthesized and structurally characterized. Circular dichroism (CD) and vibrational circular dichroism (VCD) spectra confirm the enantiomeric nature of the optically active complexes. Structural analyses reveal the formation of neutral cyano-bridged zigzag single chains in 1-(RR) and 1-(SS), and double chains in 2-(RR) and 2-(SS). Magnetic studies show that antiferromagnetic coupling is operative between RuIII and MnIII centers bridged by cyanide. Compounds 1-(RR) and 1-(SS) show metamagnetic behavior with a critical field of about 7.2 kOe at 1.9 K resulting from the intermolecular π⋯π interactions. Additionally, magnetostructural correlation for some typical cyano-bridged heterobimetallic RuIII–MnIII compounds is discussed.
Co-reporter:Xinhui Zhou, Honghui Li, Hongping Xiao, Liang Li, Qiang Zhao, Tao Yang, Jinglin Zuo and Wei Huang
Dalton Transactions 2013 - vol. 42(Issue 16) pp:NaN5723-5723
Publication Date(Web):2013/02/04
DOI:10.1039/C3DT00055A
A microporous metal–organic framework (MOF) Eu3(MFDA)4(NO3)(DMF)3 (1, H2MFDA = 9,9-dimethylfluorene-2,7-dicarboxylic acid) has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is a three-dimensional coordination polymer with pcu type rod-packing structure, through which 1D rhombic channels penetrate. The solvent-free form 1a could be obtained by direct heating of 1. Both 1 and 1a exhibit high intensity red light emissions with high quantum yields and long luminescence lifetimes when excited at 336 nm at ambient temperature. The potential of 1a for nitro explosive sensing is studied through luminescence quenching experiments, which show that 1a is a potential luminescent sensory material for nitro explosives.
Co-reporter:Fei Yu, Zi-Heng Cao, Jing-Yuan Ge, Yi-Chen Sun, Zhong-Wen Ouyang, Jing-Lin Zuo, Zhenxing Wang and Mohamedally Kurmoo
Dalton Transactions 2017 - vol. 46(Issue 13) pp:NaN4324-4324
Publication Date(Web):2017/02/28
DOI:10.1039/C7DT00110J
Three Fe(III) dimers, [Fe2(L-H)2]·2CH3CN (1), [Fe2(L-OCH3)2] (2) and [Fe2(L-OC2H5)2]·2CH3CN (3), containing the pentadentate O,N,N,O,O-donor Schiff-base ligands with variable size pendants, were synthesized and structurally characterized. The three ligands were generated in situ from 2-(iminomethyl)phenol, 2-methoxy-6-(iminomethyl)phenol and 2-ethoxy-6-(iminomethyl)phenol, respectively. All three crystal structures contain centrosymmetric dimers of edge-sharing octahedra of Fe(III) ions through a pair of μ2-phenoxido bridges. The exchange coupling is ferromagnetic for 1 (J = +0.47(1) cm−1, ∠Fe–O–Fe = 98.02°) and 2 (J = +0.86(1) cm−1, ∠Fe–O–Fe = 97.17°), but antiferromagnetic for 3 (J = −0.72(1) cm−1, ∠Fe–O–Fe = 98.53°), which are correlated by high-field electron paramagnetic resonance revealing moderate magneto-anisotropy of D = −0.24(3) cm−1, E = 0.08(1) cm−1 for 1, D = −0.38(1) cm−1, E = 0.11(1) cm−1 for 2, and D = 0.30(3) cm−1, E = 0.02(1) cm−1 for 3. The exchange couplings were further estimated by DFT calculations, which gave the finest Fe–O–Fe angle of 97.83° for the ferromagnetic–antiferromagnetic crossover.
Co-reporter:Jing Li, Rong-Min Wei, Tian-Cheng Pu, Fan Cao, Li Yang, Yuan Han, Yi-Quan Zhang, Jing-Lin Zuo and You Song
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 1) pp:NaN122-122
Publication Date(Web):2016/11/03
DOI:10.1039/C6QI00407E
The magnetic relaxation and magnetization blocking barriers of butterfly complexes, [Dy2Zn2(L)4(NO3)2(CH3OH)2] (1), [Dy2Mn2(L)4(NO3)2(DMF)2] (2) and [Dy2Co2(L)4(NO3)2(DMF)2]·2DMF (3) (H2L = (E)-2-ethoxy-6-(((2-hydroxyphenyl)imino)methyl)phenol), were systematically investigated. The change of SMM behavior originating from the purposeful replacement of two ZnII sites in 1 with MnII and CoII was elucidated by a combined experimental and theoretical study. The quantum tunnelling of magnetization (QTM) was observed in 1. Contrarily, it was quenched in 2 and 3 by spin–spin exchange. A detailed comparative study on these closely-related model complexes reveals the remarkable changes of the ligand field splitting, anisotropy of the Dy-coordinated moiety and the total exchange spectrum due to the replacement of ZnII with CoII and MnII.
