Co-reporter:Jing Xu, Li-Jun Xue, Jin-Le Hou, Zhong-Nan Yin, Xuan Zhang, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry July 17, 2017 Volume 56(Issue 14) pp:8036-8036
Publication Date(Web):June 27, 2017
DOI:10.1021/acs.inorgchem.7b00775
Although great progress has been made for charge transfer (CT) compounds of various organic donor–acceptor systems, no CT compounds containing both inorganic chalcogenide cluster anions and organic porphyrin cations have been reported. Herein, a germanium chalcogenide cluster (Ge4S104–) is chosen as an electron donor and a methylated tetrakis(4-pyridyl)porphyrin (5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin, TMPyP) is selected as an electron acceptor to create chalcogenide cluster–porphyrin CT compounds (TMPyP-Ge4S10)·5H2O (1) and (MnTMPyP-Ge4S10)·13H2O (2). Their crystal structures have been characterized by single-crystal X-ray diffraction. Compound 1 is an ionic CT salt assembled through interion interactions, and compound 2 is a neutral CT dyad formed by metal–ligand axial coordination of the chalcogenide cluster with manganese porphyrin. The strong charge transfer properties are revealed by electronic spectra, theoretical calculations, 1H NMR, and ESR. The CT intensity of the chalcogenide cluster–porphyrin system can be modulated by metalation. The fluorescence and photocurrent response properties of 1 and 2 are related to the CT intensity.
Co-reporter:Shen Yang;Hu-Chao Su;Jin-Le Hou;Wen Luo;Dan-Hong Zou;Qin-Yu Zhu
Dalton Transactions 2017 vol. 46(Issue 29) pp:9639-9645
Publication Date(Web):2017/07/25
DOI:10.1039/C7DT01603D
Titanium-oxo-clusters (TOCs), [Ti6O4(OiPr)10(Cat)2(BA)2] (1) and [Ti12M2O10(OEt)22(Cat)2(BA)4] (M = Co, Mn, Ni, 2–4; H2Cat = catechol, HBA = benzoic acid) are prepared in one step in an in situ solvothermal synthesis. Cluster structures of 2–4 can be considered as two 1 moieties merged together by two transition metal atoms. Unlike most TOCs with sphere-like structures, clusters 2–4 feature a unique single layered structure. They are not only transition metal doped TOCs but also charge transfer (CT) TOCs, CT from Cat to the TiO cluster core. Photoelectrodes were prepared by dipping the solution of clusters on a porous TiO2 substrate. Photocurrent response properties of the electrodes were studied in comparison with those of the electrodes of non-metal doped 1 and the non-Cat coordinated Ti6 cluster. The results showed that the photocurrent densities of metal doped clusters are higher than that of non-doped clusters and the highest photocurrent density was found for the redox active Co(II) doped cluster. Charge transfer also plays an effective role in photocurrent conversion under visible light irradiation.
Co-reporter:Yao Guo;Jin-Le Hou;Wen Luo;Zhao-Qi Li;Dan-Hong Zou;Qin-Yu Zhu
Journal of Materials Chemistry A 2017 vol. 5(Issue 34) pp:18270-18275
Publication Date(Web):2017/08/29
DOI:10.1039/C7TA05639G
We have reported that dyes with a titanium alkoxide moiety can improve dye-semiconductor surface properties, such as anchoring and molecular distribution. Here, we report three new titanium-alkoxide-dyes (TADs): [Ti2(OiPr)5(Az)(NO2-BA)] (1), [Ti2(OiPr)5(Az)(F-BA)] (2), [Ti2(OiPr)5(Az)(Br-BA)] (3) (H2Az = alizarin dye and HBA = benzoic acid), in which the titanium alkoxide clusters are coordinated with alizarin dye and an auxiliary ligand, namely a benzoic acid substituted with –NO2, –F or –Br. Their photo-absorption was greatly shifted to lower energy, due to the charge transfer from the π-conjugated dye moiety to Ti(IV). The structures of all these compounds could be divided into two functional parts: a conjugated organic photosensitive antenna part and a hydrolyzable anchoring part. Using 1–3 as new sensitive dyes, dye-sensitized TiO2 electrodes were prepared for measurement of the photocurrent response in an I2/I3− solution cell. In comparison with the organic dye-treated TiO2 electrode, considerable improvement in photocurrent density was observed for the TAD-treated TiO2 electrodes. The effect of different substituted auxiliary ligands on the photocurrent conversion was evaluated. Their photocurrent density was in the order NO2 > F > Br, which was in accordance with the electron-withdrawing property of the substituted groups. This work not only demonstrated the advantages of TADs but also showed, for the first time, the effect of electron-withdrawing auxiliary ligands.
Co-reporter:Zhao-Qi Li;Chong-Jiao Mo;Yao Guo;Nan-Nan Xu;Qin-Yu Zhu
Journal of Materials Chemistry A 2017 vol. 5(Issue 18) pp:8519-8525
Publication Date(Web):2017/05/10
DOI:10.1039/C7TA00247E
Supertetrahedral clusters of main-group metal chalcogenides (Tn) have been well-studied for decades. Most of them are polymerized 2D or 3D structures and have been used as porous materials for ion exchange and as ion conductors. Large discrete T5 clusters of main-group metal chalcogenides are attractive in that they might be used as nanocluster materials with uniform size and definite structures. However, until now, discrete T5 clusters have been reported only in the solid state and their dispersed solution has not yet been obtained due to their low solubility in common solvents, thus not to mention their application as nanodots. We prepare a crystal compound with discrete T5 CuInS clusters using a simple and economical way. A solution of the T5 clusters was obtained by a strategy using a medium with strong ionic strength to overcome the strong ionic force in crystals. The discrete T5 clusters in solution is proved by HRTEM and ESI-MS. The nano-T5 CuInS clusters can be easily modified on a TiO2 electrode by a wet process and the clusters show excellent photo-sensitive properties tested by photocurrent and photocatalysis.
Co-reporter:Qin-Yu Zhu, Jie Dai
Coordination Chemistry Reviews 2017 Volume 330(Volume 330) pp:
Publication Date(Web):1 January 2017
DOI:10.1016/j.ccr.2016.08.009
•An overview of main group metal chalcogenidometalates intergraded with phen/bpy complexes.•Synthetic particularities for main-group chalcogenidometalates with phen/bpy complexes.•Structural effects of phen/bpy complexes on construction of chalcogenidometalates.•Charge transfer and photocurrent properties of the chalcogenidometalates.Inorganic-organic hybrid main group metal chalcogenidometalates have attracted considerable interest due to their various topological structures and potential applications in solid electrolytes, non-oxygen zeolites, and photo- or electro-catalysts. These compounds are typically synthesized under hydro(solvo)thermal conditions at relatively low temperature using various organic amines. Comprehensive reviews have summarized the preparation and structures of these main group metal chalcogenidometalates. A particular research challenge in this field is using the chelating imines, such as 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy), in the synthesis of inorganic-organic hybrid main group metal chalcogenidometalates because their transition metal complexes can add new optical or electronic properties to the host chalcogenide compounds. Thus, a series of unique chalcogenidometalates with M-phen and M-bpy complexes (M = metal ions) have been isolated recently. These compounds have unusual optical and photoelectronic properties compared with those of the amine series. The present review focuses on recent developments in the synthesis, structures, and properties of these chalcogenidometalates. A comprehensive outline is provided of the chalcogenidometalate compounds with discrete M-phen/bpy complex cations or covalently bonded M-phen/bpy moieties. In addition, the new functional properties of these compounds are summarized.
Co-reporter:Chen-Jie Que, Chong-Jiao Mo, Zhao-Qi Li, Guang-Lin Zhang, Qin-Yu ZhuJie Dai
Inorganic Chemistry 2017 Volume 56(Issue 5) pp:
Publication Date(Web):February 20, 2017
DOI:10.1021/acs.inorgchem.6b02550
A great effort has been made to investigate 2D perovskites to improve the stability and controllability in the fabrication of photoelectronic devices. As far as we know, only small organic cations such as methylammonium can incorporate into the multilayered perovskite structure except the cations sandwiched between the inorganic layers. We report here a new layered lead iodide, (H2Aepz)3Pb4I14 (1), where larger organic cations, bis-protonated 2-(2-aminoethyl)pyrazole (Aepz), not only were sandwiched between the inorganic layers but also were incorporated within the perovskite-like PbI layered structure. Another 2D compound, (H2Aepz)PbI4 (2), was also prepared that was a one-layer perovskite. A simple Schottky device was prepared to investigate the photoelectroresponsive properties of the compounds in comparison with that of a typical organic–inorganic hybrid perovskite. In general, the energy gap is decreased with an increase in the perovskite layers, but the band gap of two-layered 1 is larger than that of one-layered 2. The photocurrent densities of the compounds are in the order of 1 < 2 < (CH3NH3)PbI3, which is discussed based on the crystal structures and band energy gaps.
Co-reporter:Hu-Chao Su, Yin-Yin Wu, Jin-Le Hou, Guang-Ling Zhang, Qin-Yu Zhu and Jie Dai
Chemical Communications 2016 vol. 52(Issue 21) pp:4072-4075
Publication Date(Web):22 Feb 2016
DOI:10.1039/C6CC00551A
An organic dye coordinated titanium iso-propoxide compound is designed and synthesized. Taking advantage of the hydrolysis of the titanium alkoxide moiety on the surface of TiO2 electrode, the dye–semiconductor surface properties, including anchoring and dispersivity, are improved, which opens a new perspective to explore dyes for DSSCs.
Co-reporter:Ting Chen, Peng Huo, Jin-Le Hou, Jing Xu, Qin-Yu ZhuJie Dai
Inorganic Chemistry 2016 Volume 55(Issue 24) pp:12758-12765
Publication Date(Web):December 2, 2016
DOI:10.1021/acs.inorgchem.6b02062
Three transition metal coordination polymers (CPs) based on the redox-active dimethylthio-tetrathiafulvalene-bicarboxylate (L) and 1,3-bi(4-pyridyl)propane (bpp) ligands, formulated as [MnL(bpp)]n (1), [CdL(bpp)]n (2), and [Cd2L(bpp)2(H2O)(C2O4)0.5]n·n(ClO4)·n(H2O) (3), are crystallographically characterized. Complexes 1 and 2 are isostructural 2-D polymers, and 3 features an unusual 3-D metal–organic framework (MOF). The 3-D MOF is constructed from tetranuclear cluster nodes built through the μ2-O bridge of the TTF ligand, which is first found for TTF coordination polymers. It is found that the channel generated by the 3-D MOF exerts a confinement effect on the formation of TTF dimers. The TTF dimers show strong intradimer interaction with partial electron transfer or charge transfer, and hence, the Cd compound 3 has relatively good photocurrent response property in comparison with that of 2-D Cd compound 2.
Co-reporter:Peng Huo, Ting Chen, Jin-Le Hou, Lei Yu, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2016 Volume 55(Issue 13) pp:6496
Publication Date(Web):June 10, 2016
DOI:10.1021/acs.inorgchem.6b00571
A systematic study on ligand-to-ligand charge-transfer (LLCT) properties of three closely related metal–organic frameworks (MOFs) is presented. These compounds are formulated as [MnL(4,4′-bpy)(H2O)]n·nCH3CN (1), [MnL(bpe)0.5(DMF)]n·2nH2O (2), and [MnL(bpa)(H2O)]n·2nH2O (3) (L = dimethylthio-tetrathiafulvalene-bicarboxylate, 4,4′-bpy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene, bpa = 1,2-bis(4-pyridyl)ethane). The X-ray single-crystal diffractions show that complexes 1–3 are all two-dimensional (2-D) coordination polymers with different frameworks in crystal lattices. Charge-transfer (CT) interactions within these MOFs are visually apparent in colors and vary according to the conjugated states of the bipyridine ligands (4,4′-bpy, bpe, and bpa). Theoretical calculations show that the charge transfer occurs from ligand L to bipyridine. The intensity of the LLCT is in the order of 2 > 1 > 3 investigated by theoretical calculations and ESR, which indicates that the intensity of CT is related to the bipyridyl conjugated state. Photocurrent responses of these compounds are consequently studied, and the results are in agreement with the intensity of charge transfer and linearly related to the LLCT energy.
Co-reporter:Zhong-Nan Yin, Yan-Hong Li, Yong-Gang Sun, Ting Chen, Jing Xu, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2016 Volume 55(Issue 18) pp:9154-9157
Publication Date(Web):September 7, 2016
DOI:10.1021/acs.inorgchem.6b01632
A tetrathiafulvalene derivative has been incorporated into a diamond-like structure for the first time. The coordination network shows highly unusual 8-fold interpenetration with redox-active and photoelectric properties.
Co-reporter:Li-Jun Xue, Peng Huo, Yan-Hong Li, Jin-Le Hou, Qin-Yu Zhu and Jie Dai
Physical Chemistry Chemical Physics 2016 vol. 18(Issue 4) pp:2940-2948
Publication Date(Web):18 Dec 2015
DOI:10.1039/C5CP06141E
Great progress has been made in combining a TTF moiety with a porphyrin unit by covalent bonds, but only a few examples were reported in which TTF and porphyrin assembled by noncovalent interactions. In contrast to the energy- and time-consuming synthetic procedures for the covalent system, the assembly of a non-covalent ionic system would be a cost-effective way to construct donor–acceptor ensembles. Herein a new type of ionic TTF–porphyrin dyad is obtained. A methylated tetra(4-pyridyl) porphyrin (5,10,15,20-tetrakis-(N-methyl-4-pyridyl)-porphyrin, TMPyP) is selected as the cation, and TTF-bicarboxylate (L1) or TTF-tetracarboxylate (L2) is used as the anion. Crystal structures of two TTF-TMPyP ionic D–A compounds, TMPyP-(HL1)4·3H2O (1) and TMPyP-(H2L2)2·5H2O (2), were characterized by single-crystal X-ray diffraction. The strong ionic interaction enhances the charge-transfer between the regular mixed-stacking donors and acceptors, which are investigated comprehensively by spectral, electrochemical and theoretical studies. The variation in properties between L1 and L2 is of great advantage to understand the influence factors for charge-transfer. The charge-transfer properties can be modulated not only by the nature of the donor or the acceptor, but also the cation–anion ratio in the salt, which shows great flexibility of the D–A ionic dyad in the design and preparation of new charge-transfer systems.
Co-reporter:Peng Huo, Yan-Hong Li, Li-Jun Xue, Ting Chen, Lei Yu, Qin-Yu Zhu and Jie Dai
CrystEngComm 2016 vol. 18(Issue 11) pp:1904-1910
Publication Date(Web):19 Feb 2016
DOI:10.1039/C6CE00180G
A series of tetrathiafulvalene (electron donor, D) charge-transfer salts with three methyl bipyridiniums (electron acceptor, A) in the basic formulas MV(HL)2 (1), MeBpe(HL)2 (2) and MeBpa(HL)2 (3) (L = dimethylthio-tetrathiafulvalene-bicarboxylate, MV = methyl viologen, MeBpe = 1,2-bi(4-pyridinium) ethene and MeBpa =1,2-bi(4-pyridinium) ethane) was synthesized and their structures were characterized by X-ray single crystal analysis. The three bipyridiniums allow the exploration of the effect of different conjugated systems on molecular packing and charge-transfer interactions. A type of –DDDD– stacking column with edge-to-edge short D⋯A⋯D contacts is found in MV compound 1, while in π-extended MeBpe compound 2, a –DADDAD– type of stacking column with face-to-face short D⋯D and A⋯D stacking is formed, which shows the most effective cation–anion interaction. No effective interaction is found for the non-conjugated MeBpa compound 3. The charge-transfer from an anion to a cation measured by UV-vis, CV and ESR is in the order of 2 > 1 ≫ 3, which is greatly in accordance with the order of the cation's conjugated state and CT interaction. It is known that charge-transfer is a key factor in obtaining photoelectric materials. Photocurrent responses of these compounds are consequently studied and the results agree with the intensity of charge-transfer. This is a systematic study of the effect of different π-conjugated systems on charge-transfer properties in terms of crystal structures.
