Co-reporter:Zhe-Yu Zhang, Jun Peng, Zhen-Yu Shi, Wan-Li Zhou, Shifa Ullah Khan and Hong-Sheng Liu
Chemical Communications 2015 vol. 51(Issue 15) pp:3091-3093
Publication Date(Web):02 Jan 2015
DOI:10.1039/C4CC09612F
Nine new Sb-bicapped α-Keggin-type heteropolyoxoniobates (HPNb) were synthesized under hydrothermal conditions. Among them, the As-centered HPNb was never reported before, and the two dimer compounds are the biggest isolated HPNbs at present.
Co-reporter:Xia Yu, Jun Peng, Zhenyu Shi, Yan Shen, Zheyu Zhang, Guangzhe Li
Journal of Luminescence 2015 160() pp: 289-292
Publication Date(Web):
DOI:10.1016/j.jlumin.2014.12.022
Co-reporter:Wanli Zhou, Zheyu Zhang, Jun Peng, Xiang Wang, Zhenyu Shi and Guangzhe Li
CrystEngComm 2014 vol. 16(Issue 47) pp:10893-10901
Publication Date(Web):06 Oct 2014
DOI:10.1039/C4CE01409J
This paper reports the preparation and X-ray single crystal structures of five organic–inorganic hybrid compounds with 3D framework, [Cu2.5(bimpy)2(H2O)2][Ln(H2O)3(α-SiW11O39)]·xH2O [Ln = EuIII and x = 3.5 for (1), Ln = SmIII and x = 2.5 for (2), Ln = HoIII and x = 3.5 for (3), Ln = YIII and x = 3.5 for (4), Ln = CeIII and x = 3 for (5)] (bimpy = 3,5-bis(1-imidazolyl)pyridine). Compounds 1–5 are isostructural, showing a 3D framework featured by {–SiW11–Ln–SiW11–}n inorganic chains and {Cu/bimpy} metal–organic ribbons stemmed from Cu2+ ions and bimpy ligands. The adjacent {Cu/bimpy} ribbons are connected by two antiparallel {–SiW11–Eu–SiW11–}n chains to create a 2D layer structure, which is extended to a (3,4,4,4,6)-connected 3D framework with (4·72)(4·6·73·8)(42·53·7)(42·72·92)(42·52·67·83·10) topology through the Cu–O covalent bonds. The magnetic and electrochemical properties of compounds 1 and 2 have been studied.
Co-reporter:Zhenyu Shi, Jun Peng, Xia Yu, Zheyu Zhang, Xiang Wang, Wanli Zhou
Inorganic Chemistry Communications 2014 Volume 41() pp:84-87
Publication Date(Web):March 2014
DOI:10.1016/j.inoche.2014.01.002
•Two new octamolybdate-based hybrids were synthesized hydrothermally.•1 is a 1D chain consisting of dinuclear silver clusters.•2 is a 2D network with tetranuclear copper cluster.Through hydrothermal reactions of d0 metal ions with 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HL), two new octamolybdate-based hybrids, namely, (H2L)2[Ag2(HL)2(β-Mo8O26)] (1) and [Cu4(HL)4(θ-Mo8O26)] · 5H2O (2), have been prepared and structurally characterized. X-ray single-crystal analyses show that compound 1 consists of discrete H2L cations and infinite one-dimensional (1D) anionic chains [Ag2(HL)2(β-Mo8O26)]2 − constructed by [β-Mo8O26]4 − bridged via dinuclear clusters {Ag2(HL)2}2 +. Compound 2 displays a 2D network generated by 1D cationic tetranuclear copper cluster chains {Cu4(HL)4}n and [θ-Mo8O26]4 − clusters. In addition, luminescent properties of both compounds have been studied.Two new octamolybdate-based hybrids have been prepared and structurally characterized. X-ray single-crystal analyses show that 1 consists of infinite 1D anionic chains constructed by [β-Mo8O26]4– bridged via dinuclear silver clusters. 2 displays a 2D network generated by 1D cationic tetranuclear copper cluster chains and [θ-Mo8O26]4–.
Co-reporter:Xia Yu, Changyun Chen, Jun Peng, Zhenyu Shi, Yan Shen, Jilan Mei, Zixing Ren
Thin Solid Films 2014 Volume 571(Part 1) pp:69-74
Publication Date(Web):28 November 2014
DOI:10.1016/j.tsf.2014.09.029
•Composite films have been fabricated by the layer-by-layer self-assembly method.•The films show an electrocatalytic reduction activity for NO2−, BrO3− and ClO3−.•The films show a distinct antibacterial effect against Escherichia coli.Organic–inorganic composite films have been fabricated from polyoxometalate (NH4)5H4PV6Mo6O40·6H2O (PV6Mo6) and Methyl Violet (MV) by the electrostatic layer-by-layer self-assembly method. The multilayer films have been characterized by ultraviolet–visible spectroscopy and atomic force microscopy. The obtained films of (PV6Mo6/MV)n show not only an electrocatalytic activity towards the reduction of NO2−, ClO3− and BrO3−, but also obviously an inhibiting effect on the growth of Escherichia coli.
Co-reporter:Haijun Pang, Carlos J. Gómez-García, Jun Peng, Huiyuan Ma, Chunjing Zhang and Qingyin Wu
Dalton Transactions 2013 vol. 42(Issue 47) pp:16596-16601
Publication Date(Web):10 Sep 2013
DOI:10.1039/C3DT51899J
The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d–4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2]·nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. A structural feature in 1 and 2 is that each [SiW11O39]8− cluster (SiW11) is connected to ten metals (five Ag+ and five Ln3+ cations), representing the highest number of connected metal atoms to any mono-lacunary Keggin anion to date. This large connectivity leads to a structure with a purely inorganic 3D framework with two kinds of channels along the [100] and [010] directions. The magnetic properties of both compounds show the expected magnetic moments (0.8 and 1.6 amu K mol−1 per Ce3+ and Pr3+ ion, respectively) and confirm the presence of isolated Ce3+ and Pr3+ ions.
Co-reporter:Zhen-yu Shi, Zhe-yu Zhang, Jun Peng, Xia Yu and Xiang Wang
CrystEngComm 2013 vol. 15(Issue 36) pp:7199-7205
Publication Date(Web):05 Jul 2013
DOI:10.1039/C3CE41008K
Two new Keggin-based hybrids with polynuclear Cu(I) clusters, formulated as [Cu4(HL)4(SiW12O40)]·6H2O (1) and [Cu6.5(HL)2(L)4(H2O)(H1.5SiW12O40)]·3H2O (2) (HL = 5-(4-imidazol-1-ylphenyl)-2H-tetrazole), have been hydrothermally synthesized and characterized by routine techniques. In 1, Keggin polyanions [SiW12O40]4− (SiW12) link adjacent [Cu4(HL)4]n chains to generate a 2D network. In 2, a cationic (2,3,11)-connected 3D framework, {Cu6.5(HL)2(L)4(H2O)}2.5+, is induced by SiW12 as the template. The differences in the structures of compounds 1 and 2 indicate that pH and the acid radical ions in the initial reaction system play a key role in determining the final structures. Interestingly, the ligand HL in 1 only adopts a μ1,2,3 bridging mode, while in 2, the ligand is in HL/L states and exhibits four different bridging modes: μ1,2,3,4,5, μ1,2,3,5, μ1,2,4,5, and μ1,2,4. The luminescent properties of compounds 1 and 2 have also been investigated. The results show that solvent-dependent luminescence properties can be found in 1. In addition, electrochemistry properties of 1 and 2 have also been studied.
Co-reporter:Zhen-yu Shi, Jun Peng, Yang-guang Li, Zhe-yu Zhang, Xia Yu, Kundawlet Alimaje and Xiang Wang
CrystEngComm 2013 vol. 15(Issue 37) pp:7583-7588
Publication Date(Web):19 Jul 2013
DOI:10.1039/C3CE41312H
Two unusual α-Keggin-based compounds with multinuclear silver clusters, {[Ag7(H2biim)5][PW11O39]}·Cl·H3O (1) and {[Ag2(H2biim)2][Ag(phnz)](PW12O40)}·H2O (2) (H2biim = 2,2′-biimidazole, phnz = phenazine), have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis and X-ray crystallography. Compound 1 displays a 2D network featuring dimerized monolacunary Keggin anions {PW11O39}2 which are connected together through pentanuclear silver clusters. Interestingly, besides {Ag5}5+ clusters, there are another kinds of argentophilic {Ag4}4+ clusters coexisting in compound 1. Compound 2 consists of four subunits: 1D cationic chains [Ag(phnz)]+, dinuclear silver-H2biim units [Ag2(H2biim)2]2+, discrete polyanions {PW12O40}3− and water molecules, which are further joined by hydrogen bonds to form a 3D supramolecular structure. The differences in the structures of compounds 1 and 2 indicate that the introduction of the secondary organic ligand plays a key role in determining the final structure. The electrochemical, electrocatalytic behaviors and luminescent properties of compounds 1 and 2 have also been investigated.
Co-reporter:Yun-lei Teng, Bao-xia Dong, Jun Peng, Shi-yang Zhang, Lu Chen, Liang Song and Jun Ge
CrystEngComm 2013 vol. 15(Issue 15) pp:2783-2785
Publication Date(Web):26 Nov 2012
DOI:10.1039/C2CE26719E
Introducing of mixed flexible and rigid achiral ligands into the hexadecavanadate skeleton leads to the isolation of two enantiomerically 3D chiral hexadecavanadate derivatives, which represent the first example of chiral polyoxometalate-based framework functionalized with mixed flexible and rigid achiral ligands.
Co-reporter:Xia Yu, Huanqiu Zhang, Zhenyu Shi, Kundawlet Alimaje, Yan Shen, Jun Peng, Bin Li, Liming Zhang
Dyes and Pigments 2013 Volume 98(Issue 3) pp:479-485
Publication Date(Web):September 2013
DOI:10.1016/j.dyepig.2013.03.020
•Three new dye-doped inorganic-organic hybrid SiMW11-F microtubes have been obtained.•These microtubes exhibit different luminescent emission properties from fluorescein.•The POM components exhibit an inhibiting effect on photobleaching of fluorescein.Three new dye-doped inorganic-organic hybrid microtubes, SiMW11-F (M = W, Mo and V; F = fluorescein), have been obtained and characterized by X-ray diffraction, ultraviolet/visible spectroscopy, elemental analysis, thermogravimetric analysis. Comparative studies have been carried out on fluorescent properties of the three SiMW11-F microtubes and fluorescein. These fluorescent hybrid microtubes exhibit luminescent emission properties which are different from raw material fluorescein in the blue spectral region, which is suggests that different luminescence centers may be formed in the hybrid microtubes. The SiW12-F and SiMoW11-F microtubes show more similar fluorescent properties than the SiVW11-F microtubes, due to the differences in ionic radius and oxidation state between W/Mo and V. Furthermore, the three polyoxometalate components in the microtubes exhibit an inhibiting effect on photobleaching of fluorescence dye in the reaction system.
Co-reporter:Zhenyu Shi, Jun Peng, Zheyu Zhang, Xia Yu, Kundawlet Alimaje, Xiang Wang
Inorganic Chemistry Communications 2013 Volume 33() pp:105-108
Publication Date(Web):July 2013
DOI:10.1016/j.inoche.2013.04.013
•Two 3D Dawson-based hybrids were synthesized and characterized.•1 consists of infinite organic-metal chains {Ag6(HL)4}n.•2 is a 3D (3,6)-connected framework with 43(4866827124) topology.•The luminescent properties of both compounds were investigated.Two new Dawson-based hybrids, namely, [Ag6(H L)4(H2O)6(P2W18O62)]·4H2O (1) and [Ag4(H2biim)4][K2(H2O)3(P2W18O62)]·H2O (2) (HL = 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole, H2biim = 2,2′-biimidazole), have been hydrothermally synthesized and characterized. X-ray diffraction analysis reveals that compound 1 is a 3D structure based on infinite organic–metal chains {Ag6(HL)4}n and Wells–Dawson anions. Compound 2 displays a 3D framework based on potassium-Dawson inorganic sheets and dinuclear silver-H2biim units. The luminescent properties of compounds 1 and 2 have also been investigated.Two new POM-based hybrids (POM = polyoxometalate), namely, [Ag6(H L)4(H2O)6(P2W18O62)]·4H2O (1) and [Ag4(H2biim)4][K2(H2O)3(P2W18O62)]·H2O (2) (HL = 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole, H2biim = 2,2′-biimidazole), have been hydrothermally synthesized and characterized. X-ray diffraction analysis reveals that compound 1 is a 3D structure based on infinite organic-metal chains {Ag6(HL)4}n and Wells–Dawson anions. Compound 2 displays a 3D framework based on potassium-POM inorganic sheets and dinuclear silver-H2biim units.