Co-reporter:Yan Zhou, Hong-Ping Xiao, Ling-Chen Kang, Jing-Lin Zuo, Cheng-Hui Li and Xiao-Zeng You
Dalton Transactions 2009(Issue 46) pp:NaN10262-10262
Publication Date(Web):2009/10/16
DOI:10.1039/B914262B
By reacting metal cyanide complexes with NaBPh4 in the presence of acid at room temperature, a new class of neutral isocyanotriphenylborate-containing complexes trans-Ru(L)4(CNBPh3)2 (L = pyridine, 1; 4-methylpyridine, 2; 4-tert-butylpyridine, 3), cis-Ru(bipy)2(CNBPh3)2 (4, bipy = 2,2′-bipyridine) and cis-M(phen)2(CNBPh3)2 (M = Ru, 5; M = Fe, 6; phen = 1,10-phenanthroline) have been synthesized. These new complexes are characterized by IR, UV spectroscopy and single-crystal X-ray diffractions. The electron withdrawing triphenylborate group on the isocyanide ligands has a pronounced effect on the photophysical properties of complexes 1–6 in comparison with other ruthenium(II) and iron(II) isocyanide complexes. The excitation energies corresponding to metal-to-ligand charge transfer (MLCT) shift to higher energies while the 3MLCT emissions are quenched at room temperature.
Co-reporter:Min-Xia Yao, Qi Zheng, Feng Gao, Yi-Zhi Li, You Song and Jing-Lin Zuo
Dalton Transactions 2012 - vol. 41(Issue 44) pp:NaN13690-13690
Publication Date(Web):2012/08/02
DOI:10.1039/C2DT31203D
Four couples of enantiomerically pure chiral seven-coordinated mononuclear lanthanide complexes, [(LOEt)Dy((R,R)-Salphen)]2·3H2O (1, LOEt = [(Cp)Co(P(O)(OEt)2)3], Cp = cyclopentadiene, Salphen = N,N′-1,2-diphenylethylenebis(salicylideneiminato) dianion), [(LOEt)Dy((S,S)-Salphen)]2·3H2O (2), [(LOEt)Dy((R,R)-5-Cl-Salcy)]·CH3OH·1/8H2O (3, Salcy = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [(LOEt)Dy((S,S)-5-Cl-Salcy)]·CH3OH·1/8H2O (4), [(LOEt)Tb((R,R)-5-Cl-Salcy)]·CH3OH·1/8H2O (5), [(LOEt)Tb((S,S)-5-Cl-Salcy)]·CH3OH·1/8H2O (6), [(LOEt)Ho((R,R)-5-Cl-Salcy)]·CH3OH·1/8H2O (7) and [(LOEt)Ho((S,S)-5-Cl-Salcy)]·CH3OH·1/8H2O (8), have been successfully synthesized by using tetradentate chiral salen-type ligands and the Kläui's tripodal ligand of LOEt. Structural analyses reveal that all compounds have a typical double-decker sandwich structure, and the Ln(III) ions exhibit a rare seven-coordinated mode, situating in a distorted monocapped triangular prism polyhedron. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes and demonstrate that the chirality is successfully transferred from the ligand to the coordination environment of the Ln(III) ions. Field-induced slow relaxation of the magnetization is observed for complexes 1–4, suggesting that they can be rare chiral single-ion magnets (SIMs) based on the seven-coordinated lanthanide ions.