Co-reporter:Peng Huo, Li-Jun Xue, Yan-Hong Li, Ting Chen, Lei Yu, Qin-Yu Zhu and Jie Dai
CrystEngComm 2016 vol. 18(Issue 16) pp:2894-2900
Publication Date(Web):31 Mar 2016
DOI:10.1039/C5CE02479J
Viologen dication derivatives with a series of alkyl chains are used to assemble charge-transfer salts and films with dimethylthio-tetrathiafulvalene-bicarboxylate which aims to explore the relationship of the alkyl chain length to molecular structures and film morphologies which are important points for the design of molecular materials and manipulation of molecular devices. Four charge-transfer salts generally formulated as [(CnV)(HL)2] [n = 4(1), 8(2), 12(3) and 16(4)] are prepared and 1–3 are characterized by single-crystal X-ray structural analysis. In the short alkyl chain compound, TTF and C4V moieties are regularly arranged and effectively stacked with strong charge-transfer interactions. Lengthening the alkyl chain of the bipyridinium cation reduces the regular and close arrangement of the cations and anions in the crystals, which weakens the charge-transfer interaction while increasing the amphiphilic assembly of the films. Their film morphologies change from crystals to fused crystals, band-like structures and finally to smooth films with the increase of the alkyl chain length. The effects of alkyl chain length on photocurrent intensity are different between the crystal sample-modified electrodes (in the order of 1 > 2 > 3 = 4) and the film-modified electrodes (in the order of 2 > 1 = 3 > 4), because both inter-ion interactions and film-forming properties should be considered for the film electrodes. This is a systematic study of the effect of alkyl chain substitution on film morphologies in terms of crystal structures.
Co-reporter:Li-Wen Qian, Xiao-Wei Zhao, Hu-Chao Su, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
RSC Advances 2016 vol. 6(Issue 20) pp:16268-16273
Publication Date(Web):09 Feb 2016
DOI:10.1039/C5RA27088J
Although a lot of thiogermanates with transition metal amine complexes have been successfully synthesized, thiogermanates with vanadium complexes are largely unexplored. Two such new thiogermanates, {[V(en)2]2O}Ge2S6 (1) (en = ethylenediamine) and [VO(dap)2]2Ge2S6·dap (2) (dap = 1,2-diaminopropane), are now synthesized and characterized crystallographically. Compound 2 shows a supramolecular structure with hexagonal nano tubes assembled through N–H⋯S hydrogen bonds. The nano-tubes are further closely packed with strong N–H⋯O hydrogen bond interactions to form a honeycomb-like structure. Although the sulfur (S)–amine systems are common in the synthesis of chalcogenidometalates, the results of this work give a new demonstration of amine induced variation in molecular structures and the valance state of vanadium, though the two amines are only different by a branched methyl group.
Co-reporter:Yan-Hong Li, Yong-Gang Sun, Peng Huo, Qin-Yu Zhu, Jie Dai
Inorganic Chemistry Communications 2016 Volume 68() pp:33-36
Publication Date(Web):June 2016
DOI:10.1016/j.inoche.2016.04.007
•Main group metal Pb(II) complexes with tetrathiafulvalene ligands are explored.•Fluorescence quenching relates to ligand-to-ligand charge-transfer (LLCT).•Pb(II) ion is a good intermediary for LLCT in comparison with Cd(II) ion in this system.Although TTF coordination complexes with transition metals have been extensively studied, coordination chemistry of p-block metal ions with TTF ligands remains largely unexplored. In this study, two Pb(II) complexes of 2,6-bis(4′-pyridyl)tetrathiafulvalene (py-TTF-py) with co-coordinated 9-anthracenecarboxylate (AC), formulated as [Pb(AC)2(py-TTF-py)2] (1), {[Pb(AC)2(py-TTF-py)0.5]·CH3CN}n (2), and a transition metal Cd(II) compound [Cd(AC)2(py-TTF-py)2]n (3) for comparison are characterized by single-crystal X-ray diffraction. Compound 1 is a monomer and 3 is a 1-D compound. Compound 2 is a 2-D coordination polymer with planar mesh-like structure. They are metal linked electron donor and fluorescent acceptor system. Traced by the intensity of fluorescence quenching of AC ligand, it was found that Pb(II) ion is a good intermediary for ligand-to-ligand charge-transfer in this system.Two Pb(II) complexes with py-TTF-py ligand are solvothermal synthesized to study the properties of TTF main-group metal complexes. It was found that Pb(II) ion is a good intermediary for ligand-to-ligand charge-transfer.
Co-reporter:Jing-Xue Yin, Peng Huo, Sheng Wang, Jing Wu, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2015 vol. 3(Issue 2) pp:409-415
Publication Date(Web):05 Nov 2014
DOI:10.1039/C4TC02009J
Many exfoliation strategies have been developed to prepare 2-D sheet materials from single crystals. However, most of the published research has used micro-scale crystals. The transformation of bulk crystals to micro- or nano-scale structures has rarely been achieved by chemical etching. We report here the preparation of a tetrathiafulvalene (TTF)-grafted titanium-oxo-cluster (TiO–TTF) that can be easily exfoliated at a millimeter scale. This is the first example of a titanium-oxo-cluster successfully combined with a TTF moiety. In an oxygen atmosphere, the red crystal of the TiO–TTF cluster changes to a black ‘crystal’ composed of regularly arranged floorboard-like micro-plates. The exfoliation properties of the material are a result of the easy oxidation of the TTF group and the catalytic properties of the TiO cluster. The TTF moiety in the cluster is not only an oxidation center, but also adds new photoelectroactive properties to the TiO material. An enhanced photocurrent response was observed for the TiO–TTF and TiO–TTF(+) materials.
Co-reporter:Yu-Hong Wang, Jing Wu, Xiao-Wei Zhao, Li-Wen Qian, Qin-Yu Zhu and Jie Dai
Chemical Communications 2015 vol. 51(Issue 53) pp:10668-10671
Publication Date(Web):05 Jun 2015
DOI:10.1039/C5CC03404C
Different from the dominating supertetrahedral structure of InSe clusters, co-assembled nano-scale In33Se60 triangular ring clusters and wheel-shaped In18Se30 clusters have been found. The unusual second-sphere coordination templating effect of the Mn(dach) complexes and the central Mn2+ ion is responsible for the formation of the triangular ring. The optical and electronic properties are discussed.
Co-reporter:Xiao-Wei Zhao, Li-Wen Qian, Hu-Chao Su, Chong-Jiao Mo, Chen-Jie Que, Qin-Yu Zhu, and Jie Dai
Crystal Growth & Design 2015 Volume 15(Issue 12) pp:5749
Publication Date(Web):November 2, 2015
DOI:10.1021/acs.cgd.5b00960
Recently, discrete large Tn clusters have become particularly attractive because they can be used as starting materials not only for constructing porous chalcogenides but also for solution processing of semiconductor film materials with electronic and optical properties. However, the discrete large clusters of main-group metal chalcogenides are difficult to stabilize because of their high negative charge. We report herein a new crystal compound co-assembled by discrete T4 [Cu4In16S35H4]14–and cubic [Cu12S8]4– clusters. It is uncommon that the negatively charged CuS cluster acts as a template to sustain a hexagonal cavity formed by negatively charged T4 clusters. Its degeneration product shows an excellent near-infrared absorption property and photocurrent responsive properties.
Co-reporter:Sheng Wang, Hu-Chao Su, Lan Yu, Xiao-Wei Zhao, Li-Wen Qian, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2015 vol. 44(Issue 4) pp:1882-1888
Publication Date(Web):19 Nov 2014
DOI:10.1039/C4DT02968B
Two 9-anthracenecarboxylate (9-AC) coordinated heterometallic TOC compounds, [Ln2Ti10O14(ClO4)2(OiPr)14(9-AC)2(CH3CN)2]·2H2O, Ln = Nd (1) and Eu (2), along with two benzoate (bza) analogues, [Ln2Ti10O14(ClO4)2(OiPr)14(bza)2(HOiPr)2], Ln = Nd (3) and Eu (4), were prepared by one step in situ solvothermal synthesis, and characterized by single crystal analysis. To date, only about ten lanthanum-titanium oxo clusters have been reported. Except for two Ti28 clusters, the compounds are all small clusters (Ti ≤ 4). The cluster structures of 1–4 adopt a Ti10Ln2 core structure with pseudo-Ci symmetry, which is similar to the fundamental structure of Ti12 clusters. Furthermore, except for their structures, the properties of lanthanum-titanium oxo clusters have never been studied. Herein, the fluorescence properties of these compounds are studied in detail. The metal centered emission of Eu(III) is completely quenched by 9-AC due to the lower triplet energy of the coordinated ligand. Enhanced ligand centered fluorescence is found for 2 in comparison with that of 1.
Co-reporter:Jing Wu, Ya-Yang Pu, Xiao-Wei Zhao, Li-Wen Qian, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2015 vol. 44(Issue 10) pp:4520-4525
Publication Date(Web):21 Jan 2015
DOI:10.1039/C4DT03333G
A lot of ternary In–Sb–Q (Q = S, Se) chalcogenido-metalates with amines or complex cations have been recently reported for their diverse structures, however, such a type of In–Sn–Q chalcogenido-metalate has been rarely announced. Herein, we report a series of 2-D In–Sn–Q compounds prepared using a metal–phenanthroline cationic template, [M(Phen)3](In2Sn2Q8)·(amine)·nH2O (M = Ni(II), Fe(II) or Co(II); amine = cyclohexylamine (Cha) or 1,6-diaminohexane (Dah); Q = S or Se). Their anions are isostructural and a 2-D porous network with large 16-tetrahedron-rings. The 2-D network joint of In–Sn–Q is a (In/Sn)3Q3 six-membered ring, which is different from the Sn3Q4 pseudosemicube of most 2-D Sn–Q binary compounds. The materials exhibit photocurrent response properties measured using a photo-electrochemical cell. The result shows that (1) the selenides exhibit more intense photocurrents than the sulfides and (2) the current intensity is related to the metal–phenanthroline cations.
Co-reporter:Jin-Le Hou, Wen Luo, Yin-Yin Wu, Hu-Chao Su, Guang-Lin Zhang, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2015 vol. 44(Issue 46) pp:19829-19835
Publication Date(Web):16 Oct 2015
DOI:10.1039/C5DT03153B
Two benzene dicarboxylate (BDC) and salicylate (SAL) substituted titanium-oxo-clusters, Ti13O10(o-BDC)4(SAL)4(OiPr)16 (1) and Ti13O10(o-BDC)4(SAL-Cl)4(OiPr)16 (2), are prepared by one step in situ solvothermal synthesis. Single crystal analysis shows that the two Ti13 clusters take a paddle arrangement with an S4 symmetry. The non-compact (non-sphere) structure is stabilized by the coordination of BDC and SAL. Film photoelectrodes are prepared by the wet coating process using the solution of the clusters and the photocurrent response properties of the electrodes are studied. It is found that the photocurrent density and photoresponsiveness of the electrodes are related to the number of coating layers and the annealing temperature. Using ligand coordinated titanium-oxo-clusters as the molecular precursors of TiO2 anatase films is found to be effective due to their high solubility, appropriate stability in solution and hence the easy controllability.
Co-reporter:Jian-Bing Jiang, Peng Huo, Peng Wang, Yin-Yin Wu, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2014 vol. 2(Issue 14) pp:2528-2533
Publication Date(Web):25 Feb 2014
DOI:10.1039/C3TC32093F
Cadmium chalcogenido C1 (Cd17) CdQ (Q = S, Se) clusters with MV2+ cations (MV = methylviologen) are prepared under solvothermal conditions, using thiourea and selenourea as S and Se sources. The anions ([Cd17Q4(SPh)24Br4]2−) are discrete homosized nano-clusters with about a 1.5 nm scale. The selenide cluster can be considered as a nano-CdSe/CdS core–shell particle with a CdSe4 core and a [Cd16(SPh)24Br4] shell. The electronic spectra show the characteristic peaks of charge transfer bands. Cyclic voltammetry exhibits a low-potential-shift due to the charge transfer from the cadmium chalcogenido cluster to the MV2+ cation. Photocurrent responses of compounds 1 and 2 are studied using a three electrode cell. The results are as follows. (1) The current intensities of the MV–CdQSPh clusters are significantly larger than those of the CdQSPh clusters with quaternary ammonium cations; (2) the photocurrent directions of 1 and 2 can change from positive to negative when the irradiation wavelength is changed from UV light to visible light due to the different photocurrent conversion mechanism. The effect of MV2+ on these properties is discussed.
Co-reporter:Shu-Fang Ji, Yong-Gang Sun, Peng Huo, Wei-Chun Shen, Yu-De Huang, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2014 Volume 53(Issue 7) pp:3611-3617
Publication Date(Web):March 20, 2014
DOI:10.1021/ic403107v
Organic low molecular weight gelators with a tetrathiafulvalene (TTF) unit have received considerable attention because the formed gels usually exhibit redox active response and conducting or semiconducting properties. However, to our knowledge, metal coordination systems have not been reported for TTF-derived gels up to date. We have designed and synthesized a series of TTF derivatives with a diamide-diamino moiety that can coordinate to specific metal ions with square coordination geometry. Gelation properties and morphologies of the films prepared by the gelators in different hydrophobic solvents are characterized. The TTF derivative with a dodecyl group shows effective gelation properties, and electrodes with the organogel films are prepared. The effect of the Ni(II) and Cu(II) coordination on the photocurrent response property of the electrodes is examined. The metal square coordination significantly increases the photocurrent response. This gel system is the first metal coordination related TTF-gel-based photoelectric material. The mechanism of the metal coordination-improved photocurrent response property is discussed based on the crystal structural analysis and theoretical calculations.
Co-reporter:Yu-De Huang, Peng Huo, Ming-Yan Shao, Jing-Xue Yin, Wei-Chun Shen, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2014 Volume 53(Issue 7) pp:3480-3487
Publication Date(Web):March 12, 2014
DOI:10.1021/ic402926n
Although charge-transfer compounds based on tetrathiafulvalene (TTF) derivatives have been intensively studied, {[cation]n+·[TTFs]n–} ion pair charge-transfer (IPCT) salts have not been reported. The aim of this research is to introduce functional organic cations, such as photoactive methyl viologen (MV2+), into the negatively charged TTF–metal coordination framework to obtain this new type of IPCT complex. X-ray structural analysis of the four compounds (MV)2[Li4(L)2(H2O)6] (1), {(MV)(L)[Na2(H2O)8]·4H2O}n (2), {(MV)[Mn(L)(H2O)2]·2H2O}n (3), and {(MV)[Mn(L)(H2O)2]}n (4), reveals that the electron donor (D) TTF moiety and the electron acceptor (A) MV2+ form a regular mixed-stack arrangement in alternating DADA fashion. The TTF moiety and the MV2+ cation are essentially parallel stacked to form the column structures. The strong electrostatic interaction is a main force to shorten the distance between the cation and anion planes. Optical diffuse-reflection spectra indicate that charge transfer occurs in these complexes. The ESR and magnetic measurements confirm that there is strong charge-transfer-induced partial electron transfer. Compounds 2, 3, and 4 show an effective and repeatable photocurrent response. The current intensities of 3 and 4 are higher than that of 2, which reflects that the coordination center of the Mn(II) ion has a great effect on the increasing photocurrent response.
Co-reporter:Yong-Gang Sun, Shu-Fang Ji, Peng Huo, Jing-Xue Yin, Yu-De Huang, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2014 Volume 53(Issue 6) pp:3078-3087
Publication Date(Web):March 4, 2014
DOI:10.1021/ic402993y
Small organic molecule-based compounds are considered to be promising materials in photoelectronics and high-performance optoelectronic devices. However, photoelectron conversion research based on functional organic molecule and metal complex dyads is very scarce. We design and prepare a series of compounds containing a tetrathiafulvalene (TTF) moiety substituted with pyridylmethylamide groups of formulas [Ni(acac)2L]·2CH3OH (1), [Cu2I2L2]·THF·2CH3CN (2), and [MnCl2L2]n·2nCH3CH2OH (3) (L = 4,5-bis(3-pyridylmethylamide)-4′,5′-bimethylthio-tetrathiafulvalene, acac = acetylacetone) to study the role of the coordination center in photocurrent behavior. Complex 1 is a mononuclear species, and complex 2 is a dimeric species. Complex 3 is a two-dimensional (2-D) coordination polymer. Spectroscopic and electrochemical properties of these complexes indicate that they are electrochemically active materials. The tetrathiafulvalene ligand L is a photoelectron donor in the presence of electron acceptor methylviologen. The effect of metal coordination centers on photocurrent response behavior is examined. The redox-active metal coordination centers should play an important role in improvement of the photocurrent response property. The different morphologies of the electrode films reflect the dimensions in molecular structures of the coordination compounds.