Co-reporter:Xiang Wang, Jun Peng, Kundawlet Alimaje, Zheyu Zhang, Zhenyu Shi
Inorganic Chemistry Communications 2013 Volume 36() pp:141-145
Publication Date(Web):October 2013
DOI:10.1016/j.inoche.2013.08.038
•Two Keggin POM-based hybrids composed of CuI/tbz segments are synthesized.•The polyoxoanions and configurations of tbz ligand play the key roles in inducing structures.•The electrochemical properties of two compounds are investigated.Two Keggin polyoxoanion-based hybrid compounds composed of CuI/tbz segments [CuI2(tbz)2][CuI(tbz)2(PMoVI10Mo2VO40CuI2)] (1) and [CuI2(tbz)3][CuI (tbz)2](PW12O40) (2), have been hydrothermally synthesized. In compound 1, a 3D supramolecular framework with 2D channels is constructed from a novel cap-to-cap {CuI(tbz)2(PMoVI10Mo2VO40CuI2)}2 −n chain via hydrogen bonding and π–π interactions, in which {CuI2(tbz)2}2 + segments are incorporated. Compound 2 is composed of one discrete PW12 polyoxoanion, one {CuI(tbz)2}+ segment and one {CuI2(tbz)3}2 + segment, displaying a 3D supramolecular structure through hydrogen bonding and π–π interactions. The results indicate that the polyoxoanions and configurations of tbz ligand play the key roles in the self-assembly processes. The electrochemical properties of compounds 1 and 2 have been investigated.Two Keggin POM-based hybrids composed of CuI/tbz segments are synthesized. The polyoxoanions and configurations of tbz ligand play the key roles in forming structures.
Co-reporter:Zhenyu Shi, Jun Peng, Xia Yu, Yan Shen, Zheyu Zhang, Kundawlet Alimaje, Xiang Wang
Inorganic Chemistry Communications 2013 Volume 28() pp:85-89
Publication Date(Web):February 2013
DOI:10.1016/j.inoche.2012.10.040
A new 3D Keggin-based metal–organic framework consisting of two kinds of Cu-H2biim chains, Cu10(H2biim)10(PW12O40)2(OH)4·5H2O 1 (H2biim = 2,2′-biimidazole), has been synthesized under hydrothermal conditions. The TGA and PXRD measurements show that the framework is stable after removal of the guest water molecules. In addition, the luminescent and electrochemical properties of 1 have also been investigated.A new 3D Keggin-based metal–organic framework with Cu···Cu interactions has been synthesized under hydrothermal conditions. Interestingly, two kinds of Cu-H2biim (H2biim = 2,2′-biimidazole) chains coexist in compound 1, which are linked together through polyanions.Highlights► A new 3D Keggin-based metal-organic framework has been synthesized. ► Two kinds of of Cu-H2biim chains with Cu(I)···Cu(I) interactions coexist. ► The luminescent and electrochemical properties of 1 have also been investigated.
Co-reporter:Kundawlet Alimaje;Xiang Wang;Zhe-Yu Zhang
Journal of Cluster Science 2013 Volume 24( Issue 4) pp:1021-1030
Publication Date(Web):2013 December
DOI:10.1007/s10876-013-0594-z
Two bisupporting Keggin-type polyoxoanion-based hybrids decorated by [Zn(phen)2]2+ complexes, [Zn(phen)2]2(PW11VIWVO40) (1) and K[Zn(phen)2(H2O)]2(OH) (SiW12O40)·H2O (2) (phen = 1,10′-phenanthroline), have been hydrothermally synthesized, and characterized by elemental analysis, IR spectra, UV–Vis spectrum, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, and single-crystal X-ray diffraction. The structural analyses reveal that compound 1 consists of a 0D bisupporting Keggin-type heteropoly blue cluster obtained by using reductant glucose, which is grafted by two [Zn(phen)2]2+ fragments; compound 2 presents a 1D infinite chain, which is constructed from bisupporting [SiW12O40]4− polyoxoanions decorated by [Zn(phen)2(H2O)]2+ fragments and K+ ions. Additionally, the electrochemical behaviors of two compounds were studied.
Co-reporter:Huanqiu Zhang, Jun Peng, Yan Shen, Xia Yu, Fang Zhang, Jilan Mei, Bin Li and Liming Zhang
Chemical Communications 2012 vol. 48(Issue 37) pp:4462-4464
Publication Date(Web):15 Mar 2012
DOI:10.1039/C2CC00132B
Fluorescent microtubes based on α-Keggin tungstosilicate and fluorescein (SiW12-F) have been obtained by using a simple method, which present tunable photoluminescence from sky blue to green to red by variation of excitation light. The SiW12 component can inhibit photobleaching of fluorescein.
Co-reporter:Yan Shen ; Jun Peng ; Huanqiu Zhang ; Xia Yu ;Alan M. Bond
Inorganic Chemistry 2012 Volume 51(Issue 9) pp:5146-5151
Publication Date(Web):April 23, 2012
DOI:10.1021/ic2027412
The synthesis and characterization of microtubes of SiMoW11 Keggin polyoxometalates containing either an Mo(V) or Mo(VI) atom is reported. The introduction of a Mo atom into the Keggin-type tungstosilicate microtubes endows them with new properties. The Mo-substituted microtubes may exert both W and Mo functionalities in electrocatalytic reactions and in the immobilization of noble metal nanoparticles. The degree of reduction of the Mo component in the SiMoW11 microtubes is controllable simply by tuning the amount of reductant present in the mother liquor. Mo-substituted Keggin tungstosilicate microtubes in their reduced state are more stable than the all-tungsten Keggin tungstosilicate heteropoly blue microtubes.
Co-reporter:Xiang Wang, Jun Peng, Ming-Guan Liu, Dan-Dan Wang, Cui-Li Meng, Yang Li and Zhen-Yu Shi
CrystEngComm 2012 vol. 14(Issue 9) pp:3220-3226
Publication Date(Web):06 Mar 2012
DOI:10.1039/C2CE06577K
By changing the polyoxoanions in the same metal–organic system (Ag/ptz), two novel inorganic–organic hybrids: [Ag10(ptz)5(HP2W18O62)(H2O)4]·2H2O (1), [Ag7(ptz)5(H2SiW12O40)(H2O)] (2) (ptz = 5-(4-pyridyl)-tetrazolate), are synthesized under hydrothermal conditions, and characterized by IR spectra, elemental analyses and single crystal X-ray diffraction. Compound 1 and 2 show 3D POM-templated framework structures. In compound 1, a 2D layer is constructed by “shield-like” metal–organic circles templated by P2W18 polyoxoanions, which is extended to a 3D structure by covalent bonds in an interdigital mode. In compound 2, a 3D network is constructed by 2D layers and a “double bridge-pillar”, the Keggin polyoxoanion templates are enveloped in pairs in nanocages. The influences of polyoxoanion templates on the frameworks are discussed. The electrochemical behavior and luminescent properties for compound 1 and 2 are investigated.
Co-reporter:Ming-guan Liu, Peng-peng Zhang, Jun Peng, Hua-xin Meng, Xiang Wang, Min Zhu, Dan-dan Wang, Cui-li Meng, and Kundawlet Alimaje
Crystal Growth & Design 2012 Volume 12(Issue 3) pp:1273-1281
Publication Date(Web):December 20, 2011
DOI:10.1021/cg2012809
Five organic–inorganic hybrids containing mixed–valence multinuclear copper complexes and Keggin polyoxometalates, [CuI5CuII3(ptz)8(H2O)][HSiW12O40] (1), [CuI10CuII2(ptz)8(Cl)3][PW12O40] (2), [CuI2CuII4(ptz)6(OH)(H2O)2][PW12O40]·2H2O (3), CuI2CuII5(ptz)6(OH)2SiW12O40·6H2O (4), and [CuI2CuII5(ptz)6][PMoV3MoVI9O40]·8H2O (5) (ptz = 5-(2-pyridyl)-tetrazole), were hydrothermally synthesized and structurally characterized. Compound 1 exhibits a three-dimensional (3D) network that features unprecedented double chains consisting of tetranuclear Cu clusters. Compound 2 displays a 3D network that has unusual Cl-centered hexanuclear Cu clusters and Cl-bridged tetranuclear Cu units. Compound 3 shows a 3D supramolecular network extended by two-dimensional (2D) grid-like sheets which are composed of mixed-valence multinuclear copper chains and PW12 polyanions. Isostructural compounds 4 and 5 exhibit a 3D network consisting of 2D ladder-like copper–ptz layers and SiW12 (PMo12 in 5) polyanions. The roles of copper ions with different oxidation states and ptz ligands with different coordination modes in the construction of the copper–ptz frameworks are discussed. Their electrochemical properties were investigated as well.
Co-reporter:Xiang Wang, Jun Peng, Kundawlet Alimaje and Zhen-Yu Shi
CrystEngComm 2012 vol. 14(Issue 24) pp:8509-8514
Publication Date(Web):04 Oct 2012
DOI:10.1039/C2CE26193F
By altering the functional groups of tetrazolate ligands in the same Ag–POM reaction system, two novel inorganic–organic hybrids: [Ag7(L1)4(H2O)(PMo12O40)] (1) and [Ag5(L2)2(PMo12O40)]·H2O (2) (HL1 = 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole, HL2 = 5-(4-triazol-1-ylmethyl-phenyl)-2H-tetrazole), have been synthesized under hydrothermal conditions, which are characterized by single crystal X-ray diffraction, IR spectra and elemental analyses. Compounds 1 and 2 both display POM-based 3D frameworks modified by different Ag–tetrazolate motifs. In compound 1, a beautiful POM-inserted 2D network is formed by {Ag6(L1)4}n chains and POM polyoxoanions, which are linked to each other through covalent bonds into a (6,6,10)-connected 3D framework. The 3D framework of compound 2 is constructed from chains of circle-connecting-circle and dimeric polyoxoanions. The different structural features of the two compounds suggest that the functional groups of tetrazolate ligands should play a key role in the process of assembly. The luminescent properties for compounds 1 and 2 are investigated.
Co-reporter:Xiang Wang, Jun Peng, Kundawlet Alimaje, Zhenyu Shi
Inorganic Chemistry Communications 2012 Volume 25() pp:5-9
Publication Date(Web):November 2012
DOI:10.1016/j.inoche.2012.09.003
A Wells–Dawson type polyoxoanion-based hybrid compound, Cu9(μ2-OH)4(μ3-OH)2(H2O)8(Hptz)8(P2W18O62)2·30H2O (ptz = 5-(4-pyridyl)-tetrazolate) (1), has been hydrothermally synthesized and characterized by routine methods. In compound 1, a novel nonanuclear copper cluster is constructed from two tetranuclear [Cu4(μ2-OH)(μ3-OH)(Hptz)3]6 + moieties, linked to each other though one Cu4 ion with the aid of two μ2-OH and two ptz ligands. Then the P2W18 polyoxoanions bridge the nonanuclear copper clusters into a 1D ladder-like chain, in which the polyoxoanions and nonanuclear clusters act as two sides and middle rail of the ladder, respectively. The 1D chain is extended to a 3D supramolecular structure via hydrogen bonding interactions. The electrochemical property and magnetic behavior of compound 1 have been studied.A Wells–Dawson polyoxoanion-based hybrid compound, containing a novel nonanuclear copper cluster, Cu9(μ2-OH)4(μ3-OH)2(H2O)8(Hptz)8(P2W18O62)2·30H2O was synthesized. The electrochemical property and magnetic behavior of compound 1 were investigated.Highlights► A new nonanuclear copper cluster was obtained. ► The Wells-Dawson polyoxoanions linked the copper clusters into a 1D chain. ► Electrochemical properties and magnetic behavior of the compound were investigated.
Co-reporter:Xiang Wang, Jun Peng, Dandan Wang, Mingguan Liu, Cuili Meng, Aixiang Tian, Kundawlet Alimaje, Zhenyu Shi
Inorganica Chimica Acta 2012 Volume 392() pp:160-164
Publication Date(Web):30 September 2012
DOI:10.1016/j.ica.2012.07.011
Two POM-tuned hybrids containing tripodal star-like ligand copper complexes, [CuII3(H2O)5(tib)2(P2Mo5O23)]·2H2O (1) and [CuI2(Htib)2(PMo11VIMoVO40)]·H2O (2) (tib = 1,3,5-tris(1-imidazolyl)benzene), have been hydrothermally synthesized. In compound 1, a 2D wave-like layer is constructed from concave belts bridged by P2Mo5 polyoxoanions in a “hand-in-hand” mode, extending to a 3D supramolecular framework via hydrogen bonding interactions. Compound 2 shows a 1D ladder-like chain formed by [Cu(tib)] chains acting as two sides of the ladder and PMo12 anions acting as middle rails, resulting in a 3D supramolecular structure through hydrogen bonding interactions. The steric hindrance of polyoxoanions, the valence states of copper ions and the coordination modes of tib ligands co-affect together the final structures of title compounds. The electrochemical properties of compounds 1 and 2 are investigated.Graphical abstractTwo polyoxomolybdate-tuned hybrids modified by tripodal star-like ligand copper complexes are successfully synthesized. The steric hindrance of polyoxoanions, the valence states of copper ions and the linking modes of tib ligands co-affect the final structure of compounds. The electrochemical properties of the title compounds are also investigated.Highlights► Two POM-based hybrids containing tripodal star-like ligand copper complexes are obtained. ► The factors of affecting the final structures of compounds are discussed. ► The electrochemistry properties of the title compounds are investigated.