Co-reporter:Xi-Li Li, Yu-Liang Gao, Xiang-Li Feng, You-Xuan Zheng, Chun-Lai Chen, Jing-Lin Zuo and Shao-Ming Fang
Dalton Transactions 2012 - vol. 41(Issue 38) pp:NaN11835-11835
Publication Date(Web):2012/08/01
DOI:10.1039/C2DT31007D
Using the enantiomeric bis-bidentate bridging ligands (+)/(−)-2,5-bis(4,5-pinene-2-pyridyl)pyrazine (LS/LR) and depending on the ratio control of reactants, two mono- and dinuclear Eu(III)-based enantiomeric pairs with the formulae Eu(dbm)3LR/S·2H2O (LR in R-1, LS in S-1 and dbm = dibenzoylmethanato) and Eu2(dbm)6LR/S·H2O (LR in R-2 and LS in S-2) have been stereoselectively synthesized and structurally characterized. The circular dichroic (CD) spectra confirmed their chiroptical activities and enantiomeric natures. The homochiral dinuclear species represents the first example of a polynuclear lanthanide β-diketonate complexes with circular dichroic and crystallographic evidences. The photoluminescent properties studies revealed that both mono- and dinuclear Eu(III) complexes exhibited the characteristic red emissions of Eu(III) ions in the solid state (at 77 K and 300 K) and CH2Cl2 solution. Notably, the photophysical properties of the mononuclear enantiomers were superior to the dinuclear species. Interestingly, R-2 displayed a ferroelectric property at room temperature, which was not observed for R-1 due to the lack of crystalline polarity. R/S-2 are the first examples of homochiral polynuclear lanthanide complexes with luminescence and ferroelectric properties, being potential multifunctional materials.
Co-reporter:Feng Gao, Yu-Yang Li, Cai-Ming Liu, Yi-Zhi Li and Jing-Lin Zuo
Dalton Transactions 2013 - vol. 42(Issue 31) pp:NaN11046-11046
Publication Date(Web):2013/07/02
DOI:10.1039/C3DT51051D
A new triple-decker dinuclear sandwich-type dysprosium complex based on both the phthalocyanine ligand and the tetradentate Schiff base ligand was synthesized, which is of interest for synthetic chemistry and also shows single-molecule magnetic behaviour.
Co-reporter:Zhi-Guo Gu, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2007(Issue 36) pp:
Publication Date(Web):
DOI:10.1039/B708789F
Co-reporter:Zhi-Guo Gu, Yi-Fan Xu, Xiu-Ju Yin, Xin-Hui Zhou, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2008(Issue 41) pp:NaN5602-5602
Publication Date(Web):2008/08/26
DOI:10.1039/B806619A
Three homochiral layered complexes, [Cu3(R-chea)2(N3)6]n (1), [Cu3(S-chea)2(N3)6]n (2) (chea = 1-cyclohexylethylamine) and [Cu3(S-phpa)2(N3)6]n (3) (phpa = 1-phenylpropylamine), and three novel cluster-based coordination polymers, [Cu6(1,2-pn)4(N3)12]n (4) (1,2-pn = 1,2-diaminopropane), {[Cu8(en)4(N3)16]·H2O}n (5) (en = ethylenediamine) and [Cu6(N-Ipren)2(N3)12]n (6) (N-Ipren = N-isopropylethylenediamine), have been synthesized by the self-assembly reactions of Cu(NO3)2·3H2O, NaN3 and small organic amine ligands. Their crystal structures are determined by single-crystal X-ray diffraction. Complexes 1–3 are composed of neutral 2D brick wall networks with only end-on azido bridges. Complexes 4 and 5 are 3D coordination polymers featuring copper–azido clusters and [Cu(diamine)2]2+ units which are linked by the azido bridges. Complex 6 is a 3D coordination framework based on the hexanuclear copper(II) clusters [Cu6(N3)12(N-Ipren)2]. Magnetic studies show that complexes 1–3 are interesting chiral ferromagnets with the magnetic transition temperature at ca. 5.0 K. Complexes 4 and 5 show ferromagnetic coupling in the copper–azido cluster units and antiferromagnetic interaction between neighboring units, while complex 6 shows ferromagnetic ordering at 3.2 K.
Co-reporter:Ling-Chen Kang, Min-Xia Yao, Xin Chen, Yi-Zhi Li, You Song, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2011 - vol. 40(Issue 10) pp:NaN2212-2212
Publication Date(Web):2010/12/13
DOI:10.1039/C0DT00954G
With the use of Kläui's tripodal ligand, [(Cp)Co(P(O)(OEt)2)3]− (LCoEt, Cp = cyclopentadiene) as the auxiliary ligand to react with different metal salts and tricyanometalate building blocks, five neutral trimetallic hexanuclear complexes: [(Tp)2Fe2(CN)6Cu2(LCoEt)2]·6H2O (1, Tp = hydridotris(pyrazolyl)borate), [(Tp*)2Fe2(CN)6Cu2(LCoEt)2]·2H2O (2, Tp* = hydridotris(3,5-dimethyl-pyrazolyl)borate), [(pzTp)2Fe2(CN)6Cu2(LCoEt)2]·H2O·3MeOH (3, pzTp = tetra(pyrazolyl)borate), [(Tp)2Fe2(CN)6Ni2(LCoEt)2(MeCN)2]·2MeCN·2H2O (4) and [(Tp)2Fe2(CN)6Mn2(LCoEt)2(MeCN)2]·2MeCN (5), have been obtained and structurally characterized. Magnetic measurements confirm that there are ferromagnetic couplings between the cyano-bridged Fe and Cu/or Ni ions and antiferromagnetic interaction between the cyano-bridged Fe and Mn ions. Slow relaxation of the magnetization is observed in complexes 1 and 4, while complex 3 exhibits metamagnetic behavior with a critical field of 17.5 kOe.