Co-reporter:Yin-Yin Wu, Xiao-Wen Lu, Miao Qi, Hu-Chao Su, Xiao-Wei Zhao, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2014 Volume 53(Issue 14) pp:7233-7240
Publication Date(Web):June 20, 2014
DOI:10.1021/ic500390j
Attention has been paid to titanium–oxo clusters (TOCs) modified with functional molecules, because they can be considered as model systems for dye-sensitized titanium oxides in terms of their information in structures and electron transfer. We select 9-anthracenecarboxylate (9-AC) as a photoactive ligand and prepare two model compounds, [Ti6O6(OiPr)6(9-AC)6] (1) and [Ti6O4(OiPr)6(cat)4(9-AC)2] (2) (where cat = catecholate). Structures of the TOCs and the dye–TOC linkage are characterized by single-crystal analysis. Solvent-induced fluorescence change is observed for the cluster solution, and the fluorescence can be turned off by irradiating and on by oxygen bubbling. Photoinduced Ti(III) is responsible for the fluorescence extinction. The photocurrent conversion property of the clusters is examined by use of a three-electrode cell with cluster-coated indium tin oxide (ITO) electrodes. The results indicate that 9-AC is an effective photosensitizer and cluster 1 shows higher photocurrent intensity for its multiantenna structure in comparison with that of 2. Density of states for cluster 1 is calculated, in which the discrete energy bands of Ti6O24 include a number of new energy levels for the contribution of 9-AC molecules.
Co-reporter:Jian-Bing Jiang, Yin-Yin Wu, Peng Wang, Peng Huo, Qin-Yu Zhu, Jie Dai
Dyes and Pigments 2014 Volume 107() pp:153-160
Publication Date(Web):August 2014
DOI:10.1016/j.dyepig.2014.04.003
•Large size cadmium chalcogenido clusters with ruthenium complex cations are prepared.•Cation–anion charge-transfer property is found for these chalcogenido materials.•The intensity of photocurrent is related to the cluster size and the chalcogenido elements of the clusters.Large cadmium chalcogenido clusters C2 (Cd32) and C1 (Cd17) CdQ (Q = S, Se) with photoactive dye cations [Ru(Phen/Bpy)3]2+ are prepared under solvothermal conditions (Phen = 1,10-phenanthroline, Bpy = 2,2′-bipyridine). All the C2 compounds are 3-D polymeric structures, while the C1 compounds are discrete Cd17 clusters. Two of the 3-D C2 clusters can be considered as homosized nano CdSe@CdS core–shell particles (2.0 nm radius) with Cd4Se10 core. Charge-transfer interaction is found between [Ru(Phen/Bpy)3]2+ cations and CdQ cluster anions. The photocurrent behaviors indicate that (1) the current intensities are greatly increased for the dye cation functionalized Cn clusters, (2) the current intensities of the 3-D C2 clusters are larger than those of the discrete C1 clusters, and (3) the current intensities of the selenide clusters are larger than those of the sulfide clusters.
Co-reporter:Xiao-Lu Sun, Qin-Yu Zhu, Wen-Qin Mu, Li-Wen Qian, Lan Yu, Jing Wu, Guo-Qing Bian and Jie Dai
Dalton Transactions 2014 vol. 43(Issue 33) pp:12582-12589
Publication Date(Web):23 Jun 2014
DOI:10.1039/C4DT01289E
As most of the chalcogenidometalate anions are well-known electron-rich systems, design and preparation of ion pair compounds, by integrating an organic acceptor (A) with an inorganic chalcogenidometalate donor (D), are an attractive strategy to obtain new functional materials. We report herein the single-crystal structures and properties of three new ion pair charge-transfer (IPCT) compounds by incorporating thiogermanates with methylviologen (MV2+, N,N′-dimethyl-4,4′-bipyridinium dication), [MV]2Ge4S10·xSol (Sol = solvent). Sharp and fast solvent-induced color changes and switchable fluorescence emission are observed for the compounds. The weak interactions that relate to the solvent and ions in the structures are likely the key points to modulate the cation–anion charge-transfer. A photocurrent response is observed for the photoelectric system of the IPCT compound upon repetitive switching of light on and off.
Co-reporter:Wei-Chun Shen, Peng Huo, Yu-De Huang, Jing-Xue Yin, Qin-Yu Zhu and Jie Dai
RSC Advances 2014 vol. 4(Issue 104) pp:60221-60226
Publication Date(Web):07 Nov 2014
DOI:10.1039/C4RA10991K
Because the pyridyl group can act as a proton acceptor and a coordination biting unit, electrodes with films of dithiolene complex [n-Bu4N][Ni(4-pedt)2] (1) (4-pedt = 1-(pyridine-4-yl) ethylene-1,2-dithiolate) are prepared to investigate the photocurrent response behaviours of a metal dithiolene compound upon protonation and transition metal coordination. The morphologies of film 1 are characterized by SEM analysis. Photoelectrochemical measurements are carried out with the electrodes of film 1. The results are as follows: (1) the stronger the medium acidity is, the weaker the photocurrent becomes. (2) Photocurrent intensities of Mn(II), Co(II) and Zn(II) treated film 1 are increased in comparison with that of the original film 1 due to the polymeric coordination. (3) When film 1 is treated by Fe(III) ions, it is oxidized to a neutral [Ni(4-pedt)2] film that shows weaker photocurrent response. In addition, a new ionic pair compound MV[Ni(4-pedt)2]2 (2) (MV2+ = methylviologen dication) synthesized by cation exchange shows good photocurrent response properties due to the improvement of electron transfer.
Co-reporter:Xiao-Lu Sun, Qin-Yu Zhu, Li-Wen Qian, Lan Yu, Zhi-Gang Ren, Guo-Qing Bian, Jie Dai
Inorganic Chemistry Communications 2014 Volume 46() pp:130-133
Publication Date(Web):August 2014
DOI:10.1016/j.inoche.2014.05.038
Co-reporter:Yin-Yin Wu, Peng Wang, Yu-Hong Wang, Jian-Bing Jiang, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2013 vol. 1(Issue 34) pp:9862-9868
Publication Date(Web):13 Jun 2013
DOI:10.1039/C3TA11571B
Much attention has been paid to titanium oxo clusters (TOCs) because of their use as model compounds of bulk nanoscale titanium oxides. On the other hand, doping of TiO2 with some metal complexes of 1,10-phenanthroline (phen) or bipyridine (bpy) results in low band-gap materials with high photovoltaic conversion efficiency. In this work, two metal–phenanthroline substituted titanium-oxo-clusters, [Ti17O28(OiPr)16(CoIIphen)2] (C1) and [Ti17O28(OiPr)18(CdIIphen)2] (C2), were successfully prepared by one-step in situ solvothermal synthesis. The structures of the compounds are best described as an oxo-isopropanoxo Ti17 parent fused with two M–phen moieties. They are the first examples of M–phen modified oxo-alkoxy titanium clusters. The band structure of the cluster is modified by the coordination of the metal complex and the absorption of the material is improved. The cluster can not only be used as a model for theoretical study, but can also be used as a precursor to prepare sensitized TiO films. Films (F1) with unique microstructures of hollow spheres, bowls, and doughnuts were obtained by a simple non-template coating method from the solution of Co–phen–TiO cluster C1. The size of the spheres is about 1–2 μm and the thickness of the shell is about 50 nm. Upon repetitive irradiation of the F1 film on the ITO electrode in a three electrode system, a clear photocurrent response was observed. The Co–phen moiety plays an important role in electron transition.
Co-reporter:Peng Wang, Yin-Yin Wu, Jing Wu, Sheng Wang, Lan Yu, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2013 vol. 1(Issue 47) pp:7973-7978
Publication Date(Web):01 Nov 2013
DOI:10.1039/C3TC31607F
A gel matrix is an appropriate medium for photoswitchable fluorescent systems, because the gel provides a wet medium for the solvent-related fluorescence emission. Although some studies have been performed on the photoswitchable fluorescence properties of dye-entrapped organo- or inorgano-gels, the gels usually act just as a matrix. We report here a new soft hybrid material, in which the inorganic TiO gel is doped with perylene tetracarboxylate (PTC). The TiO gel not only acts as a wet matrix but, more importantly, also acts as the photoactive switch or shelter. The PTC–TiO solution in ethanol is prepared by solvothermal reaction at 60 °C and 80 °C, respectively. The solution exhibits different colors and different fluorescence emission according to the reaction temperature and time, due to the different assembly of the PTC dye molecules. The solution is then gelated by a typical method for TiO2 gels, giving a material with photoswitchable fluorescence properties. The fluorescence of the perylene moiety can be switched off and on by irradiation and oxygen blowing. The photo-induced Ti(IV)/Ti(III) redox-chromic effect is the most reasonable explanation for the fluorescence emission and extinction, because Ti(III) is detected in the photo-blackened PTC–TiO gel.
Co-reporter:Ming-Yan Shao, Peng Huo, Yong-Gang Sun, Xin-Yu Li, Qin-Yu Zhu and Jie Dai
CrystEngComm 2013 vol. 15(Issue 6) pp:1086-1094
Publication Date(Web):26 Nov 2012
DOI:10.1039/C2CE26219C
A series of coordination polymers of cadmium(II) and cobalt(II) with TTF–tetracarboxylate ligand (L) were prepared using room temperature synthetic methods and solvothermal method. The room temperature methods are subdivided to controlled evaporation method and two layers diffusion method. The fundamental structures of these compounds are {[M(L)0.5(B)(S1)x]·yS2}n (1–6) (M = Cd(II) or Co(II), B (base) = 2,2′-bpy, phen or 4,4′-bpy, S1 (coordinated solvent) = C2H5OH or H2O, and S2 (co-crystallized solvent) = H2O or CH3OH, x = 1 or 2, and y = 0 to 3). Compound 7 is a known ionic pair n[Co(4,4′-)2(H2O)4]·[Co(L)(H2O)2]n. At room temperature, no matter what the metal ions are, Cd(II) or Co(II), and the synthetic methods are, controlled evaporation or two layers diffusion, the products 1–4 and 7 are 1-D coordination polymers. Both the 2-D Co(II) coordination polymer 5 and 3-D coordination polymer 6 were prepared by solvothermal method. A new type of coordination mode of the TTF–tetracarboxylate ligand is found in the structures of 2 and 3, in which two carboxyl groups have a μ2-η2:η1 bridging mode, and the other two carboxyl groups are not coordinated. Electrochemical properties of the solid-state compounds were also investigated by cyclic voltammetry using surface-modified electrodes.
Co-reporter:Li-Sheng You, Qin-Yu Zhu, Xiang Zhang, Ya-Yang Pu, Guo-Qing Bian and Jie Dai
CrystEngComm 2013 vol. 15(Issue 13) pp:2411-2415
Publication Date(Web):14 Jan 2013
DOI:10.1039/C3CE26726A
A germanium–vanadate cluster [Ge5V6O21(heda)6] (1) with covalently coordinated N-(2-hydroxyethyl)ethylenediamine (Hheda) was synthesized and crystallographically characterized. The cluster is a new type of GeVO cluster, in which there coexists various oxo-polyhedra of VIV and GeIV, octahedral VO6, VO5N, and GeO4N2, VO5 pyramid and GeO4 tetrahedron. The cluster is also an unusual neutral germanium–polyoxovanadate. The deprotonated hydroxyl group and part of the amine groups of the heda ligand covalently coordinate to the cluster. There are three coordination modes of the ligand, monodentate, chelating and multi-chelating modes. The organic ligand plays important roles in the charge balance and cluster construction.
Co-reporter:Yu-Hong Wang, Jian-Bing Jiang, Peng Wang, Xiao-Lu Sun, Qin-Yu Zhu and Jie Dai
CrystEngComm 2013 vol. 15(Issue 30) pp:6040-6045
Publication Date(Web):24 May 2013
DOI:10.1039/C3CE40270C
Four new indium chalcogenide compounds 1–4 were prepared by a similar solvothermal synthetic method in 1,2-diaminocyclohexane (dach) medium with or without the auxiliaries of germanium oxide or ionic liquid 1-butyl-3-methyl imidazolium bromide. Among them, two unusual polymeric structures assembled by Tn clusters were found. The anion of {H2dach·[Ni(dach)3]·[In12S20(dach)2]·3H2O}n (1) is a three-dimensional framework assembled by T3 clusters, in which the linkage is a unique In4(dach)4S6 cluster. The anion of {(Hdach)2·[Co(dach)3]4·[In16Co4S37]·dach·5H2O}n (3) is an unusual two-dimensional framework assembled by T4 clusters, in which the T4 clusters are linked by (S3)2− polysulfide ion. The structures of the other two new compounds are known, and they are {[Ni(dach)3]·[In2S4]·3H2O}n (2) and{(Hdach)4·[Co(dach)3]6·{[In16Co4S34]2[Co(dach)2]3}·6H2O}n (4). The auxiliaries play an important role in the structural assembly of the Tn clusters, mainly due to their effects on acidity of the reaction system and solubility of the reactants or products.
Co-reporter:Xin-Yu Li, Yong-Gang Sun, Peng Huo, Ming-Yan Shao, Shu-Fang Ji, Qin-Yu Zhu and Jie Dai
Physical Chemistry Chemical Physics 2013 vol. 15(Issue 11) pp:4016-4023
Publication Date(Web):08 Jan 2013
DOI:10.1039/C3CP44054K
The complex Et4N[Ni(4-pedt)2] (1) (4-pedt = 1-(pyridine-4-yl) ethylene-1,2-dithiolate) was synthesized to investigate the behaviour of metal dithiolene compounds upon protonation and oxidation by absorption spectroscopy, electrochemistry and structural analyses and to further understand the electronic states of the dithiolene compounds. It is unexpected that the 915 nm NIR transition band is not shifted when H+ is added, and it is only affected (blue-shifted) when the compound is oxidized. All the evidence of electronic spectra indicates that the NIR band is relevant to the central [Ni(edt)2] moiety (edt = ethylenedithiolate), not the behaviour of individual Ni ions or ligands. It is also not the band of intermolecular interaction of a dimer. The moderately intense band appearing at 655 nm upon protonation is assigned to the intramolecular charge-transfer band between the [Ni(edt)2] moiety and the pyridine. The redox potentials of the metal dithiolene are sensitive to the protonation of the pyridyl group. The structures of monocationic complex 1 and the protonated compounds [Ni(4-Hpedt)2]·ClO4·H2O (2) and [Ni(4-Hpedt)2]·PhSO3·2DMF (3) were characterized by single crystal X-ray determination. The structural data demonstrate that the oxidation of the monoanionic dithiolene complex to neutral does not change the Ni–S bond distances obviously, which further indicates that the process is not only the metal centered oxidation.
Co-reporter:Xiang Zhang, Ya-Yang Pu, Li-Shen You, Guo-Qing Bian, Qin-Yu Zhu, Jie Dai
Polyhedron 2013 Volume 52() pp:645-649
Publication Date(Web):22 March 2013
DOI:10.1016/j.poly.2012.07.092
Two wheel-shaped In18Te30 clusters with M-phen complex cations, [M(phen)3]2[In18Te30(dapn)6]·2Hdapn·dapn (M = Fe(II), and Ni(II), dapn = 1.3-diaminepropane), were prepared. The In18Te30 anion shows a double-layered ring structure that assembled by six In2Te6 subunits and six InTe3N tetrahedra. The size of the wheel-shaped clusters is about 1.6 nm. In the crystals clockwise and anticlockwise complex cations [M(phen)3]2+ are coupled through π⋯π interaction forming a dimer structure and the dimers are interacted with the clusters via C⋯Te (about 3.60 Å) short contacts. The sizes of the dimer cation and the anion are well compensated in crystal packing. Although there is wider range absorption of the In–Te anion, the MLCT transition of the Fe-phen cation still contributes to the low energy absorption.Two nano size wheel-shaped In18Te30 clusters with M-phen complex cations were prepared. In the crystals clockwise and anticlockwise complex cations [M(phen)3]2+ are coupled through π⋯π interaction forming a dimer structure and the dimers are interacted with the clusters via C⋯Te short contacts.
Co-reporter:Yu-Hong Wang, Wen Luo, Jian-Bing Jiang, Guo-Qing Bian, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2012 Volume 51(Issue 3) pp:1219-1221
Publication Date(Web):January 26, 2012
DOI:10.1021/ic202490q
The preparation and crystal structure of a large wheel-shaped indium–telluride compound are reported. The inorganic cluster is decorated with 1,2-diaminocyclohexane molecules that play an important role in the formation of the nanoring. A related new 1D polymeric InTe compound is also presented in order to understand the effect of acidity on the formation of the ring structure.