Co-reporter:Yan Shen, Jun Peng, Huanqiu Zhang, Changyun Chen, Fang Zhang and Alan M. Bond
Journal of Materials Chemistry A 2011 vol. 21(Issue 19) pp:6995-6998
Publication Date(Web):06 Apr 2011
DOI:10.1039/C1JM10114E
Silver nanoparticles (NPs)-deposited tungstosilicate (Ag/SiW12/Ag) microtubes were obtained by a redox reaction between the heteropoly blue microtubes and Ag+ ions. The Ag/SiW12/Ag microtubes were characterized by FT-IR and XPS spectroscopy. Their morphology was examined by ESEM-FEG, showing that the microtubes kept their original microtubular morphology well after reacting with Ag+ ions and the silver NPs exhibited regular spherical morphology. The current–voltage properties of the Ag/SiW12/Ag microtubes were also briefly investigated.
Co-reporter:Hai-jun Pang, Hui-yuan Ma, Jun Peng, Chun-jing Zhang, Peng-peng Zhang and Zhong-min Su
CrystEngComm 2011 vol. 13(Issue 23) pp:7079-7085
Publication Date(Web):06 Oct 2011
DOI:10.1039/C1CE05648D
Three new compounds, [Cu(bimb)]2(HPW12O40)·3H2O (1), (H2bimb)2SiW12O40 (2) and (H2bimb)3CoW12O40 (3) (bimb = 1,4-bis(imidazol-1-ylmethyl)biphenyl), have been synthesized under the same hydrothermal conditions. Structural characterizations by single-crystal X-ray diffraction show that compound 1 possesses a porous metal–organic pseudo-rotaxane framework in which [PW12O40]3−clusters are encapsulated, whereas compounds 2 and 3 are common supramolecular compounds. The distinct structure of compound 1 suggests that the porous framework may selectively encapsulate the polyoxometalate clusters, although the three polyoxometalate clusters have subtle structural differences. Catalytic photodegradation of organic dye RhB by compounds 1–3 has been studied.
Co-reporter:Peng-peng Zhang, Jun Peng, Hai-jun Pang, Jing-quan Sha, Min Zhu, Dan-dan Wang and Ming-guan Liu
CrystEngComm 2011 vol. 13(Issue 11) pp:3832-3841
Publication Date(Web):05 Apr 2011
DOI:10.1039/C1CE05093A
By introducing different polyoxotungstates into the Ag–H2biim system, four new compounds with distinct architectures, Ag2(H2biim)4(W6O19)·2H2O (1), Ag6(H2biim)6(SiW12O40)(OH)2·2H2O (2), Ag6(H2biim)6(PW12O40)(OH)3·H2O (3) and Ag6(H2biim)6(P2W18O62)·12H2O (4) (H2biim = 2,2′-biimidazole), have been hydrothermally synthesized, and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, the Lindqvist type polyoxotungstate {W6} combines with the chelate Ag–H2biim complex forming a discrete “dumbbell-like” motif. Isostructural compounds 2 and 3 are obtained by introducing Keggin polyoxotungstates ({SiW12} and {PW12}, respectively), which show a 2D layer structure. The 2D layers parallel each other to form a 3D supramolecular framework. The larger Wells–Dawson polyoxotungstate {P2W18} directs the formation of compound 4, in which one 2D layer is the inversion of the neighboring ones. Furthermore, there exist infinite Ag chains in compounds 2–4, which are quite unusual in POM-based compounds. The distinction among the final four architectures is ascribed to the structure-directing effect of different polyanions. The electrochemical properties of compounds 1–4 are studied. In addition, the antibacterial properties of the four compounds against negative Escherichia coli (E. coli) and positive Staphylococcus aureus are investigated.
Co-reporter:Peng-peng Zhang, Jun Peng, Hai-jun Pang, Jing-quan Sha, Min Zhu, Dan-dan Wang, Ming-guan Liu, and Zhong-min Su
Crystal Growth & Design 2011 Volume 11(Issue 7) pp:2736
Publication Date(Web):May 9, 2011
DOI:10.1021/cg1012445
A new compound based on the Wells–Dawson polyoxometalate, Ag7(bbi)5(OH)(P2W18O62) (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (1), has been hydrothermally synthesized and characterized by the normal physical methods and single-crystal X-ray diffraction. Compound 1 represents the first interpenetrating framework based on the Wells–Dawson POMs. The AgI···AgI interactions are crucial in the formation of the two individual motifs: in the first interpenetrating motif, the supported {Ag2}2+ dimers and the P2W18 polyanions form an infinite inorganic chain, then the Ag+ monomers and bbi ligands extend the chain to form a three-dimensional framework. The second motif is constructed by the Ag–bbi meso-helix chains which are stitched by the unsupported Ag7···Ag7 dimers to form a two-dimensional layer with huge loops. The electrochemical study exhibits that compound 1 could be used as electrocatalyst in the electrical reductions of bromate. In addition, compound 1 shows a photocatalytic action for degradation of RhB.
Co-reporter:Dan-dan Wang, Jun Peng, Hai-jun Pang, Peng-peng Zhang, Xiang Wang, Min Zhu, Yuan Chen, Ming-guan Liu, Cui-li Meng
Inorganica Chimica Acta 2011 Volume 379(Issue 1) pp:90-94
Publication Date(Web):15 December 2011
DOI:10.1016/j.ica.2011.09.032
Two isostructural Keggin-templated compounds containing a chair-like heptanuclear silver complex, [{Ag7(Hbtz)2(btz)4}{PM12O40}]·H2O (M = W, 1; Mo, 2) (Hbtz = benzotriazolate), have been hydrothermally synthesized and characterized by routine methods and single crystal X-ray diffraction. In the compounds 1 and 2, the Hbtz ligands present two types of coordination modes. A pentameric silver chain with two kinds of Ag⋯Ag weak interactions exists in the heptanuclear silver complex. The heptanuclear silver cations connect the polyoxoanions PM12O403− to a two-dimensional layer, and the adjacent layers are fused together by the pseudo wave-like chains, H-bonds and AgI–π interactions, constructing a three-dimensional net. Furthermore, electrochemical properties have been studied for compounds 1 and 2 and the two compounds display excellent electrocatalytic activities to the reduction of nitrite.Graphical abstractKeggin polyoxometalate-templated chair-like heptanuclear silver complex.Highlights► A chair-like heptanuclear silver complex is directed by POM templates. ► The {Ag7}3+ cation acts a synthon in construction of 3D structure. ► Compounds 1 and 2 exhibit electrocatalytic activity to the reduction of nitrite.
Co-reporter:Kundawlet Alimaje, Mingguan Liu, Jun Peng, Pengpeng Zhang, Xiang Wang, Min Zhu, Dandan Wang, Cuili Meng
Inorganic Chemistry Communications 2011 Volume 14(Issue 8) pp:1209-1211
Publication Date(Web):August 2011
DOI:10.1016/j.inoche.2011.04.020
A new Cu-Nb mixed complex, [{Cu2(phen)4(μ-O)2(NbF4)2}(μ-F)][NbF6] (1) (phen = 1,10-phenanthroline), was hydrothermally synthesized, and characterized by elemental analyses, IR spectra, thermogravimetric analysis and single crystal X-ray diffraction. Compound 1 exhibits a discrete barbell-like copper cluster with {(μ-F)[(μ-O)2(NbF4)2]} fragment as the handle bar, and [NbF6]− is a counter-anion. Fluorescent property, solubility, and electrochemical property of compound 1 were studied.Graphical abstractA new Cu and Nb mixed complex which exhibits a discrete barbell-like copper cluster with {(μ-F)[(μ-O)2(NbF4)2]} fragment as the handle bar was hydrothermally synthesized.Research highlights► A new Cu and Nb mixed complex was hydrothermally synthesized. ► The complex exhibits a discrete barbell-like tetrametallic cluster. ► The complex has strong fluorescence.
Co-reporter:Yan Shen, Jun Peng, Changyun Chen, Huanqiu Zhang, Cuili Meng, Xinglin Li
Inorganic Chemistry Communications 2011 Volume 14(Issue 1) pp:221-224
Publication Date(Web):January 2011
DOI:10.1016/j.inoche.2010.10.027
Metal ions doped polyoxometalate (POM) microtubes (M–SiW12; M = Zn2+, Cd2+) have been synthesized in aqueous solution by a simple method. The microtubes were characterized by FT-IR, UV/Vis, XPS, elemental analysis, and their morphology was examined by ESEM-FEG. The Zn2+ or Cd2+ doped in POM microtubes were chelated with 8-hydroxyquinoline, to obtain novel POM microtubes (MQ2–SiW12) with fluorescence.The Zn2+ and Cd2+ doped 12-tungstosilicate microtubes (Zn–SiW12 and Cd–SiW12) have been obtained from aqueous solution by a simple method, and the obtained microtubes exhibited intense fluorescence after further modifying by 8-hydroxyquinoline.Research Highlights►The Zn2+ and Cd2+ ions doped POM microtubes were synthesized. ► The doped Zn2+ and Cd2+ ions were chelated with 8-hydroxyquinoline. ► The obtained MQ2–SiW12 microtubes maintained the microtubular morphology. ► The obtained MQ2–SiW12 microtubes exhibited intense fluorescence.
Co-reporter:Min Zhu, Jun Peng, Hai-Jun Pang, Peng-Peng Zhang, Yuan Chen, Dan-Dan Wang, Ming-Guan Liu, Yong-Hui Wang
Journal of Solid State Chemistry 2011 Volume 184(Issue 5) pp:1070-1078
Publication Date(Web):May 2011
DOI:10.1016/j.jssc.2011.03.030
Three new high dimensional CuI/Ag–pz porous coordination polymers (PCPs) with different Keggin polyoxometalate templates have been hydrothermally synthesized: [CuI5(pz)6Cl][HPMoVI10MoV2O40] (1) [Ag5(pz)7(BW12O40)] (2) and [CuI5(pz)6H(H2W12O40)]·4H2O (3) (pz=pyrazine). The choice of the particular Keggin POM templates is shown to influence the structural properties of the Cu/Ag PCPs. Compound 1 shows a Cl-bridged Cu–pz–Cl double layer, between which two kinds of [HPMoVI10MoV2O40]4−(PMo12) polyanions are located. Compound 2 presents a 3D Ag–pz framework with parallelogram-like voids, into which BW12O405− (BW12) Keggin ions are incorporated. Compound 3 contains a Cu–pz cationic layer framework, between which are located [H(H2W12O40)]5− (W12) Keggin ions. Primary photocatalytic experiment indicates that compound 1 presents excellent photocatalytic activity. The photoluminescence properties and electrochemistry properties of the compounds are also discussed.Graphical abstractThe choice of the particular Keggin template is shown to influence the structural properties of the Cu/Ag PCPs. Their photocatalytic activities have been studied.Highlights► In this paper, three Keggin POM-templated metal-pyrazine frameworks are reported. ► The choice of template can influence the structural properties of the frameworks. ► Further, compound 1 exhibits excellent photocatalytic activity.
Co-reporter:Dan-dan Wang, Jun Peng, Peng-peng Zhang, Xiang Wang, Min Zhu, Ming-guan Liu, Cui-li Meng, Kundawlet Alimaje
Inorganic Chemistry Communications 2011 Volume 14(Issue 12) pp:1911-1914
Publication Date(Web):December 2011
DOI:10.1016/j.inoche.2011.09.009
A novel double-Dawson-anion-templated, triangular trinuclear Cu-trz unit-based metal–organic framework [CuII8(trz)6(μ3-O)2(H2O)12][P2W18O62]·4H2O (1) (Htrz = 1,2,4-triazole), has been hydrothermally synthesized and characterized by routine methods. Compound 1 is the first example of the Cu3-triad triangular unit-based three-dimensional (3D) metal–organic framework templated by double [P2W18O62]6− polyoxoanions. Furthermore, the electrochemical property of compound 1 has been studied.A beautiful metal–organic framework with mango-like 1D channels is based on Cu3-triad triangular units and templated by double Wells–Dawson anions.Highlights► A beautiful 3D metal organic framework with mango-like 1D channels is constructed from Cu3-triad triangular unit. ► The first example of trinuclear triangular CuII-trz unit-based MOFs with Dawson-type polyoxoanions as a double-template. ► The electrochemical behavior is also studied.
Co-reporter:Dr. Yan Shen; Jun Peng;Dr. Haijun Pang;Dr. Pengpeng Zhang;Dan Chen;Changyun Chen;Huanqiu Zhang;Cuili Meng ; Zhongmin Su
Chemistry - A European Journal 2011 Volume 17( Issue 13) pp:3657-3662
Publication Date(Web):
DOI:10.1002/chem.201001837
Abstract
In this paper, the preparation of ascorbic acid (AA)-doped polyoxometalate (SiW12-AA) microtubes is described. The SiW12-AA microtubes convert to heteropoly blue microtubes upon exposure to ammonia gas, which is an ammonia-triggered solid–solid redox reaction between AA molecules and polyoxometalates, and can possibly be applied to a chemical sensor for detecting ammonia and volatile organic amines. Furthermore, the SiW12-AA microtubes have been applied to the in situ synthesis of Ag nanoparticles (NPs) through the redox reaction between the AA component and Ag+ ions occurring on the surfaces of the SiW12-AA microtubes to give silver NPs immobilized on polyoxometalate microtubes (Ag@SiW12).