Co-reporter:Ru Wang, Ling-Chen Kang, Jing Xiong, Xiao-Wei Dou, Xiao-Yu Chen, Jing-Lin Zuo and Xiao-Zeng You
Dalton Transactions 2011 - vol. 40(Issue 4) pp:NaN926-926
Publication Date(Web):2010/12/08
DOI:10.1039/C0DT00739K
The bis(pyridyl)-substituted TTF derivative, 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (TTF(py)2), and an inorganic analogue, [Ni(4-pedt)2] (4-pedt = 1-(pyridin-4-yl)ethylene-1,2-dithiolate), were used as bridging ligands to construct two multinuclear complexes {CoII2(TpPh2)2(OAc)2[TTF(py)2]} (1, TpPh2 = hydridotri(3,5-diphenylpyrazol-1-yl)borate) and {CoII2(TpPh2)2(OAc)2[Ni(4-pedt)2]} (2), and two 1D zigzag chain complexes, {[MII(tta)2][TTF(py)2]}n (M = Cu for 3, and Mn for 4; tta = thenoyltrifluoroacetonate). X-Ray structural studies indicate that complexes 1 and 2 are very similar as a result of the isolobal analogy between TTF(py)2 and [Ni(4-pedt)2], whereas complexes 3 and 4 are isostructural. The absorption spectra, electrochemical and magnetic properties for these new complexes have been studied. The results show that the interactions between the paramagnetic ions are weak owing to the large separation of the bridging ligands of TTFs and the inorganic analogue.
Co-reporter:Cai-Feng Wang, Dong-Ping Li, Xin Chen, Xiao-Ming Li, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You
Chemical Communications 2009(Issue 45) pp:NaN6942-6942
Publication Date(Web):2009/10/22
DOI:10.1039/B916637H
The assembly of chirality into magnetic nanowires enables the formation of two new cyano-bridged heterobimetallic 3,2-chain enantiomeric complexes, representing the first example of multiferroic compounds bearing both slow magnetization relaxation and ferroelectricity.
Co-reporter:Yu-Yang Li, Feng Gao, Jonathon E. Beves, Yi-Zhi Li and Jing-Lin Zuo
Chemical Communications 2013 - vol. 49(Issue 35) pp:NaN3660-3660
Publication Date(Web):2013/03/15
DOI:10.1039/C3CC41237G
A giant metallo-supramolecular cage encapsulating a single-molecule magnet, [Ag42{Ho(W5O18)2}(t-BuCC)28Cl4]OH, is prepared and structurally characterized. It shows an interesting “peanut-like” structure and remains intact in solution as demonstrated by NMR studies.
Co-reporter:Jing Ru, Feng Gao, Tao Wu, Min-Xia Yao, Yi-Zhi Li and Jing-Lin Zuo
Dalton Transactions 2014 - vol. 43(Issue 3) pp:NaN936-936
Publication Date(Web):2013/11/01
DOI:10.1039/C3DT52951G
A pair of one-dimensional enantiomers based on the versatile chiral dicyanoruthenate(III) building block have been synthesized and they are chiral single-chain magnets with the effective spin-reversal barrier of 28.2 K.