Co-reporter:Wen-Qin Mu, Qin-Yu Zhu, Li-Sheng You, Xu Zhang, Wen Luo, Guo-Qing Bian, and Jie Dai
Inorganic Chemistry 2012 Volume 51(Issue 3) pp:1330-1335
Publication Date(Web):January 9, 2012
DOI:10.1021/ic2014682
Thiogermanates, {[Ni(phen)3]2Ge4S10}·xSol (Sol = 4MeOH·12H2O (1) and 24H2O (2)) were prepared and characterized by single-crystal structure analysis. There are large quantities of the solvent molecules that cocrystallize with the anions and cations and form a strong hydrogen bonding network (O–H···S and O···H–O–H···O). Reversible yellow-pink color change with fast speed was found for these compounds, when the crystals were immersed in alcohol solvents and water alternately. The time of the solvent-induced color change relates to the molecular size and structure of the alcohols. The smaller the molecule is, the faster the color change will be. The fastest color change was found by using the methanol solvent that took only about one second. The color change also relates to the ratio of water/alcohol. The solvatochromism phenomenon is accompanied with a rapid solvent-induced recrystallization that is verified by the XRD patterns.
Co-reporter:Wen Luo, Wen-Qin Mu, Xu Zhang, Xiang Zhang, Ya-Yang Pu, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2012 Volume 51(Issue 3) pp:1489-1494
Publication Date(Web):January 9, 2012
DOI:10.1021/ic201754z
A Ge7 germanate, [Ni(H2O)(μ-C2H6NO)2Ge7O14(C2H7NO)]·C2H5OH (1), was prepared by the solvothermal method using ethanolamine (C2H7NO) as solvent, ligand, and structure-directing agent. Compound 1 shows an unusual GeO framework fused with transition metal complex. The 2-D layers of Ge7 clusters are linked by a [Ni(H2O)(μ-C2H6NO)2] moiety, forming a 3-D architecture. The preparation and structure of 1 are discussed in comparison with the Ge9 germanates decorated with metal ethylenediamine complexes. The hydroxyl group of the ethanolamine plays an important role in formation of the 3-D structure, in which the ligand ethanolamine is coordinated directly onto the Ge cluster by the hydroxyl group. It is a new type of germanates incorporated with a TM complex bridge. The proton on the flexible amine side can be exchanged by alkali metal ions.
Co-reporter:Yin-Yin Wu, Wen Luo, Yu-Hong Wang, Ya-Yang Pu, Xiang Zhang, Li-Sheng You, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2012 Volume 51(Issue 16) pp:8982-8988
Publication Date(Web):August 7, 2012
DOI:10.1021/ic301092b
Two titanium-oxo-clusters Ti6O4(o-BDC)2(o-BDCiPr)2(OiPr)10 (1) and Ti6O3(o-BDC)2(OiPr)14 (2) (BDC = benzene dicarboxylate) were prepared by one-step in situ solvothermal synthesis. The compounds are the rare examples of the dicarboxylate-substituted titanium-oxo-clusters. Their crystal structures are successfully measured by single-crystal X-ray analysis. The Ti6 oxo-clusters of 1 and 2 are constructed by two dual corner-missing cube subunit, Ti3O3. The two subunits are linked by double μ3–O bridges for 1 and single μ2–O bridge for 2, respectively, and the latter is a new type of carboxylate substituted titanium-oxo-cluster. A photochromic effect was observed upon irradiation of the crystals in the presence of alcohol. The light irradiation changed the color of the crystals from transparent to purple-gray. The Ti(III) signal was detected after the irradiation, and when the sample was exposured in air, superoxide diatomic O2• – radical was found. Photodegradation of the methyl orange in aqueous dispersions of microcrystals of the cluster 2 was carried out under UV cut white light with the assistance of H2O2.
Co-reporter:Peng Huo, Jin-Po Wang, Ming-Yan Shao, Yong-Gang Sun, Shu-Fang Ji, Qin-Yu Zhu and Jie Dai
Physical Chemistry Chemical Physics 2012 vol. 14(Issue 47) pp:16229-16235
Publication Date(Web):22 Oct 2012
DOI:10.1039/C2CP42836A
Hydrogen bonds are important in supramolecular chemistry and responsible for proton transfer processes. This manuscript reports new hydrogen-bonding systems of redox-active acid–base assemblies consisting of dimethylthio-tetrathiafulvalene dicarboxylic acid (H2L) coupled with pyridine (py), 2,2′-bipyridine (2,2′-bpy), and 4,4′-bipyridine (4,4′-bpy). The 1H NMR chemical shifts of the pyridines and the redox potential shifts of the tetrathiafulvalene moiety indicate that proton-transfer and strong hydrogen-bonding interactions exist between the acid and the bases in aprotic solvents. The results of cyclic voltammetry show a two-step square reaction with a redox and proton transfer coupled mechanism. The nature of the hydrogen bonds was characterized by X-ray single crystal analysis. In contrast to the mono-carboxyl–py system, in this ortho-substituted dicarboxyl–py system one proton of the H2L transfers completely from the carboxyl to the py group. The conjugated intramolecular and intermolecular hydrogen bonds are responsible for the proton transfer.
Co-reporter:Qiong-Hua Han, Zheng Shi, Ming-Yan Shao, Xin-Yu Li, Qin-Yu Zhu, Jie Dai
Inorganic Chemistry Communications 2012 Volume 15() pp:190-193
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.10.021
Two coordination compounds, [Mg(HL)(phen)(H2O)3]·HL·phen (1) and [Zn2L2(phen)2(H2O)2] (2), with dimethylthio-tetrathiafulvalene-bicarboxylate ligand (L) have been prepared by temperature controlled solvothermal reaction. Crystal structure analysis revealed that compound 1 is a mononuclear octahedral complex with co-crystallized free ligands, while compound 2 is a dimer with two square pyramidal metal centers. Both the compounds show a 1-D band-like supramolecular structure assembled by hydrogen bonds. The hydrophilic carboxylate groups and water molecules are gathered at the centerline of the band, and the TTF moieties and phen molecules are arranged at the two sides. The molecules are further contacted through short S⋅⋅⋅S interaction forming a 2-D net. These metal-TTF-bicarboxylates are redox-active and can undergo two steps oxidization in solid state.Two transition metal complexes with dimethylthio-tetrathiafulvalene-bicarboxylate ligand are prepared by solvothermal reaction. Crystal structures of both the compounds show a 1-D band-like supramolecular structure, in which hydrophilic carboxylate groups and water molecules lie at the centerline of the band, and the TTF moieties and phen molecules lie at the sides.Highlights► We prepared two metal-TTF-bicarboxylate complexes by temperature controlled solvothermal reaction. ► The compounds show band-like supramolecular structure assembled by hydrogen bonds. ► These compounds are redox-active and can undergo two steps oxidization in solid state.
Co-reporter:Qin-Yu Zhu, Qiong-Hua Han, Ming-Yan Shao, Jing Gu, Zheng Shi, and Jie Dai
The Journal of Physical Chemistry B 2012 Volume 116(Issue 14) pp:4239-4247
Publication Date(Web):March 21, 2012
DOI:10.1021/jp2124179
Although tetrathiafulvalene derivatives (TTFs) have been used as the redox-active unit in a lot of ion responsive receptors, only a few such examples of TTF carboxylic acids have been reported, especially about the responses to neutral organic molecules. In this work, electrochemical and spectral properties of dimethylthio-tetrathiafulvalene monocarboxylic acid (DMT-TTFCOOH) have been studied by both experimental methods and quantum chemical calculations. A square mechanism of proton transfer and electron transfer equilibriums was proposed. It is noteworthy that the process of oxidizing the TTF moiety of DMT-TTFCOOH could be controlled to obtain TTF•+ radical cation or TTF2+ dication by choosing suitable oxidizing reagents. Supramolecular responsive properties of DMT-TTFCOOH to py/bpy were investigated by cyclic voltammetry and 1H NMR spectra. The results showed that the compound DMT-TTFCOOH is an electrochemically sensitive hydrogen bonding donor that can detect a tiny difference in the hydrogen bonding acceptor molecules. The theoretical calculations further confirm the results. The hydrogen-bonding structure of DMT-TTFCOOH-bpy in crystal was solved by X-ray diffraction analysis.
Co-reporter:Xu Zhang ; Zhi-Xin Lei ; Wen Luo ; Wen-Qin Mu ; Xiang Zhang ; Qin-Yu Zhu
Inorganic Chemistry 2011 Volume 50(Issue 21) pp:10872-10877
Publication Date(Web):October 14, 2011
DOI:10.1021/ic201404t
Two 1-D selenidoindates {[M(phen)3]In2Se5·H2O}n (M = Ni, Fe) were synthesized by a solvothermal method. The 1-D {[In2Se5]2–}n anion is a new type of single 1-D structure constituted by an alternately fused four-membered In2Se2 ring and five-membered In2Se3 ring. The chalcogenoindates were separated as mechanical racemic mixtures of single enantiomer crystals, in which the R-helix of 1-D InSe anion is directed by the related clockwise (Δ) cations of [M(phen)3]2+ or the L-helix of 1-D anion is directed by the related anticlockwise (Λ) cation. The π···π, C···Se, and C–H···Se oriented interactions of metal complex cations with selenidoindate anions play an important role in the formation of the chiral crystals. The embedded [M(phen)3]2+ cations improve the optical absorption of the 1-D semiconductor materials.
Co-reporter:Xu Zhang, Wen Luo, Ya-Ping Zhang, Jian-Bing Jiang, Qin-Yu Zhu, and Jie Dai
Inorganic Chemistry 2011 Volume 50(Issue 15) pp:6972-6978
Publication Date(Web):June 29, 2011
DOI:10.1021/ic200157v
A series of supertetrahedral polymers of chalcogenometalates (T3 cluster compounds) integrated with M-phen complexes (phen =1,10-phenanthroline; M = Ni, Fe) was prepared by a similar solvothermal technique. Compound [Fe(phen)3]4[H4In20S38]·Hphen·3HDMA·8H2O (Mp-InS-4) (DMA = dimethylamine) is a 1-D straight chain. Compounds [M(phen)3]4[In20S37]·6Hphen·4H2O (M = Ni, Mp-InS-5; Fe, Mp-InS-6) are the first reported 2-D Tn polymers integrated with complex cations of [M(phen)3]2+. Compound [Ni(phen)3]4[H4In20S38]·2Hphen·2HDMA·3H2O (Mp-InS-7) shows a zigzag 1-D structure. We find that the reaction time is an important factor in assembling of the T3 clusters. Prolonging the reaction time seems favorable to the higher condensed phases (from 0-D to 2-D). However, a longer reaction time resulted in the crack of 2-D structure. Integrating M–phen complex cations with the chalcogenido anions can improve absorption of the materials in the visible range due to the charge transfers within the cations or between cations and anions.
Co-reporter:Qin-Yu Zhu, Lei Yu, Yu-Rong Qin, Li-Bin Huo, Ming-Yan Shao and Jie Dai
CrystEngComm 2011 vol. 13(Issue 7) pp:2521-2528
Publication Date(Web):07 Feb 2011
DOI:10.1039/C0CE00424C
A series of zinc(II) complexes (1–6) with the ligands 4′,5′-diaza-9′-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene) fluorene (L1) or 4′,5′-diaza-9′-(4,5-bis(ethylthio)-1,3-dithiol-2-ylidene) fluorene (L2) have been prepared in the presence of different zinc(II) salts, [Zn(L1)2(NO3)(MeOH)](NO3)·CH2Cl2·0.5(MeOH)·0.5(EtOH) (1), [Zn(L1)2(PhCOO)]NO3·MeOH (2) (PhCOO = benzoic ion), [Zn(L1)2Cl] [Zn(L1)Cl2] [ZnCl3(MeOH)]·CH2Cl2·H2O (3), [Zn(L1)2(ClO4)2] (4), [Zn(L2)2Cl] [Zn(L2)Cl2] [ZnCl3(MeOH)]·0.5(MeOH) (5), and [Zn(L2)2(ClO4)2] (6). Five of the complexes (1–3, 5, and 6) have been structurally characterized by single-crystal X-ray diffraction. The preferred coordination geometry of the zinc(II) center is related to the coordinated anions. Complexes 1, 2 and 6 with oxo-anions display distorted octahedral geometry, while complexes 3 and 5 with chloride anions take five- and four-coordination geometries. The weak coordinated perchlorate anion prefers a trans structure, while the strong coordinated nitrate anion favors a cis structure. The intermolecular C⋯C, C⋯S, and S⋯S interactions lead to the assembly of the complexes into different supramolecular frameworks. The results of the 1H NMR, UV-vis, and fluorescent spectra display a large effect of metal coordination on the electron density of the ligand. Spectral data for the complexes is in agreement with the crystal structures. Finally, semi-empirical PM3 calculations were carried out to explain the relationship of the structures and the spectra.
Co-reporter:Qin-Yu Zhu, Jin-Po Wang, Yu-Rong Qin, Zheng Shi, Qiong-Hua Han, Guo-Qing Bian and Jie Dai
Dalton Transactions 2011 vol. 40(Issue 9) pp:1977-1983
Publication Date(Web):31 Jan 2011
DOI:10.1039/C0DT01152E
Though numerous metal–organic frameworks or polymers have been reported, the organic building blocks are usually not redox-active. On the other hand, some mono-, di- or tri-nuclear compounds with tetrathiafulvalene (TTF) have been prepared, although little is known about the coordination polymers combined with paramagnetic metals and organic TTF ligands. We report herein a series of coordination polymers of copper(II) and manganese(II) with TTF dicarboxylate ligand (L). Compound 1, [CuL(2,2-bpy)]n, is a one-dimensional (1-D) coordination polymer with five-coordinated square-pyramidal Cu(II) centers. Mn(II) complex 2, [MnL(2,2-bpy)]n, also takes a 1-D structure, showing a double-bridged mode by carboxylate groups. The 4,4-bipyridine compound 3, [MnL(4,4-bpy)(H2O)]n·CH3CN, takes a 2-D grid network. A zinc(II) compound 4, [ZnL(4,4-bpy)(H2O)]n·CH3CN, isomorphous structure with 3, is also presented. The electrochemical properties of the solid-state compounds were investigated by cyclic voltammetry using surface-modified electrodes. As usually observed in TTF derivatives, two sets of redox-waves were observed. The values of E1/2(1) of compounds 1–4 are in the order of 2(Mn) ≈ 3(Mn) < 1(Cu) < 4(Zn), indicating that the metal coordination can affect the potential shift of the TTF ligand. Weak antiferromagnetic exchanges are observed for compounds 1, 2, and 3.
Co-reporter:Zheng Shi, Qiong-Hua Han, Xin-Yu Li, Ming-Yan Shao, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2011 vol. 40(Issue 28) pp:7340-7347
Publication Date(Web):15 Jun 2011
DOI:10.1039/C1DT10353A
A bis(diamino-diamido) tetrathiafulvalene (TTF) derivative H4L2 has been designed and synthesized. Experiments of pH titration reveal that integrating the redox active TTF unit with the diamino-diamido moiety adds new properties to the traditional ligand. Oxidation of the TTF moiety increases the acidity of the amido group, and the coordination of metal ions is also sensitive to the oxidation state of the ligand. This compound is capable of acting as a leaving or accepting ligand for proton and metal ions. The electrochemistry of the protonated TTF derivative of H4L2 was studied in the presence of a series of oxo anions and metal cations. The results indicate that the redox potentials selectively respond to HC2O4− and SO42− anions, and Ni(II) and Cu(II) cations. Solid-state structures of a cation–anion salt H8L2·2SO4·8H2O and a nickel coordination compound [Ni2L2]·2DMF have been characterized by means of X-ray crystallography which are helpful in understanding the inter-ion interactions.
Co-reporter:Jian-Bing Jiang, Guo-Qing Bian, Ya-Ping Zhang, Wen Luo, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2011 vol. 40(Issue 37) pp:9551-9556
Publication Date(Web):17 Aug 2011
DOI:10.1039/C1DT10860C
Three anion–cation compounds 1–3 with formula [M(phen)3][Cd4(SPh)10]·Sol (M = Ru2+, Fe2+, and Ni2+, Sol = MeCN and H2O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π⋯π stacking and C–H⋯π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion–cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)3]2+ is enhanced when the cation interacts with the [Cd4(SPh)10]2− anion. The mechanism for the enhancement of photoluminescence has been proposed.