Co-reporter:Min Zhu, Jun Peng, Hai-Jun Pang, Peng-Peng Zhang, Yuan Chen, Dan-Dan Wang, Ming-Guan Liu, Yong-Hui Wang
Inorganica Chimica Acta 2011 370(1) pp: 260-264
Publication Date(Web):
DOI:10.1016/j.ica.2011.01.073
Co-reporter:Hai-jun Pang, Jun Peng, Chun-jing Zhang, Yang-guang Li, Peng-peng Zhang, Hui-yuan Ma and Zhong-min Su
Chemical Communications 2010 vol. 46(Issue 28) pp:5097-5099
Publication Date(Web):15 Jun 2010
DOI:10.1039/C003048A
A novel compound, [Cu(bimb)]2(HPW12O40)·3H2O (bimb = 1,4-bis(imidazol-1-ylmethyl)biphenyl) with a polyoxometalate-encapsulated 3D metal–organic pseudo-rotaxane framework that can be described as a 2-fold dianet topology showing well-defined 1D nano-scale tunnels, has been synthesized hydrothermally, and its de-/rehydration behavior has been investigated.
Co-reporter:Ai-xiang Tian, Jun Ying, Jun Peng, Jing-quan Sha, Zhong-min Su, Hai-jun Pang, Peng-peng Zhang, Yuan Chen, Min Zhu and Yan Shen
Crystal Growth & Design 2010 Volume 10(Issue 3) pp:1104-1110
Publication Date(Web):February 3, 2010
DOI:10.1021/cg900806k
Three inorganic−organic hybrids based on polyoxometalate (POM), [Cu6(bbtz)6(HPM12O40)]·2H2O (M = Mo, 1; W, 2) and [Cu6(trz)2(bbtz)2(SiW12O40)] (3) (trz = 1-H-1,2,4-triazole, bbtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), were synthesized under hydrothermal conditions, and structurally characterized. Through the use of the flexible ligand bbtz, isostructural compounds 1 and 2 with interpenetrating structures were obtained. In compound 1, ladder-like chains exist, in which the PMo12 anions act as “middle rails”. These chains are linked by wave-like [Cu(bbtz)]nn+ lines to construct a three-dimensional (3D) framework. Two such frameworks penetrate each other to construct a 2-fold interpenetrating structure. By introducing the rigid ligand trz, compound 3 with an un-interpenetrating structure is obtained. In compound 3, two-dimensional (2D) (63)2 metal organic framework (MOF) layers exist, which are linked by Keggin anions to construct a 3D (44·62)(63)2 framework. The differences between these compounds should be ascribed to the introduction of the rigid molecule trz that plays a role in restraining the formation of interpenetrating structures.
Co-reporter:Peng-peng Zhang, Jun Peng, Hai-jun Pang, Yuan Chen, Min Zhu, Dan-dan Wang, Ming-guan Liu, Yong-hui Wang
Inorganic Chemistry Communications 2010 Volume 13(Issue 12) pp:1414-1417
Publication Date(Web):December 2010
DOI:10.1016/j.inoche.2010.08.004
Co-reporter:Min Zhu, Jun Peng, Hai-Jun Pang, Peng-Peng Zhang, Yuan Chen, Dan-Dan Wang, Ming-Guan Liu, Yong-Hui Wang
Inorganica Chimica Acta 2010 Volume 363(Issue 14) pp:3832-3837
Publication Date(Web):25 November 2010
DOI:10.1016/j.ica.2010.07.027
Two new Keggin polyoxometalate-based compounds, [Ag4(phnz)6(SiW12O40)] (phnz = phenazine) (1) and [Ag(phnz)1.5][Ag(phnz)(pz)][{Ag2(phnz)(pz)(H2O)}(SiW12O40)] (2) (pz = pyrazine), have been hydrothermally synthesized. Compound 1 is a discrete cluster in which the [SiW12O40]4− (SiW12) anion symmetrically connects two dinuclear Ag2(phnz)3 fragments. All AgI in 1 adopt a trigonal geometry. By introducing the secondary bridging ligand “pz” into the above system, compound 2 was obtained. Compound 2 contains three kinds of silver complex subunits: [Ag2(phnz)(pz)(H2O)]2+, [Ag2(phnz)3]2+ and [Ag(phnz)(pz)]+. The first one extends to a wave-like chain with SiW12 anions as bi-dentate suspenders, and the last two are counter cations. Furthermore, AgI ions in 2 exhibit three kinds of coordination modes. Their electrochemistry properties have also been studied.The structural transformation from a discrete cluster to a wave-like chain played by the pz molecules.
Co-reporter:Peng-Peng Zhang, Jun Peng, Ai-Xiang Tian, Hai-Jun Pang, Yuan Chen, Min Zhu, Dan-Dan Wang, Ming-Guan Liu, Yong-Hui Wang
Journal of Molecular Structure 2010 Volume 984(1–3) pp:221-227
Publication Date(Web):15 December 2010
DOI:10.1016/j.molstruc.2010.09.031
Three compounds, [Na(bie)]2H[PW12O40] (1), [Cu(bie)]4[SiW12O40] (2) and [Cu(bie)]3H2[H3W12O40] (3) (bie = 2,2′-bis(1H-imidazolyl)ether) have been hydrothermally synthesized by introducing different metal cations and polyanions, and characterized by routine physical methods. Their crystal structures have been established by single crystal X-ray diffraction. Compound 1 shows a 1D infinite chain which is composed of Na-bie coordination polymers and PW12 polyanions. By using the CuI cation, compounds 2 and 3 which show the 2D layer architectures were obtained. Due to the different polyanions of compounds 2 and 3, the topologies of the 2D layers are distinct. Further, the electrochemical properties of compounds 1–3 were studied.
Co-reporter:Peng-Peng Zhang, Jun Peng, Ai-Xiang Tian, Hai-Jun Pang, Yuan Chen, Min Zhu, Dan-Dan Wang, Yong-Hui Wang
Journal of Molecular Structure 2010 Volume 968(1–3) pp:19-23
Publication Date(Web):8 April 2010
DOI:10.1016/j.molstruc.2010.01.014
Two new supramolecular compounds based on the Wells–Dawson polyoxometalate, [Cu(Hpbi)2]4[P2W18O62]2 (1) and (H2bbi)4[Cu2(bbi)(Hbbi)2][P2W18O62]2 (2) (pbi = 1,1′-(1,3-propanediyl)bis(imidazole), bbi = 1,1′-(1,4-butanediyl)bis(imidazole)), were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and single X-ray diffraction. The [P2W18O62]6− polyanions in both compounds play the template role inducing the metal–organic coordination polymers to array around them. The polymers form 3D supramolecular frameworks with different voids in which the polyanions reside. The difference should be attributed to the different lengths of the two organic ligands. In addition, the electrochemistry properties of the two compounds were studied, which indicates that the supramolecular compounds keep the redox properties of their parent polyanions and exhibit the electrocatalytic activities toward the reduction of bromate and nitrite.
Co-reporter:Peng-peng Zhang, Jun Peng, Hai-jun Pang, Yuan Chen, Min Zhu, Dan-dan Wang, Ming-guan Liu, Yong-hui Wang
Solid State Sciences 2010 Volume 12(Issue 9) pp:1585-1592
Publication Date(Web):September 2010
DOI:10.1016/j.solidstatesciences.2010.07.004
Two couples of new compounds templated by the polyanion [SiW12O40]4−,[Hbix][CuI(bix)]3[SiW12O40]·4H2O (1) and [CuII(H2O)(Hbix)2(bix)]2[CuII(H2O)2(Hbix)2(bix)][SiW12O40]3·4H2O (2) (bix = 1,4-Bis(imidazol-1-ylmethyl)benzene), [CuI(bbi)]4[SiW12O40]·2H2O (3) and [CuII(bbi2)]2[SiW12O40] (4) (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) were hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses and single X-ray diffraction. Compounds 1 and 2 were synthesized from the same reactants but exhibited distinct structures which could be ascribed to the different ratios of the reactant bix to CuII. In compound 1, the higher ratio of bix results in the transformation of the CuII to CuI, the [SiW12O40]4− templates direct the CuI–bix coordination polymers to form a 3D supramolecular framework with grid-like channels along two directions. The [SiW12O40]4− templates in compound 2 locate in the voids of the 3D supramolecular network constructed by CuII–bix coordination polymers, which exhibits the interdigitation fashion in both the formation of the 2D layer and the 3D framework. Compounds 3 and 4 were synthesized similar to 1 and 2, except for the change of bix to bbi. In compound 3, the CuI–bbi polymers form a supramolecular metal–organic host framework with rhombic channels in which the SiW12 templates reside. Compound 4 shows a framework with hexagonal channels constructed by CuII–bbi coordination polymers which accommodated the SiW12 templates.The different ratios of the organic ligands to CuII resulted in the different oxidation states of Cu, and further led to the distinct structures.
Co-reporter:Min Zhu, Jun Peng, Ai-Xiang Tian, Hai-Jun Pang, Peng-Peng Zhang, Yuan Chen, Dan-Dan Wang, Yong-Hui Wang
Solid State Sciences 2010 Volume 12(Issue 7) pp:1051-1057
Publication Date(Web):July 2010
DOI:10.1016/j.solidstatesciences.2010.04.031
By employing different organic amines as structure-directing agents, two new distinct 3D porous inorganic frameworks based on molybdenum(V) phosphates and MnII, (H2en)2{[Mn(H2O)]2[MnMo12O24(OH)6(H2PO4)2(HPO4)4(PO4)2]}·7H2O (en = ethylenediamine) (1) and (H3dien)2{[Mn(H3O)2][Mn3Mo12O24(OH)6(HPO4)2(PO4)6]}·5H2O (dien = diethylenetriamine) (2), have been hydrothermally synthesized, and characterized by routine physical methods. In compound 1, MnII all adopt octahedral coordination mode and each sandwich cluster Mn[Mo6P4O31]2 (abbreviated as Mn[Mo6P4]2) acts as an octa-dentate ligand linking eight MnII, which result in a 3D inorganic (4, 8)-connected framework with the (46)(410·612·86) topology. Compound 2 shows a 3D (4, 10)-connected framework with the (31·44·61)(34·49·57·617·74·84) topology, in which MnII ions exhibit both tetrahedral and octahedral coordination modes, and each Mn[Mo6P4]2 links ten MnII. Interestingly, there exist channels along the a and b axes in 1, while along the a and c axes in 2. The differences between the two compounds should be ascribed to the distinctions of the organic amines. Primary de-/rehydration behaviors and electrochemistry properties have also been studied for the two compounds.
Co-reporter:Ling Han;Peng-Peng Zhang;Hong-Sheng Liu;Hai-Jun Pang
Journal of Cluster Science 2010 Volume 21( Issue 2) pp:81-91
Publication Date(Web):2010 June
DOI:10.1007/s10876-010-0322-x
Two polynuclear manganese(II) sandwiched heteropolytungstates, Na10(HC3H4N2){[Na(H2O)][Mn(C3H4N2)]3[SbW9O33]2}·20H2O (1) and (C4H7N2)10[Mn4(H2O)2(PW9O34)2] (2), have been obtained by conventional aqueous synthesis method and characterized by IR spectra, TG, elemental analyses and single crystal X-ray diffraction. In compound 1, the three-nuclear manganese cluster is sandwiched by two [B-α-SbW9O33]9− units, and each manganese (II) is coordinated by one imidazole (im) molecule. Differently, compound 2 has a four-nuclear manganese (II) cluster with two coordination water molecules. The 2-methylimidazole (mim) molecules float around the polyanions and connect them into a 3D supramolecular framework by hydrogen bondings. The magnetic investigation for compound 1 indicates the existence of weak antiferromagnetic interaction in the sandwiched three-nuclear [Mn(C3H4N2)]3 cluster.
Co-reporter:Ai-xiang Tian, Jun Ying, Jun Peng, Jing-quan Sha, Hai-jun Pang, Peng-peng Zhang, Yuan Chen, Min Zhu and Zhong-min Su
Inorganic Chemistry 2009 Volume 48(Issue 1) pp:100-110
Publication Date(Web):December 1, 2008
DOI:10.1021/ic801338b
Four inorganic−organic hybrid compounds, [CuI4(bte)4(SiW12O40)] (1), [CuII2(bte)4(SiW12O40)]·4H2O (2) [bte = 1,2-bis(1,2,4-triazol-1-yl)ethane], [CuI4(btb)2(SiW12O40)]·2H2O (3), and [CuII2(btb)4(SiW12O40)]·2H2O (4) [btb = 1,4-bis(1,2,4-triazol-1-yl)butane], were hydrothermally synthesized through use of the same Keggin polyoxometalate as the template and tuning the molar ratio of the bis(triazole) ligand to the CuII ion. The ratio of the bis(triazole) ligand to CuII has a crucial influence on the structures of this series. Single-crystal X-ray diffraction analyses indicate that compound 1 is constructed by tetranuclear ring-connecting chains and polymerized [Cu(bte)]+ chains, between which SiW12 anions are inserted to form a three-dimensional (3D) structure. Compound 2 shows a (44·62) two-dimensional grid sheet. The discrete SiW12 anions are sandwiched by the sheets, just like “hamburgers”. Compound 3 presents channel-like [Cu2(btb)]2+ polymerized chains, which are further connected by SiW12 anions to construct a 3D framework. Compound 4 exhibits a (66) 3D Cu-btb framework with hexagonal channels, into which the tetradentate SiW12 anions are incorporated. The thermal stabilities of the compounds are discussed.