Co-reporter:Long Cui, Zhong-Peng Lv, Chanel F. Leong, Jing Ru, Deanna M. D'Alessandro, You Song and Jing-Lin Zuo
Dalton Transactions 2016 - vol. 45(Issue 42) pp:NaN16584-16584
Publication Date(Web):2016/06/09
DOI:10.1039/C6DT01756H
The π-conjugated tetrathiafulvalene (TTF) annulated ligand was introduced into a dicyanometallate for the first time, leading to the synthesis of the versatile redox-active dicyanideferrite building block [(n-Bu)4N][Fe(TTFbp)(CN)2] (H2TTFbp = N-(2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-5-(picolinamido) benzo[d][1,3]dithiol-6-yl) picol inamide). The incorporation of the new precursor with chiral MnIII Schiff-base complexes resulted in two enantiopure one-dimensional complexes, [Mn((R,R)-salphen)Fe(TTFbp)(CN)2]n (2-(RR)) and [Mn((S,S)-salphen)Fe(TTFbp)(CN)2]n (2-(SS)) (Salphen = N,N′-1,2-diphenylethylene-bis(salicylideneiminato) dianion), which were synthesized and structurally characterized. Circular dichroism (CD) and vibrational circular dichroism (VCD) spectra confirmed the enantiomeric nature of the optically active complexes, and structural analyses revealed the formation of neutral cyanide-bridged double chains in 2-(RR) and 2-(SS). Solution and solid state CV studies revealed the redox-active characteristics of the complexes. Antiferromagnetic couplings were detected between FeIII and MnIII centers within a chain, and a field-induced magnetic phase transition was observed (TN = 4.8 K). The introduction of electroactivity and chirality into cyanide-bridged complexes with interesting magnetic properties leads the way towards new multifunctional materials.
Co-reporter:Long Cui, Jing-yuan Ge, Chanel F. Leong, Deanna M. D'Alessandro and Jing-Lin Zuo
Dalton Transactions 2017 - vol. 46(Issue 12) pp:NaN3988-3988
Publication Date(Web):2017/02/20
DOI:10.1039/C6DT04903F
An oxamato unit has been introduced into a tetrathiafulvalene (TTF) system for the first time via direct condensation, generating a new π-extended TTF ligand, TTF-Et2H2opba (opba = ortho-phenylenebis-oxamato). On the basis of this ligand, the Cu(II) complex [(n-Bu)4N]2[Cu(TTF-opba)] (1) has been obtained. By employing this complex as a “metalloligand”, we have successfully prepared an interesting heterometallic one-dimensional complex {[Cu(TTF-opba)][Mn(CH3OH)2]}n (2), via coordination of the free carbonyl-oxygen atoms of the two oxamato groups with Mn(II) ions. The new compounds have been structurally characterized, and their electrochemical and magnetic properties probed. Complex 2 shows a ferrimagnetic behavior with g = 1.96 and J = −22.36 cm−1.
Co-reporter:Jing-Yuan Ge, Hai-Ying Wang, Jing Li, Jia-Ze Xie, You Song and Jing-Lin Zuo
Dalton Transactions 2017 - vol. 46(Issue 10) pp:NaN3362-3362
Publication Date(Web):2017/02/17
DOI:10.1039/C7DT00298J
Three dinuclear lanthanide complexes, [Ln2(thd)4Pc]·2C6H6 (Hthd = 2,2,6,6-tetramethylheptanedione, Ln = Sm (1), Tb (2), Dy (3)), have been synthesized based on phthalocyanine (Pc). They can be reversibly transformed into [Ln2(thd)4Pc] (Ln = Sm (1′), Tb (2′), Dy (3′)) via desolvation and resolvation of the lattice benzene molecules. This change generates dramatic influences on the structural and magnetic properties of the dysprosium analogue. In complex 3, one crystallographically independent metal center is observed, and it exhibits a single relaxation process of magnetization with an energy barrier of 55.7 K. Upon desolvation, the resulting complex 3′ contains two types of metal centers, and shows the field-induced single-molecule magnetic behavior with two thermally activated magnetic relaxation processes. The anisotropy barriers for 3′ are as high as 63.3 K and 109.6 K, respectively. This work confirms that the solvated molecules can finely tune the magnetic relaxation mechanisms.
Co-reporter:Zhong-Peng Lv, Tao Wang, Jing-Yuan Ge, Zhong-Zhi Luan, Di Wu, Jing-Lin Zuo and Shouheng Sun
Journal of Materials Chemistry A 2017 - vol. 5(Issue 29) pp:NaN7206-7206
Publication Date(Web):2017/06/30
DOI:10.1039/C7TC01021D
We report a solution phase based assembly method to tune the transport mechanism and magnetoresistance (MR) of Fe3O4 nanoparticles (NPs). The NP topological arrangement is altered by the NP coating of tetrathiafulvalene carboxylic acid (TTFCOOH) or its dicarboxylic analogue (TTF(COOH)2). Consequently, the transport mechanism of the assembly switches from tunneling to Mott hopping. The MR ratios of the Fe3O4 NP assemblies can be further tuned by the polarity of the solvent used in the ligand exchange process. The TTF(COO)2-coated Fe3O4 NP assembly has a 5% room temperature MR ratio, which is the highest value among all TTF-COO-Fe3O4 NP assemblies reported so far.
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