Co-reporter:Ya-Ping Zhang, Zhi-Xin Lei, Jian-Bing Jiang, Qin-Yu Zhu, Xu Zhang, Guo-Qing Bian, Jie Dai
Inorganica Chimica Acta 2011 Volume 376(Issue 1) pp:645-650
Publication Date(Web):1 October 2011
DOI:10.1016/j.ica.2011.06.049
We have reported main group metal chalcogenido clusters of cubic [InQ(phen)Cl]4 (Q = S (1) and Se (2); phen = 1,10-phenanthroline). Herein two new cubic clusters with ligand of 2,2′-bipyridine (bpy) have been synthesized by solvothermal technique, [InSe(bpy)Cl]4 (3) and [InS(bpy)Cl]4·H2O (4). The molecular structures and electronic states of compounds 3 and 4 are presented by comparing with those of 1 and 2. Though the clusters of 1–4 are similar, their packing structures show diverse modes. Spectroscopic study and theoretical calculation indicate that introducing phen/bpy to chalcogenido clusters can decrease the energy gap of frontier orbitals from HOMO to LUMO due to the cluster to ligand charge-transfer (CLCT). Increasing the conjugated system of the organic ligand or using the heavier chalcogenido element might improve the photophysical absorption of the materials.Graphical abstractCubic clusters [InQ(L)Cl]4 (Q = S, Se; L = bipyridine) have been synthesized by solvothermal technique. The molecular structures and the cluster to ligand charge-transfer (CLCT) of these compounds are discussed in comparing with those of the phenanthroline analog.Highlights► Cubic In4Q4 (Q = S, Se) clusters with bipyridine ligand were synthesized. ► Main-group metal cubanes were prepared by solvothermal technique. ► Charge-transfer was found from cluster to bipyridine ligand.
Co-reporter:Zheng Shi, Zhe-Jun Lu, Qin-Yu Zhu, Li-Bin Huo, Qiong-Hua Han, Guo-Qing Bian, and Jie Dai
The Journal of Physical Chemistry B 2011 Volume 115(Issue 12) pp:3020-3026
Publication Date(Web):March 8, 2011
DOI:10.1021/jp110010z
A new cation- and anion-sensitive system based on a TTF derivative with a diamino−diamido moiety (H2L) has been studied. The results of cyclic voltammetry indicated that the redox potentials of the protonated H2L (H4L2+) selectively respond to later transition metal cations and some oxo anions. Solid-state structures of the cation−anion compounds formed by H4L2+ and oxo anions were characterized crystallographically, which is helpful to understand the matter of the sensitivity for the anion. There are two types of hydrogen bonds in these compounds, one is with an amino group and the other is with an amido group. The shift of the redox potential is obviously related to formation of hydrogen bonding with the amido group. The packing structures of these cation−anion compounds are arranged to layered sandwiched structures assembled by an oxo-anion layer and two TTF layers through hydrogen bonding.
Co-reporter:Yu-Hong Wang ; Ming-Hui Zhang ; Yun-Meng Yan ; Guo-Qing Bian ; Qin-Yu Zhu
Inorganic Chemistry 2010 Volume 49(Issue 21) pp:9731-9733
Publication Date(Web):October 4, 2010
DOI:10.1021/ic100088n
Tn clusters are usually connected into frameworks by sulfur bridges. A new type of T4 compounds in which the clusters are linked by both sulfur bridges and transition metal complexes are described.
Co-reporter:Zhi-Xin Lei ; Qin-Yu Zhu ; Xu Zhang ; Wen Luo ; Wen-Qin Mu
Inorganic Chemistry 2010 Volume 49(Issue 10) pp:4385-4387
Publication Date(Web):April 16, 2010
DOI:10.1021/ic902572m
A new type of indium−sulfur supertetrahedral compound with unique optical absorption property has been synthesized and characterized crystallographically, in which discrete or polymeric InS-T3 clusters are integrated with metal complex cations of 1,10-phenanthroline.
Co-reporter:Zhi-Xin Lei ; Qin-Yu Zhu ; Ming-Hui Zhang ; Jian-Bing Jiang ; Ya-Ping Zhang
Inorganic Chemistry 2010 Volume 49(Issue 2) pp:353-355
Publication Date(Web):December 11, 2009
DOI:10.1021/ic901143h
Most metal−1,10-phenanthroline-complex-sensitized inorganic semiconductors are multicomponent materials. This fundamental study was devoted to the single-phase materials fused with moieties of the phen complex and inorganic chalcogenide. Compounds 1 and 2 are new types of cubic clusters with cluster-to-ligand charge transfer.
Co-reporter:Yu-Rong Qin ; Qin-Yu Zhu ; Li-Bin Huo ; Zheng Shi ; Guo-Qing Bian
Inorganic Chemistry 2010 Volume 49(Issue 16) pp:7372-7381
Publication Date(Web):July 22, 2010
DOI:10.1021/ic100546r
The synthesis of the transition metal coordination polymers containing a tetrathiafulvalene (TTF) moiety substituted with a tetracarboxylate group of the formulas [Mn(L)0.5(phen)(H2O)2]n·nH2O (1), [Mn(L)0.5(bpy)]n·nH2O (2), [Mn(L)0.5(bpy)(CH3OH)]n·2nH2O (3), and [Cu(L)0.5(bpy)(DMF)]n·n(DMF) (4) (L4− = TTF-tetracarboxylate; phen = 1,10-phenanthroline; bpy = 2,2′-bipyridine) is reported. Complex 1 is a two-dimensional (2-D) coordination polymer constructed of infinite carboxylate bridged Mn(II) chains and TTF moiety linkages. Complex 2 possesses a 3-D polymeric structure formed by infinite −Mn−(O−C−O)2−Mn− bridged one-dimensional (1-D) chains, which are further coordinated by TTF-tetracarboxylate ligands of two different orientations. Both complexes 3 and 4 show 1-D extended chain structures but are constituted by different dinuclear metal(II) units with a −Mn−(O−C−O)2−Mn− bridge in 3 and a −Cu−(O)2−Cu− bridge in 4. Electrochemical study of the solid-state compounds attests to the redox activity of the coordination system. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in complexes 3 and 4, while in 1, the paramagnetic metallic centers are isolated, in agreement with the solid-state structure.
Co-reporter:Jin-Po Wang, Zhe-Jun Lu, Qin-Yu Zhu, Ya-Ping Zhang, Yu-Rong Qin, Guo-Qing Bian and Jie Dai
Crystal Growth & Design 2010 Volume 10(Issue 5) pp:2090
Publication Date(Web):March 25, 2010
DOI:10.1021/cg901018s
Four coordination compounds of calcium and magnesium with tetrathiafulvalene (TTF) bicarboxylate ligand have been synthesized and characterized by single-crystal analysis. As well-studied bicarboxylate complexes, the carboxylate groups in this ligand coordinate to alkaline earth metal ions in multidentate modes forming compounds 1−4. Calcium compounds [CaL(DMF)2] (1) and [Ca2L2(H2O)2(EtOH)]·MeOH (2) take a seven-coordinated sphere with a pentagonal bipyramid geometry, while magnesium compounds [Mg2L2(H2O)7]·EtOH·4H2O (3) and [Na2(DMF)2(H2O)9][MgL2(DMF)2] (4) are six-coordinated with an elongated octahedral geometry. The effect of metal ion radii on the coordination structure is clearly exhibited. The molecules of these alkaline-earth metal complexes are assembled to a sandwiched structure with hydrophobic layers of a sulfur-rich TTF matrix and hydrophilic layer of the metal carboxylate. Equilibriums of the metal coordination, acid dissociation, and ligand oxidation have been studied in the solution systems of these compounds. At a neutral state of the TTF moiety, TTF-carboxylate is an appropriate ligand for Ca(II) ion, but when the TTF moiety is oxidized, it switches the alkaline earth metal ion to the solution.
Co-reporter:Zhe-Jun Lu, Jin-Po Wang, Qin-Yu Zhu, Li-Bin Huo, Yu-Rong Qin and Jie Dai
Dalton Transactions 2010 vol. 39(Issue 11) pp:2798-2803
Publication Date(Web):09 Feb 2010
DOI:10.1039/B921745B
A new bifunctional tetrathiafulvalene (TTF) derivative has been designed and synthesized, in which the TTF moiety (a redox functional group) is integrated with a dioxotetraamine (a coordination functional group) structure. Like other dioxotetraamine compounds, it is capable of acting as an ion leaving and accepting ligand for protons and Cu(II) and Ni(II) ions in solution. Experiments of pH titration have shown that the TTF unit adds new redox properties to the traditional ligand. Oxidation of the ligand increases the acidity of the imido group and the coordination of metal ions is also sensitive to the oxidation state of the ligand. The ligand forms either a square coordinated Ni(II) complex with two deprotonated imido groups and two amino groups, or a pentacoordinated Cu(II) complex with an additional solvent molecule. The compounds form a belt structure with strong N–H⋯O hydrogen bonds, which is a basic character for this type of compound in the crystalline form.
Co-reporter:Qin-Yu Zhu, Yu Liu, Zhe-Jun Lu, Jin-Po Wang, Li-Bin Huo, Yu-Rong Qin, Jie Dai
Synthetic Metals 2010 Volume 160(7–8) pp:713-717
Publication Date(Web):April 2010
DOI:10.1016/j.synthmet.2010.01.006
A new paddlewheel dinuclear complex with a pyridyl-tetrathiafulvalene (TTF-py) ligand has been obtained and characterized crystallographically as [(DMT-TTF-py)2Cu2(OAc)4]·2C6H6 (1). Meanwhile a mononuclear compound [(DMT-TTF-py)2Cu(PhCOO)2(CH3OH)2]·2CH2Cl2 (2) was also isolated. UV–vis spectra and cyclic voltammogram of the paddlewheel complex were studied, showing that compound 1 can undergo an oxidization to form a stable cation of [(DMT-TTF-py)2Cu2(OAc)4]2+. By this strategy, compound 3, [(DMT-TTF-py)2Cu2(OAc)4](I3)2 as a radical salt, has been prepared and its conductivity of powder sample was 1.02 × 10−3 ohm−1 cm−1. Antiferromagnetic coupling of Cu(II)–Cu(II) was found from the results of ESR spectra, but the coupling between the radical–Cu(II) was very weak.
Co-reporter:Qin-Yu Zhu, Li-Bin Huo, Yu-Rong Qin, Ya-Ping Zhang, Zhe-Jun Lu, Jin-Po Wang and Jie Dai
The Journal of Physical Chemistry B 2010 Volume 114(Issue 1) pp:361-367
Publication Date(Web):December 10, 2009
DOI:10.1021/jp908399r
An A−D−A triad compound comprising a tetrathiafulvalene (TTF) moiety and two pyridyl groups, py−TTF−py (1), has been studied in view of intramolecular charge transfer (ICT). The compound shows a sharp and multicolor change in different solvents and at different pH values, exhibiting good solvatochromism. The results of electronic absorption spectroscopy, cyclic voltammetry, and theoretical calculations confirm that there exists predominantly a monoprotonated A−D−A triad that displays a strong ICT effect, which is tunable as a function of pH. The equilibrium of protonation of 1 has been further studied by means of pH titration, and the result confidently supports the conclusion that only one equivalent H+ combines with py−TTF−py in dilute solution, even when excessive acid is added. However, unlike the state in dilute solution, the crystal structure of the protonated 1 is a diprotonated A−D−A triad, (1·2H+)·(CF3SO3−)2·H2O (2), that has been structurally characterized.
Co-reporter:Yong Zhang;Jian Zhou;Ai-Bin Tang;Guo-Qing Bian
Journal of Chemical Crystallography 2010 Volume 40( Issue 6) pp:496-500
Publication Date(Web):2010 June
DOI:10.1007/s10870-009-9684-z
Two new thiostannates [M(tepa)]2(μ-Sn2S6) (tepa = tetraethylenepentamine, M = Fe2+1 and Co2+2) were prepared by solvothermal method. Compounds 1 and 2 are isostructural. Both the compounds crystallize in the tetragonal system, space group I41/a (no. 88) with the crystal parameters of 1: a = 25.683(2) Å, b = 25.683(2) Å, c = 9.9860(9) Å, V = 6,586.7(11) Å3, Z = 8, and 2: a = 25.742(3) Å, b = 25.742(3) Å, c = 9.8977(12) Å, V = 6,558.5(14) Å3, Z = 8. The Sn2S64− anion acts as a bidentate bridging ligand connecting two transition metal complex cations by trans terminal S atoms to form neutral centrosymmetric [M(tepa)]2(μ-Sn2S6) moieties.
Co-reporter:Jian Zhou, Jie Dai, Guo-Qing Bian, Chun-Ying Li
Coordination Chemistry Reviews 2009 Volume 253(9–10) pp:1221-1247
Publication Date(Web):May 2009
DOI:10.1016/j.ccr.2008.08.015
Inorganic–organic hybrid chalcogenidometalate materials have attracted considerable interest, because they are a new type of materials with unique topologic structures. The syntheses of these materials are typically carried out under hydro(solvo)thermal conditions at relatively low temperatures. Organic amines have been demonstrated to be successful and versatile molecules to be used in template-directed synthesis of numerous chalcogenide-based open-framework materials. Some comprehensive reviews have summarized the preparation and structures of the chalcogenidometalates with non-chelating amines. Extended and embedded researches on the chelating amines containing a different number of N-donor atoms have recently attracted more interest in synthetic chemistry. A series of unique inorganic–organic hybrid chalcogenidometalate materials are successfully isolated lately. This review focuses on the recent developments in solvothermal synthesis of main group chalcogenidometalates in the presence of organic chelating amines or polyamines as reaction medium. In contrast to the non-chelating amines, the roles of the chelating amines in the syntheses and the effects of the chelating amines on the crystal structures are discussed. A comprehensive outline of the chalcogenidometalate compounds with metal complex cations is also presented.
Co-reporter:Fei Lin, Guo-Qing Bian, Zhi-Xin Lei, Zhe-Jun Lu, Jie Dai
Solid State Sciences 2009 Volume 11(Issue 5) pp:972-975
Publication Date(Web):May 2009
DOI:10.1016/j.solidstatesciences.2009.02.017
Solvothermal growth of cuprous selenide films on copper substrate has been succeeded by treating copper foil in the mixture of selenium powder and amines or hydrazine. The films were characterized by methods of XRD, SEM, TEM and optical spectra (Cu2Se, JCPDS 47-1448). Films with hexagonal microcrystals can be obtained in hydrazine/water reaction system. When CTAB (CTAB = cetyltrimethylammonium bromide) is added to the system, the film is composed of thin leaf-like microcrystals. When ethylenediamine (en) is used as solvent, the leaf-like microcrystals are crimped.
Co-reporter:Jian Zhou, Guo-Qing Bian, Qin-Yu Zhu, Yong Zhang, Chun-Ying Li, Jie Dai
Journal of Solid State Chemistry 2009 Volume 182(Issue 2) pp:259-264
Publication Date(Web):February 2009
DOI:10.1016/j.jssc.2008.10.025
A low temperature solvothermal method has been successfully used for preparation of two semiconductor compounds CuSbQ2 (Q=S(1), Se(2)) by the reactions of Cu, Sb and S(or Se) powders in 1,2-diaminopropane at 160 °C for 10 days. The crystal structure of 2 was determined first time using single crystal X-ray diffraction analyses. The structures of 1 and 2 are discussed in the view of covalent bonds and weak interactions. Double CuSbQ2 layers are assembled to a 3-D network structure by Cu⋯Sb and Q⋯Sb secondary bonds. In contrast with the isostructure of the two materials, the crystal morphology of them is quite different, brick-like crystals for CuSbS2 and plank-like crystals for CuSbSe2. The phenomenon is related to their different inter-planar interactions. Semiconductor properties of the microcrystal samples are measured and the band gaps of 1 and 2 are 1.38 and 1.05 eV, respectively.Two isostructural compounds, CuSbQ2 (Q=S, Se), display different morphologies in crystals, which is explained by comparing the strength of the interlayer interactions based on the crystal structure data.
Co-reporter:Chun-Ying Li ; Xiao-Xia Chen ; Jian Zhou ; Qin-Yu Zhu ; Zhi-Xin Lei ; Yong Zhang
Inorganic Chemistry 2008 Volume 47(Issue 19) pp:8586-8588
Publication Date(Web):August 28, 2008
DOI:10.1021/ic801121q
Coordination of unsaturated [In(amine)]3+ onto indium telluride structure, where the complex ion has higher positive charge, not only forms an organic−inorganic hybrid polymeric structure, but also offers an indium telluride with positive charge. Based on this strategy, cationic networks of metal chalcogenide may be expected.