Co-reporter:Peng-Peng Zhang, Jun Peng, Jing-Quan Sha, Ai-Xiang Tian, Hai-Jun Pang, Yuan Chen and Min Zhu
CrystEngComm 2009 vol. 11(Issue 5) pp:902-908
Publication Date(Web):07 Feb 2009
DOI:10.1039/B817653A
Two new polyoxometalate-templated compounds, (bix)[Cu(bix)]3[PW12O40]·4H2O (1), and [Cu(bix)]3[PMo12O40] (2) (bix = 1,4-bis(imidazol-1-ylmethyl)benzene), were hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and single X-ray diffraction. In compound 1, the Keggin polyanions [PW12O40]3− direct the [Cu(bix)] coordination polymeric chains to form a 3D supramolecular framework with grid-like 2D channels. By changing the polyanions into [PMo12O40]3−, compound 2 is obtained, in which the [Cu(bix)] coordination polymeric chains array around the polyanions to construct a 3D supramolecular framework with 1D hexagon-like channels. Their different structures show the template effect of the polyanions. Additionally, the cyclic voltammetry measurements indicate that the supramolecular compounds keep the redox properties of their parent polyanions.
Co-reporter:Jingquan Sha, Jun Peng, Yu Zhang, Haijun Pang, Aixiang Tian, Pengpeng Zhang and Hong Liu
Crystal Growth & Design 2009 Volume 9(Issue 4) pp:1708-1715
Publication Date(Web):February 27, 2009
DOI:10.1021/cg800576b
By employing the polyoxometalates (POMs) with different sizes as structural motifs, three new organic−inorganic hybrids based on the multiply Cu-bipy coordination polymeric chain-modified POMs, [Cu(bipy)]2[HPMo12O40] (1), {[Cu(bipy)]4[GeW12O40]}·H2O (2), and {[Cu(bipy)]4[Mo15O47]}·2H2O (3) (bipy = 4,4′-bipyridine), have been hydrothermally synthesized and characterized by routine physical methods. Compound 1 exhibits 1D chain in which Keggin POMs are modified by bitrack Cu-bipy chains. Compound 2 represents a 2D layer of tetra-track Cu-bipy chain modified Keggin POMs. And compound 3 shows an infinite-track Cu-bipy chain-modified molybdenum oxides 3D structure, namely, a modifying state of high point. Because the differences of POMs affect the structures of the hybrids—the number of Cu-bipy chains from bi- to infinite-track, and the dimension from 1D to 3D—their successful isolation demonstrates that members of the vast family of POMs may be employed as structural motifs in designing more solid-state materials. Additionally, their electrochemical properties have been studied.
Co-reporter:Hai-jun Pang;Chun-jing Zhang, ;Yong-hui Wang;Jing-quan Sha;Ai-xiang Tian;Peng-peng Zhang;Yuan Chen;Min Zhu ;Zhong-min Su
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 34) pp:5175-5180
Publication Date(Web):
DOI:10.1002/ejic.200900559
Abstract
Two isostructural compounds, {[Cu2(DF)2H2O]2SiW12O40}·2H2O (1) and {[Cu2(DF)2H2O]2GeMo12O40}·2H2O (2) (DF = 4,5-diazafluoren-9-one), were synthesized and characterized by routine methods and single-crystal X-ray diffraction. In the compounds, each Keggin cluster links five copper dimers [Cu2(DF)2H2O]2+ in an unusual asymmetrical pentacoordination mode to form 3D networks with left- and right-handed helical chains. Notably, by comparing 1 and 2 with other helical compounds with Keggin clusters as connectors, we found that the pitches of those compounds are mainly dominated by the coordination modes of the Keggin clusters, suggesting that the Keggin clusters are pitch-tunable synthons. Furthermore, the luminescent and electrochemical properties of the title compound were studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Pengpeng Zhang, Jun Peng, Xiaoqing Shen, Zhangang Han, Aixiang Tian, Haijun Pang, Jingquan Sha, Yuan Chen, Min Zhu
Journal of Solid State Chemistry 2009 Volume 182(Issue 12) pp:3399-3405
Publication Date(Web):December 2009
DOI:10.1016/j.jssc.2009.09.032
A new compound based on polyoxometalates, [Cu(bbi)]5H[H2W12O40] (1) (bbi=1,1′-(1,4-butanediyl)bis(imidazole)), has been hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and single X-ray diffraction. Compound 1 shows a twofold 3D+3D topology, and it represents the first interpenetrating network based on the isopolytungstate. The electrochemical property of compound 1 modified carbon paste electrode (1−CPE) was investigated in 1 M H2SO4 solution, and the results indicate that 1−CPE exhibits the electrocatalytic activity toward the reduction of bromate and nitrite. Further, the non-isothermal kinetics of the thermal decomposition of compound 1 provides the dynamic parameters E (activation energy) and A (pre-exponential factor) for the pyrolytic reaction of the organic ligands.The 3D+3D structure representation of the first example of interpenetrating framework based on the isopolytungstate.
Co-reporter:Haijun Pang, Jun Peng, Jingquan Sha, Aixiang Tian, Pengpeng Zhang, Yuan Chen, Min Zhu
Journal of Molecular Structure 2009 Volume 921(1–3) pp:289-294
Publication Date(Web):17 March 2009
DOI:10.1016/j.molstruc.2009.01.008
A new hybrid constructed from Wells–Dawson polyanions and silver complexes, [Ag(bipy)]2[Ag(bipy)(Hbipy)][P2W18O62]·[H2bipy] (1) (bipy = 4,4′-bipyridine), has been hydrothermally synthesized, and characterized by IR, TG, XRPD and single-crystal X-ray diffraction. Structural analysis reveals that compound 1 possesses left- and right-helical chains constructed by Ag(bipy) complexes. Furthermore, these helical chains are linked together by Ag atoms via sharing O atoms of the Wells–Dawson polyanions to form two-dimensional (2D) sheets. Finally, a 3D framework is obtained with (41·64·81)(46·62·82·105) topology, which is constructed by the 2D sheets through the O atoms of the Wells–Dawson polyanions. Also, the electrochemical behavior and electrocatalysis of 1 modified carbon paste electrode (1-CPE) have been studied in detail. The results indicate that 1-CPE has remarkable stability and good electrocatalytic activities.
Co-reporter:Hongsheng Liu, Carlos J. Gómez-García, Jun Peng, Jingquan Sha, Lixia Wang, Yechao Yan
Inorganica Chimica Acta 2009 Volume 362(Issue 6) pp:1957-1962
Publication Date(Web):20 April 2009
DOI:10.1016/j.ica.2008.09.014
A Co-monosubstituted Keggin polyoxometalate with an antenna ligand linked to the Co(II) center with a Co(II)-containing cation has been prepared. The title compound, formulated as {Co(H2O)4(4,4′-bpy)}2(4,4′-Hbpy)2[SiW11Co(4,4′-bpy)O39] · 5H2O (1) (4,4′-bpy = 4,4′-bipyridine), was synthesized and characterized by elemental analysis, IR spectra, TG analysis, X-ray single crystal structure analysis and magnetic measurements. As far as we know, the title compound represents the first Co(II) substituted Keggin polyoxometalate with an antenna ligand structurally and magnetically characterized.A Co-monosubstituted Keggin polyanion with a 4,4′-bipyridine molecule as an antenna ligand, formulated as [SiW11Co(4,4′-bpy)O39]6− (4,4′-bpy = 4,4′-bipyridine), has been prepared and characterized by elemental analysis, IR spectra, TG analysis, X-ray single crystal structure analysis and magnetic measurements. This is the first crystallographically characterized example of grafting the 4,4′-bpy molecule into the 3d-metal-monosubstituted heteropolyanions, isolated under aqueous solution conditions.
Co-reporter:Hai-jun Pang, Jing Chen, Jun Peng, Jing-quan Sha, Zhen-yu Shi, Ai-xiang Tian, Peng-peng Zhang
Solid State Sciences 2009 Volume 11(Issue 4) pp:824-828
Publication Date(Web):April 2009
DOI:10.1016/j.solidstatesciences.2008.11.008
A Ag-bridged V-centred tungstovanadate dimer capped by [Ag(phen)] unit, [Ag(phen)2]7{Ag[Ag(phen)(VW10V2O40)]2} (1) (phen = 1,10-phenanthroline), has been hydrothermally synthesized, and characterized by IR, TG and single-crystal X-ray diffraction. Structural analysis reveals that the compound is composed of one dimeric {Ag[Ag(phen)(VW10V2O40)]2}7− anion and seven [Ag(phen)2]+ cations, which represents the first V-centred tungstovanadate grafted by transition metal coordination polymers. Furthermore, the electrochemical properties of 1 have been studied in the paper.
Co-reporter:Jingquan Sha, Lin Huang, Jun Peng, Haijun Pang, Aixiang Tian, Pengpeng Zhang, Yuan Chen, Min Zhu
Solid State Sciences 2009 Volume 11(Issue 2) pp:417-421
Publication Date(Web):February 2009
DOI:10.1016/j.solidstatesciences.2008.07.007
Two novel polyoxometalate(POM)-templated coordination polymers: [Cu2(phnz)3][M6O19] (M = Mo for 1, W for 2; phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In the compounds, Lindqvist POMs as templates induce the [Cu2(phnz)3] complexes to 2D hexagonal metal-organic framework (MOF), which represents 63 topologies of dimensions ca. 13.515 × 13.515 × 13.515 Å. Furthermore, the 2D sheets are held together by Lindqvist POMs into 3D supramolecular networks with 1D channel, and Lindqvist POMs site in the channels. The successful syntheses and isolation of two compounds provide a novel example of the utility of POM clusters as templates for self-assembly extended framework with cavities.Based on Lindqvist POM and phenazine, a porous metal-organic framework with standard hexagon is formed, in which POM as guest molecules occupy all of the voids. Additionally, POMs play dual role, namely, POMs as template induce the formation of the honeycomb cavities in the same sheet; and as linkers connect the 2D sheet motifs into 3D structures in the different sheets.
Co-reporter:Hai-jun Pang, Jing-quan Sha, Jun Peng, Ai-xiang Tian, Chun-jing Zhang, Peng-peng Zhang, Yuan Chen, Min Zhu, Yong-hui Wang
Inorganic Chemistry Communications 2009 Volume 12(Issue 8) pp:735-738
Publication Date(Web):August 2009
DOI:10.1016/j.inoche.2009.06.002
Co-reporter:Hongsheng Liu, Jun Peng, Jingquan Sha, Lixia Wang, Ling Han, Dan Chen, Yan Shen
Journal of Molecular Structure 2009 Volume 923(1–3) pp:153-161
Publication Date(Web):17 April 2009
DOI:10.1016/j.molstruc.2009.02.018
Two new compounds based on Weakley-sandwich-type polyanion (WSP), H2[Mn(en)2]2[Mn(en)2(H2O)]2[Mn4(H2O)2(PW9O34)2]·9H2O (1) and Na2[Co(en)2]2[{Co(en)2(H2O)]2[Co4(H2O)2(PW9O34)2]·9H2O (2) (en = ethylenediamine), have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [a-A-PW9O34]9− with transition metal ions and en, and structurally characterized by routine physical methods and single-crystal X-ray diffraction. Compound 1 represents a 1D chain structure made up of WSPs and [Mn(en)2]2+ ions. Compound 2 represents a 2D layer structure formed by the interconnection of WSPs, [Co(en)2]2+ and Na+ ions. Compounds 1 and 2 represent the first example of high-dimensional construction based on WSPs and transition metal complexes (TMCs), in which the water molecules located on the featured tetra-metal unit are still remained, and exhibit the property of sorption/desorption of water molecules.
Co-reporter:Jing Chen, Jing-quan Sha, Jun Peng, Zhen-yu Shi, Ai-xiang Tian, Peng-peng Zhang
Journal of Molecular Structure 2009 Volume 917(Issue 1) pp:10-14
Publication Date(Web):9 January 2009
DOI:10.1016/j.molstruc.2008.06.022
Two new supramolecular assemblies based on Keggin-type polyoxometalates, [Ag3(4,4′-bipy)2(2,2′-bipy)2][Ag(2,2′-bipy)2][{Ag(2,2′-bipy)}HSiW11VO40] (1) and [Ag3(4,4′-bipy)2(2,2′-bipy)2][Ag(2,2′-bipy)2][{Ag(2,2′-bipy)}PW11VO40] (2) (4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been synthesized under the hydrothermal conditions and structurally characterized by IR, XPS, TG and single-crystal X-ray diffraction. Compound 1 has a 2D layer network structure via weak Ag...O interactions. Compound 2 is isostructural with compound 1. In addition, the fluorescence of compound 1 is reported.
Co-reporter:Haijun Pang, Jun Peng, Jingquan Sha, Aixiang Tian, Pengpeng Zhang, Yuan Chen, Min Zhu
Journal of Molecular Structure 2009 Volume 922(1–3) pp:88-92
Publication Date(Web):30 March 2009
DOI:10.1016/j.molstruc.2009.01.026
Through using rigid and flexible bis(pyridine) ligands, two new Keggin POM-based hybrid compounds: [Cu(bipy)]2[H2SiW12O40]·2H2O (1) and [Cu(bpp)2][H2PW12O40]·2H2O (2) (bipy = 4,4′-bipyridine and bpp = 1,3-bis(4-pyridyl)propane) have been synthesized and characterized by routine methods. In compound 1, each rigid bipy molecule links two Cu ions into an unbent Cu–bipy coordination polymeric chain, which are further covalently connected by SiW12 clusters resulting in a ladder-like chain. In compound 2, the flexible organic ligand bpp with (CH2)3 spacer is used. The PW12 cluster as a template is wrapped by two “S”-style [Cu(bpp)2]+ fragments in a pseudo-parallelogram grid. Furthermore, these grids are fused together by sharing [Cu(bpp)2]+ fragments resulting in a 1D chain. Also, the electrochemical properties of these two compounds have been studied in the paper.
Co-reporter:Peng-peng Zhang, Ai-Xiang Tian, Jun Peng, Hai-Jun Pang, Jing-Quan Sha, Yuan Chen, Min Zhu, Yong-Hui Wang
Inorganic Chemistry Communications 2009 Volume 12(Issue 9) pp:902-904
Publication Date(Web):September 2009
DOI:10.1016/j.inoche.2009.07.007
A polyoxometalate-based compound, (bix)[Cu(bix)][Cu2(bix)2(P2W18O62)]·2H2O (1) (bix = 1,4-bis(imidazol-1-ylmethyl)benzene), was hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analysis, and single X-ray diffraction. Compound 1 exhibits the 1D + 1D polypseudo-rotaxane structure consists of two parts: the P2W18–Cu2–(bix)2 chain which contains 26-membered Cu2(bix)2 macrocycles and the 1D Cu-bix line. Remarkably, it represents the first polypseudo-rotaxane structure based on the Wells–Dawson polyoxometalate.The first polypseudo-rotaxane structure based on the Wells–Dawson polyoxometalate was hydrothermally synthesized.
Co-reporter:Yuan Chen, Jun Peng, Hai-jun Pang, Ai-xiang Tian, Peng-peng Zhang, Dan Chen, Min Zhu, Yonghui Wang, Huiyuan Ma
Inorganic Chemistry Communications 2009 Volume 12(Issue 12) pp:1242-1245
Publication Date(Web):December 2009
DOI:10.1016/j.inoche.2009.09.032
A new compound, H4{[Cu3(2-Hpzc)2(H2O)4](H2W12O42)}·13H2O (1) (2-Hpzc = 2-pyrazinecarboxylic acid), was synthesized in conventional condition and characterized by elemental analyses, IR spectroscopy, thermal gravimetric analysis, X-ray powder diffraction (XRPD) and single X-ray diffraction. In the structure of compound 1, each paradodecatungstate anion acts as a quadridentate ligand coordinating to four Cu2+ cations through its terminal oxygen atoms to form a two-dimensional (2D) layer. The infinite [Cu(2-Hpzc)]2+ chains connect adjacent layers forming a three-dimensional (3D) architecture. There exist two kinds of channels with sizes of ca. 5.737 × 4.628 Å2 and 9.104 × 8.640 Å2 along the b and c directions, respectively. The magnetic behavior of 1 exhibits antiferromagnetic interaction.A new compound with three-dimensional framework has been synthesized, which represents the first high-dimensional hybrids based on paradodecatungstate modified by [Cu(2-Hpzc)]2+ complexes.
Co-reporter:Ai-xiang Tian ; Jun Ying ; Jun Peng ; Jing-quan Sha ; Zhan-gang Han ; Jian-fang Ma ; Zhong-min Su ; Ning-hai Hu ;Heng-qing Jia
Inorganic Chemistry 2008 Volume 47(Issue 8) pp:3274-3283
Publication Date(Web):March 11, 2008
DOI:10.1021/ic7023082
Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu6(btp)3(P2W18O62)]·3H2O (1) (btp = 1,3-bis(1,2,4-triazol-1-y1)propane), [Cu6(btb)3((P2W18O62)]·2H2O (2), [Cu3(btb)6(P2W18O62)]·6H2O (btb = 1,4-bis(1,2,4-triazol-1-y1)butane) (3), and [Cu3(btx)5.5((P2W18O62)]·4H2O (btx = 1,6-bis(1,2,4-triazol-1-y1)hexane) (4), were synthesized and structurally characterized. In compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P2W18O62]6− anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu−btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu−btb layers to construct a 3D structure. Compound 3 exhibits a (42·62·82) 3D Cu−btb framework with square and hexagonal channels arranged alternately. The hexa-dentate polyoxoanions incorporate only into the hexagonal channels. In compound 4, there exist two sets of (61·102)2(61·82·103) 3D Cu−btx frameworks to generate a 2-fold interpenetrated structure into which the penta-dentate polyoxoanions are inserted to construct a 3D structure. The structural analyses reveal that the length of flexible bis(triazole) ligands and metal ion coordination geometries have a synergic influence on the structures of this series. To our knowledge, they have the highest connectivity for the Wells-Dawson polyoxometalate coordination polymers to date.
Co-reporter:Jingquan Sha, Jun Peng, Yaqan Lan, Zhongmin Su, Haijun Pang, Aixiang Tian, Pengpeng Zhang and Min Zhu
Inorganic Chemistry 2008 Volume 47(Issue 12) pp:5145-5153
Publication Date(Web):May 16, 2008
DOI:10.1021/ic702407y
Four new hybrids based on the Wells-Dawson polyoxometalate [P2W18O62]6− (P2W18), {[Ag(bipy)]2[P2W18O62]}·2[H2bipy]·4H2O (1), {[Ag(bipy)]4[P2W18O62]}·2[Hbipy] (2), K[P2W18O62]·2.5[H2bipy]·2H2O (3), and [P2W18O62]2·[H2bipy]4·[Hbipy]4·3H2O (4), were hydrothermally synthesized and structurally characterized by routine techniques and single-crystal X-ray diffraction. Compounds 1 and 2 are isolated at lower pH values. 1 represents a 3D (4,4)-net structure with NbO topology, in which the P2W18 clusters are modified by four Ag−N coordination polymeric chains, and 2 exhibits a 3D (3,4)-net structure with the (92·12)(8·104·12)(32·102·112)(3·6·102·122) topology, in which Ag-bipy layers are intercalated by the dimer of P2W18 clusters in a staggering mode, and the P2W18 clusters show the highest coordination number to date. By increasing the pH value, compounds 3 and 4 are obtained as supramolecular compounds. Their structural differences reveal that the pH value of the reaction system is the key factor influencing the structure and topology of these compounds, which can be explained by the acid−base chemistry of the molecular building units and silver chemistry.
Co-reporter:Ai-xiang Tian, Jun Ying, Jun Peng, Jing-quan Sha, Hai-jun Pang, Peng-peng Zhang, Yuan Chen, Min Zhu and Zhong-min Su
Crystal Growth & Design 2008 Volume 8(Issue 10) pp:3717-3724
Publication Date(Web):August 23, 2008
DOI:10.1021/cg800353y
Through tuning the spacer length of flexible bis(triazole) ligands, three Keggin anion-based coordination polymers with different dimensionalities, [Cu4(H2O)4(bte)2(HPMoVI10MoV2O40)]·2H2O (1) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), [Cu(btb)][Cu2(btb)2(PMo12O40)] (2) (btb = 1,4-bis(1,2,4-triazol-1-y1)butane), and [Cu5(btx)4(PMoVI10MoV2O40)] (3) (btx = 1,6-bis(1,2,4-triazol-1-y1)hexane), were synthesized and structurally characterized. Compound 1 exhibits a ladder-like chain, in which the polyoxometalate (POM) anions act as the “middle rails” of the ladder. The bte ligand with shortest spacer length acts as not only the bridging linker but also the chelator, which terminates the dimensional extension. Compound 2 exhibits a 2D POM-based framework, containing POM/Cu/btb grid-like layers. In compound 3, there exist three sets of (123)(121)2 2D Cu-btx frameworks to generate a 3-fold interpenetrating structure, into which the hexadentate POM anions are inserted to construct a 3D structure. The structural analyses reveal that the spacer length of flexible bis(triazole) ligands has influence on the dimensionality of these compounds.
Co-reporter:Hongsheng Liu, Carlos J. Gómez-García, Jun Peng, Jingquan Sha, Yangguang Li and Yechao Yan
Dalton Transactions 2008 (Issue 44) pp:6211-6218
Publication Date(Web):25 Sep 2008
DOI:10.1039/B805714A
Three new organic–inorganic hybrid complexes based on 3d-transition metal monosubstituted Keggin polyoxometalates (POMs) with imidazole (Im) as pendant ligands, formulated as (HIm)6[SiW11O39NiIm]0.8[SiW11O39Ni(H2O)]0.2·7H2O (1), (Im)4Na6[SiW11O39MnIm]0.69[SiW11O39Mn(H2O)]0.31·7.5H2O (2) and (HIm)6[SiW11O39CoIm]0.63[SiW11O39Co(H2O)]0.37·7H2O (3), have been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy, elemental analysis, TG analysis, cyclic voltammetry, magnetic properties, EPR and single-crystal/powder X-ray diffraction. The structural analyses indicate that the 3d metal atoms are incorporated into the vacancy of the α-[SiW11O39]8− (SiW11). Complexes 1–3 are the first examples of crystallographically characterized 3d-transition metal mono-substituted POMs with an antenna organic ligand synthesized under normal bench conditions.
Co-reporter:Jingquan Sha, Jun Peng, Haijun Pang, Aixiang Tian, Jing Chen, Pengpeng Zhang, Min Zhu
Solid State Sciences 2008 Volume 10(Issue 11) pp:1491-1498
Publication Date(Web):November 2008
DOI:10.1016/j.solidstatesciences.2008.01.023
Two new organic–inorganic hybrid compounds based on the Keggin POMs modified by hexad-track Ag–N coordination polymeric chains, {[Ag(bipy)]3[HXW12O40]}[bipy] (X = Si 1, Ge 2) (bipy = 4,4′-bipyridine), have been hydrothermally synthesized and structurally characterized. Crystal data for compound 1: C40H33Ag3N8O40SiW12, triclinic, space group P-1, a = 11.369, b = 12.087, c = 13.110, α = 112.88, β = 94.43, γ = 99.49, V = 1617.2; for compound 2: C40H33Ag3N8O40SiW12, triclinic, space group P-1, a = 11.383, b = 12.119, c = 13.136, α = 112.95, β = 94.35, γ = 99.51, V = 1626.0. They represent important examples of the POM family which are modified by Ag complexes. By changing POMs, compound 3 (H2bipy)2[SiMo12O40] has been obtained, which exhibits a supramolecular structure. Their structural differences reveal that the abilities of oxidation of POMs play a major role in their modification of POMs by the transition metal Ag.Based on the Keggin POMs and Ag salt, three new compounds were obtained. Compounds 1 and 2 exhibit two novel 3D organic–inorganic hybrids with (4,6)-connected (41·64·81)(42·63·810) topology and compound 3 shows one supramolecular structure. Their successful isolation gives a good example for understanding the inter-relation between the POM chemistry and metal chemistry.
Co-reporter:Aixiang Tian, Zhangang Han, Jun Peng, Jingquan Sha, Yulong Zhao, Haijun Pang, Pengpeng Zhang, Min Zhu
Solid State Sciences 2008 Volume 10(Issue 10) pp:1352-1357
Publication Date(Web):October 2008
DOI:10.1016/j.solidstatesciences.2008.01.018
This article reports two new bicapped Keggin-based hybrid compounds, {[Cu4I(cppy)4][PMo7VIMo5VO40(VIVO)2]}·2H2O (1) and {[Cu4I(cppy)4][SiMo8VIMo4VO40(VIVO)2]}·2H2O (2) (cppy = 4-(5-(4-chlorophenyl)pyridin-2-yl)pyridine), synthesized under hydrothermal conditions and characterized by X-ray single-crystal diffraction, elemental analyses, IR, XPS, TG and CV analyses. Structural characterization shows that the two compounds are isostructural, consisting of square tetranuclear [Cu4I(cppy)4]4+ circuits and reduced bivanadyl Keggin clusters. The tetranuclear [Cu4I(cppy)4]4+ circuit is ‘windstick’-style. The polyoxoanions acting as junctures connect the tetranuclear circuits to construct a chain. These chains are further connected through π⋯π interactions, halogen bonding and hydrogen bonding interactions to construct a 3D superamolecular structure. The electrochemical behaviors of the 1-CPE have been studied in detail.The Cu(I) ions and the cppy molecules construct the square tetranuclear [Cu4I(cppy)4]4+ circuit, with ‘windstick’-style. The circuits are connected by the bicapped polyoxoanions to construct a 1D chain. The two neighboring chains arrange across like a ‘zipper’.