Co-reporter:Jian Zhou, Yong Zhang, Guo-Qing Bian, Chun-Yin Li, Xiao-Xia Chen and Jie Dai
Crystal Growth & Design 2008 Volume 8(Issue 7) pp:2235
Publication Date(Web):June 14, 2008
DOI:10.1021/cg700821n
Four new gallium chalcogenides [H2dap]4Ga4Se10 (1), [Mn(dap)3]0.5GaSe2 (2), {[Ni(tepa)]2SO4}[Ni(tepa)(Ga4S6(SH)4)] (3) and [Mn(atep)]Ga2S4 (4) (dap = 1,2-diaminopropane, tepa = tetraethylenepentamine, atep = 4-(2-aminoethyl)triethylenetetramine) have been synthesized by solvothermal methods and structurally characterized. The effects of the strong chelating amines on the topology of gallium chalcogenidometalates have been enumerated. First, in the absence of transition metal ions, the chelating amine can offer more N−H groups than the monoamines to form hydrogen bonds; therefore, compound 1 takes a 2-D polymeric structure constructed by supertetrahedral clusters ([Ga4Se10]8−, T2). Second, when transition metals are incorporated into the chelating amine system, larger [M(dap)3]2+complex cations are formed, which force the anions of compound 2 to adopt a 1-D structure ([GaSe2]− chain). Third, when an appropriate chelating amine (e.g., tepa) is selected, unsaturated transition metal complex cations can be obtained, which not only act as a large cation but also form the covalently linked organic−inorganic hybrid compounds 3 and 4. The anion in 3 is a T2 {[Ga4S6(SH)4]4−} cluster connected to a [Ni(tepa)]2+ complex cation, while the structure of 4 consists of 1-D sinusoidal [Ga4S84−]n anion combined with [Mn(atep)]2+ complex cations.
Co-reporter:Qin-Yu Zhu;Wen Lu;Yong Zhang;Guo-Qing Bian;Jing Gu;Xiao-Min Lin
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 2) pp:230-238
Publication Date(Web):
DOI:10.1002/ejic.200700862
Abstract
Four complexes with 4′,5′-diaza-9′-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]fluorene (L1) or 4′,5′-diaza-9′-[4,5-bis(ethylthio)-1,3-dithiol-2-ylidene]fluorene (L2) were synthesized. The complexes [Co(L1)2Cl2]·2CH3OH (1), [Cu(L2)2Cl2]·CH3OH·0.5CH2Cl2 (3), and [Cu(L2)2Br2]·CH3OH (4) adopt a trans configuration and the compound [Cd(L1)2(NO3)2] (2) is a cis structure. Short S···S, C···C, and C···S contacts were found to be important in the molecular packing. Both the solution and solid-state electronic spectra show a redshift in the intramolecular CT bands when forming metal complexes. This intramolecular charge transition in the solid state is enhanced relative to that in solution. Their third-order nonlinear optical properties of compounds 1–4 were studied, and the results reveal that these complexes exhibit negative γ values (about 10–30) and are self-defocusing samples. These γ values are comparable to those of the known cluster compounds. The trans coordination of the two ligands to the metal center would be beneficial to the NLO properties. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:Jing Gu, Qin-Yu Zhu, Yong Zhang, Wen Lu, Gai-Yan Niu, Jie Dai
Inorganic Chemistry Communications 2008 Volume 11(Issue 2) pp:175-178
Publication Date(Web):February 2008
DOI:10.1016/j.inoche.2007.12.002
Comparing with the TTF-pyridyl metal complexes, very few compounds have been prepared with TTF-carboxylate ligands. We using 8,9-dimethylthio-2,3-dicarboxylate-tetrathiafulvalene sodium salt as starting material prepared two Co(II) and Ni(II) metal complexes, [Co(H2O)6][Co(L)2(DMF)2] and [Ni(H2O)6][Ni(L)2(DMF)2]. X-ray structure analysis has revealed that the metal ion is coordinated by four carboxylate groups from two ligands in the equatorial plane and two DMF molecules in the apical positions. The molecules are assembled by short S⋯S contacts forming a 2D sheet with rectangular grid net. The hexaaquometal cations [Co(H2O)6]2+ reside in the cavities of the 2D network and are fixed by O–H⋯O hydrogen bonds. Cyclic voltammogram and spectra of the ligand are affected when the metal ion coordinated.Two Co(II) and Ni(II) metal complexes, [Co(H2O)6][Co(L)2(DMF)2] and [Ni(H2O)6][Ni(L)2(DMF)2] were prepared, which are assembled to a 2D sheet by S⋯S contacts with rectangular grid net. The hexaaquometal cations [Co(H2O)6]2+ reside in the cavities of the 2D network and are fixed by O–H⋯O hydrogen bonds.
Co-reporter:Chun-Ying Li, Jian Zhou, Guo-Qing Bian, Ming-Hui Zhang, Jie Dai
Inorganic Chemistry Communications 2008 Volume 11(Issue 11) pp:1327-1329
Publication Date(Web):November 2008
DOI:10.1016/j.inoche.2008.08.011
The title compound, [Dy2(en)6(μ2-OH)2]Ga4S8 (en = ethylenediamine), contains 1D infinite sinusoidal [GaS2-]n anions and hydroxy bridged dinuclear dysprosium complex cations. Two bridging hydroxy ions connect two inversion-related Dy3+ ions to form a centrosymmetric dimer, in which a Dy2O2 rhomboidal core is formed. The title compound is the only example of the thiogallates with lanthanide-containing counter cation.Although some thiogallates with transition metal complex cation have been reported, the title compound, containing 1D infinite sinusoidal [GaS2]-[GaS2]- anions and hydroxy bridged dinuclear dysprosium complex cations, is the only example of the thiogallates with lanthanide-containing counter cation.
Co-reporter:Na Chen;Wen Lu;Qin-Yu Zhu;Yong Zhang;Jing Gu;Xiao-Min Lin
Structural Chemistry 2008 Volume 19( Issue 2) pp:219-223
Publication Date(Web):2008 April
DOI:10.1007/s11224-007-9275-6
At room temperature, the reaction of 2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene-]-4,5-bis(2-cyanoethylsulfanyl)-1, 3-dithiole (CM-TTF) with mercury chloride resulted in a black radical salt constructed by dimeric cations and chloromercurate anions in formula (CM-TTF)2Hg2Cl6. The S···S stacking of 3.289(3) and 3.334(3) Å within the TTF dimer are very strong in comparing with those of other TTF radical salts. Effective C···C stacking (3.349(10) Å) was also found within the dimeric structure.
Co-reporter:Lei Yu, Qin-Yu Zhu, Yong Zhang, Zhi-Xin Lei, Gai-Yan Niu and Jie Dai
The Journal of Physical Chemistry A 2008 Volume 112(Issue 51) pp:13672-13678
Publication Date(Web):December 2, 2008
DOI:10.1021/jp8073283
Proton effects on an intramolecular donor−acceptor molecular system 4′,5′-diaza-9′-(4,5-dialkylthio-1,3-dithiol-2-ylidene)fluorenes (methylthio = L1 (1), ethylthio = L2 (2)) have been experimentally and theoretically studied. Structures of L2 (2) and three protonated salts, [L2·H]CF3SO3 (3), [L1·H]CF3SO3 (4), and [L1·H]ClO4 (5), were characterized by single-crystal X-ray determination. In all these salts the cations are found to be monoprotonated even in an excessive amount of acid. The protonated imine group forms strong N−H···O or N−H···N hydrogen bonds, which enhance the interaction between cations and anions and play an important role in the molecular packing. The measurement of UV−vis spectra indicates a two-step red shift of the absorption bands, which corresponds to the two-step protonation of L in solution. The intramolecular charge-transfer (ICT) property is enhanced when the compounds are protonated. Compound L is also a proton sensible fluorescent system with two-step remarkable changes in band energy and intensity. The study on the effect of protonation is further complemented by theoretical calculation with the DFT/TDDFT method.
Co-reporter:Qianxin Zhao, Dingxian Jia, Yong Zhang, Lifeng Song, Jie Dai
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:1895-1901
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.09.023
Three new lanthanide thiostannates [Ln2(en)6(μ2-OH)2]Sn2S6 (Ln = Nd (1), Gd (2); en = ethylenediamine) and [Gd(dien)3]2[(Sn2S6)Cl2] (3) (dien = diethylenetriamine) were first synthesized by treating LnCl3 with SnCl4 and S under mild solvothermal conditions. Compounds 1 and 2 are isostructural. They consist of a binuclear lanthanide(III) complex [Ln2(en)6(μ2-OH)2]4+ cation and a dimeric [Sn2S6]4− anion. The anion is built up by two SnS4 tetrahedra sharing a common edge. The Nd3+ and Gd3+ ions are in an eight-coordinated environment forming distorted bicapped trigonal prisms. Compound 3 is composed of two monouclear [Gd(dien)3]3+ complex cations, a [Sn2S6]4− anion, and two chlorine ions. The Gd3+ ion has a nine-coordinated environment forming a distorted tricapped trigonal prism. In compounds 1–3, extensive hydrogen bonds are formed leading to three-dimensional networks of anions and cations. The band gaps of 2.42 eV for 1 and 3.17 eV for 2 have been derived from optical absorption spectra. The new lanthanide compounds might be the precursors for ternary lanthanide thiostannates by the heat treatment under nitrogen atmosphere to get rid of organic components.Three new lanthanide thiostannates [Nd2(en)6(μ2-OH)2]Sn2S6, [Gd2(en)6(μ2-OH)2]Sn2S6 and [Gd(dien)3]2[(Sn2S6)Cl2] (where, en = ethylenediamine; dien = diethylenetriamine) have been first synthesized by the solvothermal method with the reaction of SnCl4, S with NdCl3 and GdCl3, respectively. Their crystal structures, optical properties and thermal decomposition are reported.
Co-reporter:Wen Lu;Yong Zhang;Qin-Yu Zhu;Guo-Qing Bian;De-Qing Zhang
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 8) pp:
Publication Date(Web):21 FEB 2006
DOI:10.1002/ejic.200500945
A new dinuclear metal complex including tetrathiafulvalene (TTF) radicals as ligands has been prepared and characterized, [{DMT-TTF(CONH2)2}2Cu2Cl6] (1), DMT-TTF(CONH2)2 = o-bis(amido)-appended dimethylthio-tetrathiafulvalene. The compound is an uncommon example in which TTF radicals directly coordinate to the copper(II) halide by the amido group. Crystal structure analysis shows that it is a unique coordination bond/H-bond/S···S stacking cooperative system with two radicals and two paramagnetic transition metal ions, TTF+·–CuII–CuII–TTF+·. In the structure of 1, the DMT-TTF units form dimers with very strong S···S interactions. The CuII–O(amide) distance of the coordination bond is 2.271(2) Å and the S···S stacking distances between the radicals are in the range 3.345–3.489 Å. The metal–metal ions are mildly antiferromagnetically coupled (2J1 =–58.4 cm–1), while the radical pairs are strongly antiferromagnetically coupled (2J2 > –1000 cm–1).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Qin-Yu Zhu, Hai-Hong Lin, Jie Dai, Guo-Qing Bian, Yong Zhang and Wen Lu
New Journal of Chemistry 2006 vol. 30(Issue 8) pp:1140-1144
Publication Date(Web):17 Jul 2006
DOI:10.1039/B604258A
Solid state and solution chemistry of a supramolecular system, a sodium complex with ligands of tetrathiafulvalene (TTF) dicarboxylate and benzotriazole molecules, have been studied. The well characterized host–guest response in H2O–CH3CN (1 ∶ 1 v/v) was monitored by electronic spectra and cyclic voltammetry. The host–guest reaction occurred immediately under the experimental conditions, which took only about 15 min to form high quality and large scale crystals. By the coordination of sodium cations and the water bridges, an unusual one dimensional structure formed. The compound is a coordination bonding, hydrogen-bonding assembled and, especially, topological cooperated supramolecule. The reaction selectivity of the TTF-dicarboxylate with small organic molecules has also been discussed.
Co-reporter:Qin-Yu Zhu, Guo-Qing Bian, Yong Zhang, Jie Dai, De-Qing Zhang, Wen Lu
Inorganica Chimica Acta 2006 Volume 359(Issue 7) pp:2303-2308
Publication Date(Web):25 April 2006
DOI:10.1016/j.ica.2006.01.034
The synthesis and crystal structure of a new tetrathiafulvalene (TTF) derivative with an acetylacetone substituent are reported (3-(dimethylthio-TTF-thio)-2,4-pentane-dione, DMT-TTF-acac (1)). Compound 1 consists of a TTF plane and an acac plane, which are bridged by a sulfur atom. The bond distances and angles of 1 clearly indicate that the acetylacetone group adopts a keto–enol structure with an O–H⋯O intramolecular hydrogen bond. As usually observed for TTF derivatives, compound 1 exhibits two-step reversible redox waves on CV measurement, which are sensible to the metal ions being added. The stronger the metal coordination is, the larger the potential shift would be. Two complexes of 1, [M(DMT-TTF-acac)2] M = Mn(II) and Cu(II), have been prepared and they are very stable even in the state in which the ligands are oxidized. The iodine-doped compound of Mn(II) is a new organic–inorganic system consisting of paramagnetic metal ions and organic radicals.The synthesis and crystal structure of a new tetrathiafulvalene (TTF) derivative, (DMT-TTF-acac (1)), are reported. The redox potentials of 1 are sensible to the metal ions being added. The stronger the metal coordination, the larger the potential shift would be. As an effective ligand, compound 1 coordinates to Mn(II) and Cu(II) ions forming redox active complexes.
Co-reporter:Wen Lu;Zhe-Min Yan;Yong Zhang;Qin-Yu Zhu;Ding-Xian Jia;Wen-Juan Guo
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 12) pp:
Publication Date(Web):15 JUN 2005
DOI:10.1002/ejic.200401002
The sulfur-rich ligand C12H12O4S6 (1) and complexes [(C12H12O4S6)CuI]2 (2) and [(C7H6O4S3)CuI]∞ (3) have been synthesized and characterized crystallographically. Molecules of compound 1, a tetrathiafulvalene (TTF) derivative, have a boat-shaped configuration and are packed discretely within the crystal. Compound 1 coordinates to a rhomboid CuI center forming a dimeric TTF derivative 2. In complex 2 the boat-shaped configuration of 1 is flattened. Molecules of 2 are packed regularly and compactly in the crystal and are arranged side by side with short S···S contacts, which assemble the molecules into a 1D ribbon structure. This provides evidence that metal coordination or assembly is a useful stratagem for changing the molecular configuration and packing that further influence the intermolecular interactions. Complex 3 has a step-like polymeric structure formed by copper-iodine bridges and copper-sulfur bridges (coordinated thiocarbonyl). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Hai-Hong Lin, Zhe-Min Yan, Jie Dai, De-Qing Zhang, Jing-Lin Zuo, Qin-Yu Zhu and Ding-Xian Jia
New Journal of Chemistry 2005 vol. 29(Issue 3) pp:509-513
Publication Date(Web):18 Jan 2005
DOI:10.1039/B411380B
The properties of a water-soluble TTF dicarboxyl salt, Na2[C10H6O4S6]·3H2O, have been explored. The cyclic voltammogram of the salt shows two quasi-reversible redox waves at E1/2(1) = 0.280 V and E1/2(2) = 0.556 V with ΔE (Eox−Ere) = 78 and 68 mV, respectively, in H2O–CH3CN (1∶1 v/v). The redox potential of this compound is strongly dependent on the proton concentration. An ECEC square reaction, a redox-coupled association/dissociation of proton, was found for the second redox cycle. The redox active salt forms a mono-protonated anion in the pH range of 2–5. The calculated pKb constant of the salt is 5.93, corresponding to pKa(2)
= 8.07 of the original binary acid. A single crystal structure of Bu4N[C10H7O4S6] was also obtained, which confirms that the mono-protonated compound has a stable conjugated structure.
Co-reporter:Li-Hui Cao, Yong Zhang, Jie Dai, Hai-Hong Lin, Wen Lu, Wen-Juan Guo
Journal of Molecular Structure 2005 Volume 737(2–3) pp:153-157
Publication Date(Web):4 March 2005
DOI:10.1016/j.molstruc.2004.10.023
A dimeric TTF derivative of bis{2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-4-(methylsulfanyl)-5-(methylenesulfanyl)-1,3-dithiole} (1) was synthesized and characterized. The sulfur atom of a methylthio group interacts with CC double bond of the neighboring TTF moiety exhibiting a S–π interactions within a molecular chain. The molecules are further assembled to a 2D structure by an S⋯S interaction (3.3441(17) Å). Open and folded model for the molecular conformation is discussed based on the results measured in the solid state (crystal structure) and in solution (cyclic voltammogram).