Co-reporter:Jingquan Sha, Jun Peng, Yangguang Li, Pengpeng Zhang, Haijun Pang
Inorganic Chemistry Communications 2008 Volume 11(Issue 8) pp:907-910
Publication Date(Web):August 2008
DOI:10.1016/j.inoche.2008.04.005
A novel 3D hybrid compound based on TMCs modified Wells-Dawson polyoxometalate, [{Ag(H2O)(phnz)}{Ag(phnz)}5(P2W18O62)][phnz]0.5 · 4H2O (1) (phnz = phenazine), has been synthesized and characterized. X-ray diffraction analysis reveals that the periphery of the Wells-Dawson POMs contains nine Ag-phnz units, which represents the highest connection of the Wells-Dawson POMs up to now. In the crystal engineering point of view, Ag atoms exhibit rich and novel coordination geometries, which facilitate the formation of the highest coordination number of the Wells-Dawson POMs. Additionally, the electrochemical behavior of 1 modified CPE (1-CPE) has been studied.A novel 3D POM/TMC hybrid based on the highest connected Wells-Dawson POMs is reported for the first time. The rich coordination fashions of Ag+ ions and the nature of Wells-Dawson POMs and phnz molecules together lead to the formation of the high-connected Wells-Dawon POMs.
Co-reporter:Aixiang Tian, Zhangang Han, Jun Peng, Jun Ying, Jingquan Sha, Baoxia Dong, Jiangli Zhai, Hongsheng Liu
Inorganica Chimica Acta 2008 Volume 361(Issue 5) pp:1332-1338
Publication Date(Web):1 April 2008
DOI:10.1016/j.ica.2007.08.033
A new α-Keggin POM derivative [Cu2I(DF)2H2O][HPMo10VIMo2VO40{CuII(DF)}] (1) (DF = 4,5-diazafluoren-9-one) has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR, XPS spectra, thermogravimetric analysis and cyclic voltammetry. In compound 1, the polyoxoanion cluster [PMo10VIMo2VO40]5- is decorated by a single capping {Cu(DF)}2+ subunit via four bridging oxygen atoms on a {Mo4O4} pit. The isolated copper dimer unit {Cu2I(DF)2H2O}2+acts as counter cation, in which the organic ligand DF exhibits a rare coordination mode. Furthermore, the capped Keggin polyoxoanions [PMo10VIMo2VO40{CuII(DF)}]3- are fused together via the copper dimers through the weak Cu ⋯ O interactions to form chains. Hybrid 1 was used as a solid bulk modifier to fabricate a carbon paste electrode (1-CPE) by direct mixing. The electrochemical and electrocatalytic behaviors of the 1-CPE have been studied in detail.Compound [Cu(IDF)2H2O][HPMo10VIMo2VO40{CuII(DF)}] (1) consists of a copper capped polyoxoanion [PMo10VIMo2VO40{CuII(DF)}]3− and one discrete copper dimer unit {Cu2I(DF)2H2O}2+, in which the organic ligand DF exhibits a rare coordination mode. The electrochemical and electrocatalytic behaviors of the 1-CPE have been studied in detail.
Co-reporter:Aixiang Tian, Jun Ying, Jun Peng, Jingquan Sha, Dongxia Zhu, Haijun Pang, Pengpeng Zhang, Yuan Chen, Min Zhu
Inorganic Chemistry Communications 2008 Volume 11(Issue 10) pp:1132-1135
Publication Date(Web):October 2008
DOI:10.1016/j.inoche.2008.06.014
A new Wells–Dawson polyoxometalate-templated compound, (H3btb)[Fe(btb)3(P2W18O62)] · 4H2O (1) (btb = 1,4-bis(1,2,4-triazol-1-y1)butane), was synthesized under hydrothermal conditions. Compound 1 presents an interesting zigzag chain [Fe(btb)]∞3+ through using bi-dentate “bridging” btb ligands, while the mono-dentate pendant btb molecules act as arms “hugging” the polyanion templates.Compound 1 presents an interesting zigzag chain [Fe(btb)]∞3+ through using bi-dentate “bridging” btb ligands, while the mono-dentate pendant btb molecules act as arms “hugging” the polyanion templates.
Co-reporter:Jingquan Sha;Shujing Zhou;Min Zhu;Ling Han
Journal of Cluster Science 2008 Volume 19( Issue 3) pp:499-509
Publication Date(Web):2008 September
DOI:10.1007/s10876-008-0192-7
Two new bivanadyl capped Keggin polyoxometalate-based inorganic–organic hybrid compounds, [M(2,2′-bipy)2(H2O)]2[AsMo12O40(VO)2]}(M = Co 1, Zn 2; bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Li3[AsMo12O40] · nH2O as starting materials. Single crystal X-ray analysis revealed that compounds 1 and 2 were isostructural, consisting of a neutral bivanadyl capped Keggin POMs bigrafted by [M(2,2′-bipy)2(H2O)]2+ fragments. Other characterizations by elemental analysis, IR spectra, XPS spectra, power X-ray diffraction and TG analysis were also described in the paper. The study of the electrochemical properties of compounds 1 and 2 exhibit similar redox behaviors, undergoing three two-electron reversible redox processes, and the electrocatalysis of 1 has also been studied in detail.
Co-reporter:Jingquan Sha, Jun Peng, Aixiang Tian, Hongsheng Liu, Jing Chen, Pengpeng Zhang and Zhongmin Su
Crystal Growth & Design 2007 Volume 7(Issue 12) pp:2535
Publication Date(Web):November 15, 2007
DOI:10.1021/cg070438b
By introducing different long rigid ligands into polyoxometalate (POM) systems, four novel inorganic–organic hybrids containing multitrack Cu−N coordination polymeric chain-modified POMs, {[Cu(4,4′-bipy)]3[HGeMo12O40]}·0.5H2O (1), [Cu(4,4′-bipy)]{[Cu(4,4′-bipy)]2[W6O19]}·4H2O (2) (bipy = bipyridine), [Cu(bpe)]{[Cu(bpe)]2[GeMo12O40(VO)2]} (3) (bpe = bis(4-pyridyl)ethylene), and [Cu2(phnz)3]2[SiW12O40] (4) (phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods. The crystal structures of 1–4 have been established by single crystal X-ray diffraction. Compound 1 exhibits a tritrack Cu−N chain-modified Keggin POM 1D structure. Compound 2 represents the first example of a 2D framework constructed from a Lindquist polyoxoanion modified by double bitrack Cu−N chains via its terminal oxygen and bridge oxygen atoms. The rail-like 1D structure of compound 3 is formed from Keggin clusters modified by double monotrack Cu−N chains. Compound 4 shows a pseudo-1D structure of double monotrack Cu−N chain-modified Keggin POMs through offset face-to-face π−π stacking interactions between the adjacent phnz molecules. Investigation of their structural differences shows the important roles of the size of POMs and the unit length of the Cu−N chains in the assembly process of the solid structures. Furthermore, the electrochemical properties of 1−4 were studied.
Co-reporter:Jingquan Sha;Hongsheng Liu;Jing Chen;Baoxia Dong;Aixiang Tian;Zhongmin Su
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 9) pp:
Publication Date(Web):16 FEB 2007
DOI:10.1002/ejic.200601017
Two novel complexes based on the Keggin POMs modified by the Cu(4,4′-bipy) moiety, {[Cu(4,4′-bipy)]3[HSiMo12O40]}·1.5H2O (1) and {[Cu(4,4′-bipy)]4[SiW12O40]}·3H2O (2) (bipy = bipyridine), have been hydrothermally synthesized and characterized by routine physical methods and single-crystal X-ray diffraction. Complexes 1 and 2 represent the first examples of fully oxidized Keggin POM anions as pendant polydentate ligands covalently bonded to a multitrack Cu(bipy) polymer chain(s) through linearly arrayed Od···Oc···Od (Od, terminal oxygen; Oc, bridging oxygen) atoms of single M3O13 triad(s). In the crystalline lattice of 1, the 1D chain is constructed from a α-[SiMo12O40]4– (SiMo12) cluster as a pendant tridentate ligand covalently bonded to three CuI(4,4′-bipy) subunits, and the neighbouring polymer strands interconnect with the Keggin fragments geared like the teeth of a zipper. In compound 2, the 2D extended layer structure is composed of a α-[SiW12O40]4– (SiW12) cluster as a pendant hexadentate ligand covalently bonded to four CuI(4,4′-bipy) subunits and forms a 2D net-texture structure with a large vacancy (30.9 × 10.6 Å), and the 2D layers are arranged in a parallel staggering fashion to form a 3D framework.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Jingquan Sha, Jun Peng, Jing Chen, Hongsheng Liu, Aixiang Tian, Pengpeng Zhang
Solid State Sciences 2007 Volume 9(Issue 11) pp:1012-1019
Publication Date(Web):November 2007
DOI:10.1016/j.solidstatesciences.2007.07.017
Two novel inorganic–organic hybrid compounds composed of Keggin tungstocobaltate framework and cobalt(II)–N coordination complexes, K[Co(phen)2(H2O)]2[HCoW12O40]·2H2O (1) (phen = 1,10-phenanthroline) and [Co(2,2′-bipy)3]1.5{[Co(2,2′-bipy)2(H2O)][HCoW12O40]·0.5H2O (2) (bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials, which were characterized by elemental analyses, IR, TG analyses and X-ray single crystal diffraction. Crystal data for compound 1: C48H41Co3KN8O44W12, triclinic, space group P-1, a = 10.918(5) Å, b = 13.401(5) Å, c = 13.693(5) Å, α = 69.291(5)°, β = 71.568(5)°, γ = 78.421(5)°, V = 1768.9(12) Å3, Z = 1; for compound 2: C130H104Co7N26O83W24, orthorhombic, space group, C2/c, a = 46.839(9) Å, b = 14.347(3) Å, c = 26.147(5) Å, α = β = γ = 90°, V = 17,570(6) Å3, Z = 4. Compound 1 exhibits a pseudo-1D chainlike structure, in which potassium ions act as linkages of Keggin unit doubly grafted by [Co(phen)2(H2O)] complex. Compound 2 represents a [Co(2,2′-bipy)2(H2O)]2+ mono-grafted Keggin tungstocobaltate derivative with 1.5[Co(2,2′-bipy)3]2+ countercations. The cyclic voltammetric behavior of 1-CPE is similar to the parent 3-CPE, but the cyclic voltammetric behavior of CoII shows a little difference. Variable-temperature magnetic susceptibility measurement of compound 1 demonstrates the presence of antiferromagnetic interactions.Two novel Keggin tungstocobaltate hybrid compounds grafted cobalt(II) coordination groups: K[Co(phen)2(H2O)]2[HCoW12O40]·2H2O (1) and [Co(2,2′-bipy)3]1.5{[Co(2,2′-bipy)2(H2O)] [HCoW12O40]·0.5H2O (2)(phen = 1,10′phenanthroline, bipy = bipyridine) have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials. Compound 1 exhibits interesting pseudo-1D chainlike architectures assembled by potassium ions bridged bi-grafted Keggin units. Compound 2 represents mono-grafted Keggin tungstocobaltate derivatives with one point five [Co(2,2′-bipy)3]2+ counteractions which construct 1D supermolecular chain via H-bonding interactions
Co-reporter:Jingquan Sha, Jun Peng, Hongsheng Liu, Bo Xue, Jing Chen, Aixiang Tian, Baoxia Dong, Pengpeng Zhang
Journal of Molecular Structure 2007 Volume 871(1–3) pp:85-91
Publication Date(Web):15 December 2007
DOI:10.1016/j.molstruc.2007.01.059
Two novel three-dimensional (3D) hexad-supporting organic–inorganic hybrid compounds based on the Keggin POMs modified by copper(I) transition metal and N-ligand organic moiety, {[Cu(4,4′-bipy)]3[PW12O40]}[4,4′-bipy]·2H2O (1) and {[Cu(4,4′-bipy)]3[HSiW12O40]}[4,4′-bipy]·2H2O (2) (bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials. The two compounds are isomorphous and crystallized in the space group P1¯. They represent an important example of the family of polyanion-supported transition-metal solids, in which POMs covalently link six transitional metal-complex fragments. It is also interesting that the 3D structure constructed by hexad-supporting {[Cu(4,4′-bipy)]3[HnXW12O40]} subunits presents 1D channels in which neutral 4,4′-bipy molecules are located. They exhibit similar redox behavior, undergoing two one-electron reversible redox processes.