Co-reporter:Ding-Xian Jia, Jie Dai, Qin-Yu Zhu, Li-Hui Cao, Hai-Hong Lin
Journal of Solid State Chemistry 2005 Volume 178(Issue 3) pp:874-881
Publication Date(Web):March 2005
DOI:10.1016/j.jssc.2004.07.045
Three new thiogermanates (enH)4Ge2S6 (1) and [M(en)3]2Ge2S6 (M=Mn (2), Ni (3); en=ethylenediamine) were synthesized using GeO2 and S8 as starting materials in molar ratio of 1:0.5 under solvothermal conditions. These compounds suggest that the dimeric [Ge2S6]4− anion is likely to be the main germanium-containing species in en system and it also might be preferred as counter anions by the transition metal complex cations in crystallization. The cations of [Mn(en)3]2+ and [Ni(en)3]2+ are even better mineralizers than the protonated amine of [enH]+. The crystal systems of [Ge2S6]4− compounds are related to entities of cations and intermolecular reactions between cations and [Ge2S6]4− anions. The compounds remove ethylenediamine and H2S molecules in multi steps when being heated under nitrogen stream.Three new thiogermanates were synthesized using GeO2 and S8 as starting materials in molar ratio of 1:0.5 under solvothermal conditions (ethylenediamine) at 150 °C.
Co-reporter:Qin-Yu Zhu;Ding-Xian Jia;Li-Hui Cao;Hai-Hong Lin
European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 24) pp:
Publication Date(Web):15 NOV 2004
DOI:10.1002/ejic.200400330
Manganese(II) complexes with the ligand 9′-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-4′,5′-diazafluorene (L) have been synthesized, and the single-crystal structures of complexes [Mn(L)2(H2O)2](ClO4)2·(L)2·2C2H5OH·2CH3CN (1), [Mn(L)2Cl2]·1.5CH2Cl2 (2) and [Mn(L)2(NO3)2] (3) have been characterized. Complex 1 is trans-coordinated with N···H−O and S···S contacts, while the other two complexes are cis-coordinated with short π···π stacking. Solvent-free powder samples were also obtained and these complexes showed catalytic activity in the decomposition of H2O2 in the presence of added imidazole; the perchlorate compound was the most effective. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Co-reporter:Ding-Xian Jia, Yong Zhang, Jie Dai, Qin-Yu Zhu, Xiao-Mei Gu
Journal of Solid State Chemistry 2004 Volume 177(Issue 7) pp:2477-2483
Publication Date(Web):July 2004
DOI:10.1016/j.jssc.2004.04.009
Thioantimonate compounds of [Mn(en)3]2Sb2S5 (1) and [Ni(en)3(Hen)]SbS4 (2) (en=ethylenediamine) were prepared by reaction of transition metal chloride with Sb and S8 powders under solvothermal conditions. Compound 1 consists of discrete [Sb2S5]4− anion, which is formed by corner-sharing SbS3 trigonal pyramids. Compound 2 is composed of discrete tetrahedral [SbS4]3− anion. The compounds 1 and 2 are charge compensated by [M(en)3]2+ cations, whereas in the crystal of 2 there is another counter ion of [Hen]+. The results of the synthesis suggest that the temperature, the concentration and the existing states of the starting materials and so on are important for the structure and composition of the final products. In addition, the oxidation-state of antimony might be related to the molar ratio of the reactants. Excess amount of elemental S is beneficial to the higher oxidation-state of thioantimonate (V). Compound 1 decomposes from 150°C to 350°C, while compound 2 decomposes from 200°C to 350°C remaining Sb2S3 and NiSbS as residues.
Co-reporter:Jie Dai, Guo-Qing Bian, Min-Yan Zhou, Qin-yu Zhu, Lin Guo, Jia-Sheng Zhang
Synthetic Metals 2004 Volume 140(Issue 1) pp:53-56
Publication Date(Web):6 January 2004
DOI:10.1016/S0379-6779(02)01312-7
Four binuclear dmit complexes of palladium(II), having μ-X or -S bridges, have been synthesized and characterized. The complexes, (Bu4N)[Pd2X2(dmit)2] (X=Cl (1) and Br (2)), were prepared by metathesis reaction from bridged precursors, [(Bu4N)2(Pd2X6)]. The complexes, D2[Pd2(Sph)2(dmit)2] (D=Bu4N (3) and Et4N (4)), were prepared by cracking reaction of polymeric precursor [Pd2Cl2(Sph)2]n. The benzenthiolate-bridged anions of 3 and 4 exhibit dinegative ionic charge (2−), which can be deduced from the precursor. On the other hand, the halogen-bridged anions of 1 and 2 are oxidized during the synthetic reaction and show uninegative ionic charge (1−).
Co-reporter:Bian Guo-Qmg;Zhu Qin-Yu;Wang Xin;Yang Wei;Yan Ze-Min;Dai Jie;Sun Zhen-Rong;Munakata Megumu;Maekawa Masahiko
Chinese Journal of Chemistry 2003 Volume 21(Issue 5) pp:
Publication Date(Web):26 AUG 2010
DOI:10.1002/cjoc.20030210513
A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)2[M(Ln)(SPh)2] (M = Cd and Zn, L1 = dmit = 1,3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh= thiophenolate) (1–4) were characterized by elemental analysis, IR, UV NMR spectra and so on. The advantages of this method are summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although dmid is an analogue to dmit.
Co-reporter:Guo-Qing Bian, Jie Dai, Qin-Yu Zhu, Wei Yang, Ze-Min Yan, Megumu Munakata and Masahiko Maekawa
Chemical Communications 2002 (Issue 14) pp:1474-1475
Publication Date(Web):10 Jun 2002
DOI:10.1039/B202698H
Novel binuclear dithiolate complexes (Me4N)2[M2(SPh)2(S2TTF(SMe)2)2] (M = Cd and Zn) have been synthesized by a new cluster-cracking method.
Co-reporter:Chong-Jiao Mo, Zhao-Qi Li, Chen-Jie Que, Guang-Lin Zhang, Qin-Yu Zhu, Jie Dai
Dyes and Pigments (June 2017) Volume 141() pp:
Publication Date(Web):June 2017
DOI:10.1016/j.dyepig.2017.01.073
•1,10-Phenanthroline coordinated tin halides as photosensitive dyes.•Halide to phen charge transfer organic-inorganic hybrid.•Color and fluorescence adjustable photoelectro active materials.A series of organic-inorganic hybrid tin halides formulated as Sn(phen)XmYn (phen = 1,10-phenanthroline, X/Y = Cl, Br, I, m + n = 4) were designed and prepared to study main group metal halides as photosensitive dyes. The colors of compounds are tunable with the change of mole ratio of the halides due to the ligand to ligand charge-transfer (LLCT). Intense visible-range absorption can be obtained by increasing the mole ratio of iodine and intense ultraviolet fluorescence emission can be obtained by increasing the mole ratio of chlorine. DFT calculations suggest that the LLCT occurs from electron-rich halide ion to π* orbit of phen. The iodide materials have narrow energy gap and suitable energy level of the excited state for exciton transfer to TiO2 semiconductor. Photocurrent responses experiments using the compounds treated TiO2 electrodes showed that upon irradiation stable photocurrent generated and Sn(phen)I4 has the best photosensitive behavior.A series of hybrid tin halides Sn(phen)XmYn were designed and prepared. Their absorption and fluorescence spectra are continuously adjustable by changing the composition of different halide elements. These main-group metal halides have ligand to ligand charge-transfer properties and can be used as photoelectrosensitizers.
Co-reporter:Zhao-Qi Li, Chong-Jiao Mo, Yao Guo, Nan-Nan Xu, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2017 - vol. 5(Issue 18) pp:NaN8525-8525
Publication Date(Web):2017/04/03
DOI:10.1039/C7TA00247E
Supertetrahedral clusters of main-group metal chalcogenides (Tn) have been well-studied for decades. Most of them are polymerized 2D or 3D structures and have been used as porous materials for ion exchange and as ion conductors. Large discrete T5 clusters of main-group metal chalcogenides are attractive in that they might be used as nanocluster materials with uniform size and definite structures. However, until now, discrete T5 clusters have been reported only in the solid state and their dispersed solution has not yet been obtained due to their low solubility in common solvents, thus not to mention their application as nanodots. We prepare a crystal compound with discrete T5 CuInS clusters using a simple and economical way. A solution of the T5 clusters was obtained by a strategy using a medium with strong ionic strength to overcome the strong ionic force in crystals. The discrete T5 clusters in solution is proved by HRTEM and ESI-MS. The nano-T5 CuInS clusters can be easily modified on a TiO2 electrode by a wet process and the clusters show excellent photo-sensitive properties tested by photocurrent and photocatalysis.
Co-reporter:Shen Yang, Hu-Chao Su, Jin-Le Hou, Wen Luo, Dan-Hong Zou, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2017 - vol. 46(Issue 29) pp:NaN9645-9645
Publication Date(Web):2017/07/13
DOI:10.1039/C7DT01603D
Titanium-oxo-clusters (TOCs), [Ti6O4(OiPr)10(Cat)2(BA)2] (1) and [Ti12M2O10(OEt)22(Cat)2(BA)4] (M = Co, Mn, Ni, 2–4; H2Cat = catechol, HBA = benzoic acid) are prepared in one step in an in situ solvothermal synthesis. Cluster structures of 2–4 can be considered as two 1 moieties merged together by two transition metal atoms. Unlike most TOCs with sphere-like structures, clusters 2–4 feature a unique single layered structure. They are not only transition metal doped TOCs but also charge transfer (CT) TOCs, CT from Cat to the TiO cluster core. Photoelectrodes were prepared by dipping the solution of clusters on a porous TiO2 substrate. Photocurrent response properties of the electrodes were studied in comparison with those of the electrodes of non-metal doped 1 and the non-Cat coordinated Ti6 cluster. The results showed that the photocurrent densities of metal doped clusters are higher than that of non-doped clusters and the highest photocurrent density was found for the redox active Co(II) doped cluster. Charge transfer also plays an effective role in photocurrent conversion under visible light irradiation.
Co-reporter:Peng Huo, Jin-Po Wang, Ming-Yan Shao, Yong-Gang Sun, Shu-Fang Ji, Qin-Yu Zhu and Jie Dai
Physical Chemistry Chemical Physics 2012 - vol. 14(Issue 47) pp:NaN16235-16235
Publication Date(Web):2012/10/22
DOI:10.1039/C2CP42836A
Hydrogen bonds are important in supramolecular chemistry and responsible for proton transfer processes. This manuscript reports new hydrogen-bonding systems of redox-active acid–base assemblies consisting of dimethylthio-tetrathiafulvalene dicarboxylic acid (H2L) coupled with pyridine (py), 2,2′-bipyridine (2,2′-bpy), and 4,4′-bipyridine (4,4′-bpy). The 1H NMR chemical shifts of the pyridines and the redox potential shifts of the tetrathiafulvalene moiety indicate that proton-transfer and strong hydrogen-bonding interactions exist between the acid and the bases in aprotic solvents. The results of cyclic voltammetry show a two-step square reaction with a redox and proton transfer coupled mechanism. The nature of the hydrogen bonds was characterized by X-ray single crystal analysis. In contrast to the mono-carboxyl–py system, in this ortho-substituted dicarboxyl–py system one proton of the H2L transfers completely from the carboxyl to the py group. The conjugated intramolecular and intermolecular hydrogen bonds are responsible for the proton transfer.
Co-reporter:Jing-Xue Yin, Peng Huo, Sheng Wang, Jing Wu, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2015 - vol. 3(Issue 2) pp:NaN415-415
Publication Date(Web):2014/11/05
DOI:10.1039/C4TC02009J
Many exfoliation strategies have been developed to prepare 2-D sheet materials from single crystals. However, most of the published research has used micro-scale crystals. The transformation of bulk crystals to micro- or nano-scale structures has rarely been achieved by chemical etching. We report here the preparation of a tetrathiafulvalene (TTF)-grafted titanium-oxo-cluster (TiO–TTF) that can be easily exfoliated at a millimeter scale. This is the first example of a titanium-oxo-cluster successfully combined with a TTF moiety. In an oxygen atmosphere, the red crystal of the TiO–TTF cluster changes to a black ‘crystal’ composed of regularly arranged floorboard-like micro-plates. The exfoliation properties of the material are a result of the easy oxidation of the TTF group and the catalytic properties of the TiO cluster. The TTF moiety in the cluster is not only an oxidation center, but also adds new photoelectroactive properties to the TiO material. An enhanced photocurrent response was observed for the TiO–TTF and TiO–TTF(+) materials.
Co-reporter:Hu-Chao Su, Yin-Yin Wu, Jin-Le Hou, Guang-Ling Zhang, Qin-Yu Zhu and Jie Dai
Chemical Communications 2016 - vol. 52(Issue 21) pp:NaN4075-4075
Publication Date(Web):2016/02/22
DOI:10.1039/C6CC00551A
An organic dye coordinated titanium iso-propoxide compound is designed and synthesized. Taking advantage of the hydrolysis of the titanium alkoxide moiety on the surface of TiO2 electrode, the dye–semiconductor surface properties, including anchoring and dispersivity, are improved, which opens a new perspective to explore dyes for DSSCs.
Co-reporter:Yu-Hong Wang, Jing Wu, Xiao-Wei Zhao, Li-Wen Qian, Qin-Yu Zhu and Jie Dai
Chemical Communications 2015 - vol. 51(Issue 53) pp:NaN10671-10671
Publication Date(Web):2015/06/05
DOI:10.1039/C5CC03404C
Different from the dominating supertetrahedral structure of InSe clusters, co-assembled nano-scale In33Se60 triangular ring clusters and wheel-shaped In18Se30 clusters have been found. The unusual second-sphere coordination templating effect of the Mn(dach) complexes and the central Mn2+ ion is responsible for the formation of the triangular ring. The optical and electronic properties are discussed.
Co-reporter:Sheng Wang, Hu-Chao Su, Lan Yu, Xiao-Wei Zhao, Li-Wen Qian, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2015 - vol. 44(Issue 4) pp:NaN1888-1888
Publication Date(Web):2014/11/19
DOI:10.1039/C4DT02968B
Two 9-anthracenecarboxylate (9-AC) coordinated heterometallic TOC compounds, [Ln2Ti10O14(ClO4)2(OiPr)14(9-AC)2(CH3CN)2]·2H2O, Ln = Nd (1) and Eu (2), along with two benzoate (bza) analogues, [Ln2Ti10O14(ClO4)2(OiPr)14(bza)2(HOiPr)2], Ln = Nd (3) and Eu (4), were prepared by one step in situ solvothermal synthesis, and characterized by single crystal analysis. To date, only about ten lanthanum-titanium oxo clusters have been reported. Except for two Ti28 clusters, the compounds are all small clusters (Ti ≤ 4). The cluster structures of 1–4 adopt a Ti10Ln2 core structure with pseudo-Ci symmetry, which is similar to the fundamental structure of Ti12 clusters. Furthermore, except for their structures, the properties of lanthanum-titanium oxo clusters have never been studied. Herein, the fluorescence properties of these compounds are studied in detail. The metal centered emission of Eu(III) is completely quenched by 9-AC due to the lower triplet energy of the coordinated ligand. Enhanced ligand centered fluorescence is found for 2 in comparison with that of 1.
Co-reporter:Jing Wu, Ya-Yang Pu, Xiao-Wei Zhao, Li-Wen Qian, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2015 - vol. 44(Issue 10) pp:NaN4525-4525
Publication Date(Web):2015/01/21
DOI:10.1039/C4DT03333G
A lot of ternary In–Sb–Q (Q = S, Se) chalcogenido-metalates with amines or complex cations have been recently reported for their diverse structures, however, such a type of In–Sn–Q chalcogenido-metalate has been rarely announced. Herein, we report a series of 2-D In–Sn–Q compounds prepared using a metal–phenanthroline cationic template, [M(Phen)3](In2Sn2Q8)·(amine)·nH2O (M = Ni(II), Fe(II) or Co(II); amine = cyclohexylamine (Cha) or 1,6-diaminohexane (Dah); Q = S or Se). Their anions are isostructural and a 2-D porous network with large 16-tetrahedron-rings. The 2-D network joint of In–Sn–Q is a (In/Sn)3Q3 six-membered ring, which is different from the Sn3Q4 pseudosemicube of most 2-D Sn–Q binary compounds. The materials exhibit photocurrent response properties measured using a photo-electrochemical cell. The result shows that (1) the selenides exhibit more intense photocurrents than the sulfides and (2) the current intensity is related to the metal–phenanthroline cations.
Co-reporter:Jin-Le Hou, Wen Luo, Yin-Yin Wu, Hu-Chao Su, Guang-Lin Zhang, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2015 - vol. 44(Issue 46) pp:NaN19835-19835
Publication Date(Web):2015/10/16
DOI:10.1039/C5DT03153B
Two benzene dicarboxylate (BDC) and salicylate (SAL) substituted titanium-oxo-clusters, Ti13O10(o-BDC)4(SAL)4(OiPr)16 (1) and Ti13O10(o-BDC)4(SAL-Cl)4(OiPr)16 (2), are prepared by one step in situ solvothermal synthesis. Single crystal analysis shows that the two Ti13 clusters take a paddle arrangement with an S4 symmetry. The non-compact (non-sphere) structure is stabilized by the coordination of BDC and SAL. Film photoelectrodes are prepared by the wet coating process using the solution of the clusters and the photocurrent response properties of the electrodes are studied. It is found that the photocurrent density and photoresponsiveness of the electrodes are related to the number of coating layers and the annealing temperature. Using ligand coordinated titanium-oxo-clusters as the molecular precursors of TiO2 anatase films is found to be effective due to their high solubility, appropriate stability in solution and hence the easy controllability.
Co-reporter:Xiao-Lu Sun, Qin-Yu Zhu, Wen-Qin Mu, Li-Wen Qian, Lan Yu, Jing Wu, Guo-Qing Bian and Jie Dai
Dalton Transactions 2014 - vol. 43(Issue 33) pp:NaN12589-12589
Publication Date(Web):2014/06/23
DOI:10.1039/C4DT01289E
As most of the chalcogenidometalate anions are well-known electron-rich systems, design and preparation of ion pair compounds, by integrating an organic acceptor (A) with an inorganic chalcogenidometalate donor (D), are an attractive strategy to obtain new functional materials. We report herein the single-crystal structures and properties of three new ion pair charge-transfer (IPCT) compounds by incorporating thiogermanates with methylviologen (MV2+, N,N′-dimethyl-4,4′-bipyridinium dication), [MV]2Ge4S10·xSol (Sol = solvent). Sharp and fast solvent-induced color changes and switchable fluorescence emission are observed for the compounds. The weak interactions that relate to the solvent and ions in the structures are likely the key points to modulate the cation–anion charge-transfer. A photocurrent response is observed for the photoelectric system of the IPCT compound upon repetitive switching of light on and off.
Co-reporter:Qin-Yu Zhu, Jin-Po Wang, Yu-Rong Qin, Zheng Shi, Qiong-Hua Han, Guo-Qing Bian and Jie Dai
Dalton Transactions 2011 - vol. 40(Issue 9) pp:NaN1983-1983
Publication Date(Web):2011/01/31
DOI:10.1039/C0DT01152E
Though numerous metal–organic frameworks or polymers have been reported, the organic building blocks are usually not redox-active. On the other hand, some mono-, di- or tri-nuclear compounds with tetrathiafulvalene (TTF) have been prepared, although little is known about the coordination polymers combined with paramagnetic metals and organic TTF ligands. We report herein a series of coordination polymers of copper(II) and manganese(II) with TTF dicarboxylate ligand (L). Compound 1, [CuL(2,2-bpy)]n, is a one-dimensional (1-D) coordination polymer with five-coordinated square-pyramidal Cu(II) centers. Mn(II) complex 2, [MnL(2,2-bpy)]n, also takes a 1-D structure, showing a double-bridged mode by carboxylate groups. The 4,4-bipyridine compound 3, [MnL(4,4-bpy)(H2O)]n·CH3CN, takes a 2-D grid network. A zinc(II) compound 4, [ZnL(4,4-bpy)(H2O)]n·CH3CN, isomorphous structure with 3, is also presented. The electrochemical properties of the solid-state compounds were investigated by cyclic voltammetry using surface-modified electrodes. As usually observed in TTF derivatives, two sets of redox-waves were observed. The values of E1/2(1) of compounds 1–4 are in the order of 2(Mn) ≈ 3(Mn) < 1(Cu) < 4(Zn), indicating that the metal coordination can affect the potential shift of the TTF ligand. Weak antiferromagnetic exchanges are observed for compounds 1, 2, and 3.
Co-reporter:Zheng Shi, Qiong-Hua Han, Xin-Yu Li, Ming-Yan Shao, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2011 - vol. 40(Issue 28) pp:NaN7347-7347
Publication Date(Web):2011/06/15
DOI:10.1039/C1DT10353A
A bis(diamino-diamido) tetrathiafulvalene (TTF) derivative H4L2 has been designed and synthesized. Experiments of pH titration reveal that integrating the redox active TTF unit with the diamino-diamido moiety adds new properties to the traditional ligand. Oxidation of the TTF moiety increases the acidity of the amido group, and the coordination of metal ions is also sensitive to the oxidation state of the ligand. This compound is capable of acting as a leaving or accepting ligand for proton and metal ions. The electrochemistry of the protonated TTF derivative of H4L2 was studied in the presence of a series of oxo anions and metal cations. The results indicate that the redox potentials selectively respond to HC2O4− and SO42− anions, and Ni(II) and Cu(II) cations. Solid-state structures of a cation–anion salt H8L2·2SO4·8H2O and a nickel coordination compound [Ni2L2]·2DMF have been characterized by means of X-ray crystallography which are helpful in understanding the inter-ion interactions.
Co-reporter:Jian-Bing Jiang, Guo-Qing Bian, Ya-Ping Zhang, Wen Luo, Qin-Yu Zhu and Jie Dai
Dalton Transactions 2011 - vol. 40(Issue 37) pp:NaN9556-9556
Publication Date(Web):2011/08/17
DOI:10.1039/C1DT10860C
Three anion–cation compounds 1–3 with formula [M(phen)3][Cd4(SPh)10]·Sol (M = Ru2+, Fe2+, and Ni2+, Sol = MeCN and H2O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π⋯π stacking and C–H⋯π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion–cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)3]2+ is enhanced when the cation interacts with the [Cd4(SPh)10]2− anion. The mechanism for the enhancement of photoluminescence has been proposed.
Co-reporter:Zhe-Jun Lu, Jin-Po Wang, Qin-Yu Zhu, Li-Bin Huo, Yu-Rong Qin and Jie Dai
Dalton Transactions 2010 - vol. 39(Issue 11) pp:NaN2803-2803
Publication Date(Web):2010/02/09
DOI:10.1039/B921745B
A new bifunctional tetrathiafulvalene (TTF) derivative has been designed and synthesized, in which the TTF moiety (a redox functional group) is integrated with a dioxotetraamine (a coordination functional group) structure. Like other dioxotetraamine compounds, it is capable of acting as an ion leaving and accepting ligand for protons and Cu(II) and Ni(II) ions in solution. Experiments of pH titration have shown that the TTF unit adds new redox properties to the traditional ligand. Oxidation of the ligand increases the acidity of the imido group and the coordination of metal ions is also sensitive to the oxidation state of the ligand. The ligand forms either a square coordinated Ni(II) complex with two deprotonated imido groups and two amino groups, or a pentacoordinated Cu(II) complex with an additional solvent molecule. The compounds form a belt structure with strong N–H⋯O hydrogen bonds, which is a basic character for this type of compound in the crystalline form.
Co-reporter:Yin-Yin Wu, Peng Wang, Yu-Hong Wang, Jian-Bing Jiang, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2013 - vol. 1(Issue 34) pp:NaN9868-9868
Publication Date(Web):2013/06/13
DOI:10.1039/C3TA11571B
Much attention has been paid to titanium oxo clusters (TOCs) because of their use as model compounds of bulk nanoscale titanium oxides. On the other hand, doping of TiO2 with some metal complexes of 1,10-phenanthroline (phen) or bipyridine (bpy) results in low band-gap materials with high photovoltaic conversion efficiency. In this work, two metal–phenanthroline substituted titanium-oxo-clusters, [Ti17O28(OiPr)16(CoIIphen)2] (C1) and [Ti17O28(OiPr)18(CdIIphen)2] (C2), were successfully prepared by one-step in situ solvothermal synthesis. The structures of the compounds are best described as an oxo-isopropanoxo Ti17 parent fused with two M–phen moieties. They are the first examples of M–phen modified oxo-alkoxy titanium clusters. The band structure of the cluster is modified by the coordination of the metal complex and the absorption of the material is improved. The cluster can not only be used as a model for theoretical study, but can also be used as a precursor to prepare sensitized TiO films. Films (F1) with unique microstructures of hollow spheres, bowls, and doughnuts were obtained by a simple non-template coating method from the solution of Co–phen–TiO cluster C1. The size of the spheres is about 1–2 μm and the thickness of the shell is about 50 nm. Upon repetitive irradiation of the F1 film on the ITO electrode in a three electrode system, a clear photocurrent response was observed. The Co–phen moiety plays an important role in electron transition.
Co-reporter:Jian-Bing Jiang, Peng Huo, Peng Wang, Yin-Yin Wu, Guo-Qing Bian, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2014 - vol. 2(Issue 14) pp:NaN2533-2533
Publication Date(Web):2014/02/25
DOI:10.1039/C3TC32093F
Cadmium chalcogenido C1 (Cd17) CdQ (Q = S, Se) clusters with MV2+ cations (MV = methylviologen) are prepared under solvothermal conditions, using thiourea and selenourea as S and Se sources. The anions ([Cd17Q4(SPh)24Br4]2−) are discrete homosized nano-clusters with about a 1.5 nm scale. The selenide cluster can be considered as a nano-CdSe/CdS core–shell particle with a CdSe4 core and a [Cd16(SPh)24Br4] shell. The electronic spectra show the characteristic peaks of charge transfer bands. Cyclic voltammetry exhibits a low-potential-shift due to the charge transfer from the cadmium chalcogenido cluster to the MV2+ cation. Photocurrent responses of compounds 1 and 2 are studied using a three electrode cell. The results are as follows. (1) The current intensities of the MV–CdQSPh clusters are significantly larger than those of the CdQSPh clusters with quaternary ammonium cations; (2) the photocurrent directions of 1 and 2 can change from positive to negative when the irradiation wavelength is changed from UV light to visible light due to the different photocurrent conversion mechanism. The effect of MV2+ on these properties is discussed.
Co-reporter:Peng Wang, Yin-Yin Wu, Jing Wu, Sheng Wang, Lan Yu, Qin-Yu Zhu and Jie Dai
Journal of Materials Chemistry A 2013 - vol. 1(Issue 47) pp:NaN7978-7978
Publication Date(Web):2013/11/01
DOI:10.1039/C3TC31607F
A gel matrix is an appropriate medium for photoswitchable fluorescent systems, because the gel provides a wet medium for the solvent-related fluorescence emission. Although some studies have been performed on the photoswitchable fluorescence properties of dye-entrapped organo- or inorgano-gels, the gels usually act just as a matrix. We report here a new soft hybrid material, in which the inorganic TiO gel is doped with perylene tetracarboxylate (PTC). The TiO gel not only acts as a wet matrix but, more importantly, also acts as the photoactive switch or shelter. The PTC–TiO solution in ethanol is prepared by solvothermal reaction at 60 °C and 80 °C, respectively. The solution exhibits different colors and different fluorescence emission according to the reaction temperature and time, due to the different assembly of the PTC dye molecules. The solution is then gelated by a typical method for TiO2 gels, giving a material with photoswitchable fluorescence properties. The fluorescence of the perylene moiety can be switched off and on by irradiation and oxygen blowing. The photo-induced Ti(IV)/Ti(III) redox-chromic effect is the most reasonable explanation for the fluorescence emission and extinction, because Ti(III) is detected in the photo-blackened PTC–TiO gel.
Co-reporter:Li-Jun Xue, Peng Huo, Yan-Hong Li, Jin-Le Hou, Qin-Yu Zhu and Jie Dai
Physical Chemistry Chemical Physics 2016 - vol. 18(Issue 4) pp:NaN2948-2948
Publication Date(Web):2015/12/18
DOI:10.1039/C5CP06141E
Great progress has been made in combining a TTF moiety with a porphyrin unit by covalent bonds, but only a few examples were reported in which TTF and porphyrin assembled by noncovalent interactions. In contrast to the energy- and time-consuming synthetic procedures for the covalent system, the assembly of a non-covalent ionic system would be a cost-effective way to construct donor–acceptor ensembles. Herein a new type of ionic TTF–porphyrin dyad is obtained. A methylated tetra(4-pyridyl) porphyrin (5,10,15,20-tetrakis-(N-methyl-4-pyridyl)-porphyrin, TMPyP) is selected as the cation, and TTF-bicarboxylate (L1) or TTF-tetracarboxylate (L2) is used as the anion. Crystal structures of two TTF-TMPyP ionic D–A compounds, TMPyP-(HL1)4·3H2O (1) and TMPyP-(H2L2)2·5H2O (2), were characterized by single-crystal X-ray diffraction. The strong ionic interaction enhances the charge-transfer between the regular mixed-stacking donors and acceptors, which are investigated comprehensively by spectral, electrochemical and theoretical studies. The variation in properties between L1 and L2 is of great advantage to understand the influence factors for charge-transfer. The charge-transfer properties can be modulated not only by the nature of the donor or the acceptor, but also the cation–anion ratio in the salt, which shows great flexibility of the D–A ionic dyad in the design and preparation of new charge-transfer systems.
Co-reporter:Xin-Yu Li, Yong-Gang Sun, Peng Huo, Ming-Yan Shao, Shu-Fang Ji, Qin-Yu Zhu and Jie Dai
Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 11) pp:NaN4023-4023
Publication Date(Web):2013/01/08
DOI:10.1039/C3CP44054K
The complex Et4N[Ni(4-pedt)2] (1) (4-pedt = 1-(pyridine-4-yl) ethylene-1,2-dithiolate) was synthesized to investigate the behaviour of metal dithiolene compounds upon protonation and oxidation by absorption spectroscopy, electrochemistry and structural analyses and to further understand the electronic states of the dithiolene compounds. It is unexpected that the 915 nm NIR transition band is not shifted when H+ is added, and it is only affected (blue-shifted) when the compound is oxidized. All the evidence of electronic spectra indicates that the NIR band is relevant to the central [Ni(edt)2] moiety (edt = ethylenedithiolate), not the behaviour of individual Ni ions or ligands. It is also not the band of intermolecular interaction of a dimer. The moderately intense band appearing at 655 nm upon protonation is assigned to the intramolecular charge-transfer band between the [Ni(edt)2] moiety and the pyridine. The redox potentials of the metal dithiolene are sensitive to the protonation of the pyridyl group. The structures of monocationic complex 1 and the protonated compounds [Ni(4-Hpedt)2]·ClO4·H2O (2) and [Ni(4-Hpedt)2]·PhSO3·2DMF (3) were characterized by single crystal X-ray determination. The structural data demonstrate that the oxidation of the monoanionic dithiolene complex to neutral does not change the Ni–S bond distances obviously, which further indicates that the process is not only the metal centered oxidation.
![1,3-Dithiole-4,5-diacetic acid, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-, sodium salt (1:2)](/data/chemimg/3781600/2049502-43-2.png)
![1,3-Dithiole-4,5-diacetic acid, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-, sodium salt (1:2)](/data/chemimg/3781600/2049502-43-2_b.png)
![Pyridine, 4-[(2E)-2-[4-(4-pyridinyl)-1,3-dithiol-2-ylidene]-1,3-dithiol-4-yl]-](/data/chemimg/3781600/956366-11-3.png)
![Pyridine, 4-[(2E)-2-[4-(4-pyridinyl)-1,3-dithiol-2-ylidene]-1,3-dithiol-4-yl]-](/data/chemimg/3781600/956366-11-3_b.png)
![1,3-Dithiole-4-carboxylic acid,2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-](/data/chemimg/1318300/774578-89-1.png)
![1,3-Dithiole-4-carboxylic acid,2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-](/data/chemimg/1318300/774578-89-1_b.png)
![Pyridine, 4-[2-[4-(4-pyridinyl)-1,3-dithiol-2-ylidene]-1,3-dithiol-4-yl]-](/data/chemimg/3777500/235095-68-8.png)
![Pyridine, 4-[2-[4-(4-pyridinyl)-1,3-dithiol-2-ylidene]-1,3-dithiol-4-yl]-](/data/chemimg/3777500/235095-68-8_b.png)
![1,3-Dithiole-4,5-dicarboxylic acid, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-](/data/chemimg/3781600/850303-71-8.png)
![1,3-Dithiole-4,5-dicarboxylic acid, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-](/data/chemimg/3781600/850303-71-8_b.png)
![1,3-Dithiole-4,5-dicarboxylic acid, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-, sodium salt (1:2)](/data/chemimg/3781600/910635-18-6.png)
![1,3-Dithiole-4,5-dicarboxylic acid, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-, sodium salt (1:2)](/data/chemimg/3781600/910635-18-6_b.png)