Co-reporter:Baoxia Dong, Carlos J. Gómez-García, Jun Peng, Samia Benmansour, Yumei Kong
Journal of Molecular Structure 2007 Volume 827(1–3) pp:50-55
Publication Date(Web):17 February 2007
DOI:10.1016/j.molstruc.2006.05.011
Two new hexadecavanadate derivatives, (bpy)[Zn(4,4′-bpy)2]2[H4ClV16O38]·6H2O 1 and (bpy)[Co(4,4′-bpy)2]2[H4ClV16O38]·6H2O 2 (bpy = 4,4′-bipyridine), were synthesized under the hydrothermal conditions and structurally characterized by IR, XPS and EPR spectroscopy, redox titration and single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the tetragonal non-centrosymmetric space group P-4n2 (No. 118) with a = 17.124(2), b = 17.124(2), c = 14.724(3) Å, V = 4317.5(12) Å3 and Z = 1 for the compound 1, and a = 17.038(2), b = 17.038(2), c = 14.754(3) Å, V = 4282.9(12) Å3 and Z = 1 for the compound 2. Compounds 1 and 2 were constructed from 4-connected {H4ClV16O38} clusters and 6-connected Zn(II) or Co(II) ions, extending in the three dimensions. Square channels with an opening of ca. 7.2 × 7.2 Å were formed through the twining double left-handed helical chains composed of MII octahedral complexes bridged by bpy molecules, which were filled by water and free bpy molecules. Magnetic property was also studied.
Co-reporter:Yumei Kong, Lina Pan, Jun Peng, Bo Xue, Jun Lu, Baoxia Dong
Materials Letters 2007 Volume 61(11–12) pp:2393-2397
Publication Date(Web):May 2007
DOI:10.1016/j.matlet.2006.09.023
Three nanorod-amino acid phosphomolybdates (nanorod-AA-PMo12) (HGly)3[PMo12O40]·(Gly)9 (nanorod-Gly-PMo12, 1), (HLys)3[PMo12O40]·(Lys)4·9H2O (nanorod-Lys-PMo12, 2) and (HHis)3[PMo12O40]·(His)3·H2O (nanorod-His-PMo12, 3), were prepared by the solvent-thermo technique, using reverse micelles as a template, and characterized by transmission electron microscopy (TEM), FT-IR spectroscopy, X-ray diffraction (XRD), cyclic voltammetry (CV), elemental analysis and thermogravimetric analysis (TGA). Antibacterial experiments of the nanorod-AA-PMo12 against Escherichia coli indicated remarkable activity. The {nanorod-Gly-PMo12/PEI}n films were also prepared (PEI = polyethyleneimine) and their antibacterial activity was studied which exhibited potential of solid antimicrobial.
Co-reporter:Yumei Kong, Jun Peng, Zhifeng Xin, Bo Xue, Baoxia Dong, Fengshan Shen, Li Li
Materials Letters 2007 Volume 61(Issue 10) pp:2109-2112
Publication Date(Web):April 2007
DOI:10.1016/j.matlet.2006.08.028
The selective controlled syntheses of crystalline CoMoO4 nanorods (rod-CoMoO4)/nanowhiskers (whiskers-CoMoO4) by using reverse micelles in different molar ratios (w) of [H2O]/[CTAB] under mild hydrothermal conditions are reported for the first time. The obtained rod-CoMoO4/whiskers-CoMoO4 have a monoclinic structure (α-CoMoO4), with diameter range from 10 to 80 nm and their lengths range from several tens of nanometers to 1 μm. The synthesis conditions and formation mechanism of the nanorods/nanowhiskers were discussed. The electrochemistry behaviors of Co2+ and CoMoO4 in nanoscale and in macroscale are compared, from which an interesting result is obtained. Furthermore, the efficient antibacterial property of the nanorods against Escherichia coli (E. coli) was first found.
Co-reporter:Hongsheng Liu;Zhongnin Su;Yanhui Chen;Baoxia Dong;Aixiang Tian;Zhangang Han;Enbo Wang
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 23) pp:
Publication Date(Web):12 OCT 2006
DOI:10.1002/ejic.200600717
Three novel [γ-SiW10O36]8– dimers, [{K(H2O)}2{(μ3-H2O)M(H2O)}(γ-Si2W20O70)]8– (M = Mn2+, 1; Co2+, 2; Ni2+, 3), are isolated from an aqueous acidic medium without isomerization, which is different from most reactions of [γ-SiW10O36]8– with first-row transition metals. They are isomorphous and crystallize in the orthorhombic system, space group Pnma. These species are the first examples of imidazole–potassium mixed salts of Keggin-γ-type dimers having an analogous open structure related to the Wells–Dawson anionic cluster. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Zhenyu Shi;Xiaojun Gu;Xia Yu;Enbo Wang
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 2) pp:
Publication Date(Web):28 NOV 2005
DOI:10.1002/ejic.200500662
A new three-dimensional coordination polymer, {Cu3(4,4′-bpy)3(H2O)[PMo12O40(VO)2]·5H2O}n (1) (4,4′-bpy = 4,4′-bipyridine), which represents the first example of 3D polycatenation generated by unprecedented parallel catenation of the 1D double ladders, has been hydrothermally synthesized. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Zhangang Han, Aixiang Tian, Jun Peng, Xueliang Zhai
Journal of Solid State Chemistry 2006 Volume 179(Issue 10) pp:3209-3213
Publication Date(Web):October 2006
DOI:10.1016/j.jssc.2006.05.014
A three-dimensional (3D) cobalt phosphate: Co5(OH2)4(HPO4)2(PO4)2 (1), has been synthesized by hydrothermal reaction and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic techniques. The title compound is a template free cobalt phosphate. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO6 and PO4 polyhedra. The magnetic susceptibility measurements indicated that the title compound obeys Curie–Weiss behavior down to a temperature of 17 K at which an antiferromagnetic phase transition occurs.A 3D cobalt phosphate with a neutral framework: Co5(OH2)4(HPO4)2(PO4)2 (1), has been synthesized and characterized. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO6 and PO4 polyhedra. Its magnetic property was researched.
Co-reporter:Zhenyu Shi, Jun Peng, Carlos J. Gómez-García, Samia Benmansour, Xiaojun Gu
Journal of Solid State Chemistry 2006 Volume 179(Issue 1) pp:253-265
Publication Date(Web):January 2006
DOI:10.1016/j.jssc.2005.09.051
Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)2]2{[Cu(phen)]2 [SiMo12O40(VO)2]} (1), {[Zn(phen)2]2[GeMo12O40(VO)2]}{[Zn(phen)2(H2O)]2 [GeMo12O40(VO)2]}·3H2O (2) and {[Co(phen)2]2[PMo12O40(VO)2]}{[Co(phen)2(OH)]2 [PMo12O40(VO)2]}·2.5H2O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo12O40(VO)2] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo12O40(VO)2]2− linked to two [Cu(phen)]+ complexes with two [Cu(phen)2]+ countercations. Compound 2 contains two bicapped Keggin anions [GeMo12O40(VO)2]4−, one linked to two [Zn(phen)2(H2O)]2+ cations and the other one linked to two [Zn(phen)2]2+ cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo12O40(VO)2]4− connected by [Co(phen)2]2+ cations. Discrete bicapped Keggin anions [PMo12O40(VO)2] linked to two [Co(phen)2(OH)]+ cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions.Three new Keggin polyoxometalate-based compounds have been synthesized under hydrothermal condition. These three compounds present the bicapped Keggin anions [XMo12O40(VO)2] (X=Si, Ge and P) as building blocks. Among the three compounds, compound 3 is a two-dimensional polyoxometalate-based square network formed by bicapped Keggin anions [PMo12O40(VO)2]4− connected by [Co(phen)2]2+ cations. Discrete bicapped Keggin anions [PMo12O40(VO)2] linked to two [Co(phen)2(OH)]+ cations are located between the layers.
Co-reporter:Bo Xue, Jun Peng, Zhengfeng Xin, Yumei Kong, Li Li and Bin Li
Journal of Materials Chemistry A 2005 vol. 15(Issue 45) pp:4793-4798
Publication Date(Web):04 Oct 2005
DOI:10.1039/B511659G
The creation of new materials for lightweight and high performance displays is an extremely active research field. Inorganic electrochromic ultra-thin film displays possess a keen advantage over other technologies because of their multiple color, fast switching, improved durability, high contrast, high coloration efficiency and low cost. Here we present the successful fabrication of multiple colored electrochromic multilayer films consisting of molybdenum-doped hexagonal tungsten bronze formulated as Na0.2MoxW1−xO3·ZH2O (x
= 0.05)
(Mo0.05–HTB), using a layer-by-layer (LBL) assembly method. The resultant organic–inorganic films exhibit a linear increase in film thickness with assembly progressing. The color and electrochromic contrast of the films are adjustable by changing the mole ratio of Mo to W. Electrochromic contrast, coloration efficiency, switching speed, stability and optical memory for the as-prepared films were carefully investigated. The Mo–HTB/polyethyleneimine films undergo a color transition from colorless to light blue, and finally to dark blue over the potential range from −1.0 to 1.0 V vs Ag/AgCl reference electrode. These results exhibit the validation of an LBL-assembly based intermixing strategy for the design of multiple-hue electrochromic films.
Co-reporter:Zhangang Han, Yulong Zhao, Jun Peng, Aixiang Tian, Qun Liu, Jianfang Ma, Enbo Wang and Ninghai Hu
CrystEngComm 2005 vol. 7(Issue 63) pp:380-387
Publication Date(Web):14 Jun 2005
DOI:10.1039/B501922B
A new series of supramolecular architectures based on Keggin polyoxometalates (POMs): (Hbpy)3[PMo12O40]·2.2H2O (1), (H3/4bppy)4H2[PMo12O40]·3H2O (2), (Hbppy)4H2[SiW12O40]·3H2O (3) and (Hppy)4H2[SiMo12O40]
(4)
(bpy = 4-(5-chloropyridin-2-yl)pyridine, ppy = 4-(5-phenylpyridin-2-yl)pyridine and bppy = 4-(5-(4-bromophenyl)pyridin-2-yl)pyridine), has been prepared and characterized. In compound 1, no direct interaction occurs among POM anion clusters, and the anions together with organic molecule bpys construct the supramolecular frameworks to accommodate guest water molecules. In compounds 2 and 3, Keggin anions form one-dimensional pillar-like inorganic chains as a ‘guest’ to occupy the supramolecular spaces formed by compact organic array, while POMs form two-dimensional layers and alternative array with organic layers in compound 4. Noncovalent interactions of hydrogen bonding, aryl packing and halogen bonding coexist in compounds 1–3. The C–X⋯O (X = Cl or Br) synthon is introduced for the first time to drive self-assembly process of POMs. The crystal structure analyses reveal that the substituted groups of organic bipyridine have a major influence on the packing arrangement of crystals. Additionally, the different cation ∶ anion ratios (3 in 1, and 4 in the other compounds) may also in part affect the packing modes of the organic and inorganic moieties.
Co-reporter:Yuhua Feng, Jun Peng, Zhangang Han, Huiyuan Ma
Journal of Colloid and Interface Science 2005 Volume 286(Issue 2) pp:589-595
Publication Date(Web):15 June 2005
DOI:10.1016/j.jcis.2005.01.062
A novel photosensitive organic–inorganic composite film incorporating polyoxometalate, K7[SiW11O39Co(H3P2O7)] (SiW11CoPP), and diazoresin (DR) has been prepared via layer-by-layer (LBL) self-assembly. Under UV irradiation, followed the decomposition of diazonium in DR, the ionic bonds between the adjacent interfaces of the multilayer film convert to covalent bonds. The LBL multilayers were characterized by UV–vis spectroscopy, X-ray photoelectron spectra (XPS), atomic force microscopy (AFM), FTIR spectrum, cyclic voltammograms (CV), and electron spin resonance (ESR) measurements. UV spectroscopy shows that the deposition process is regular and highly reproducible from layer to layer. XPS spectra confirm the incorporation of DR and SiW11CoPP into the films. Atomic force microscopy image indicates that the film surface is uniform and smooth. Solvent etching experiment proves that the film has significant stability towards polar solvent. Electrochemical behavior of the multilayers is investigated.
Co-reporter:Zhenyu Shi;Xiaojun Gu;Zhifeng Xin
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 19) pp:
Publication Date(Web):29 AUG 2005
DOI:10.1002/ejic.200500330
An unprecedented one-dimensional chainlike compound with green fluorescent emission, (H3O)[Ag3(2,2′-bpy)2(phnz)2(β-Mo8O26)] (bpy = bipyridine, phnz = phenazine) has been synthesized under hydrothermal conditions. The compound is constructed from β-octamolybdate clusters linked through two kinds of silver-ligand subunits, [Ag(2,2′-bpy)(phnz)]+ and [Ag(phnz)]+. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Zhangang Han;Yulong Zhao;Huiyuan Ma;Qun Liu;Enbo Wang;Ninghai Hu;Hengqing Jia
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 2) pp:
Publication Date(Web):18 NOV 2004
DOI:10.1002/ejic.200400471
A 1D double-chain assembly based on the monosubstituted Keggin polyoxometalate (POM) with pendant ligands and of formula {[Ag2(bppy)3][Ag(bppy)2][Ag(bppy)]2PW11Co(bppy)O39}·2H2O (1) [bppy = 5-(4-bromophenyl)-2-(4-pyridinyl)pyridine] has been synthesised and characterised. The crystals of 1 belong to the space group P , Mr = 5801.06, a = 18.720(4) Å, b = 19.474(4) Å, c = 19.815(4) Å, α = 96.30(3), β = 96.07(3), γ = 90.12(3)°, V = 7139(2) Å3, Z = 2, Dcalcd. = 2.699 Mg·m−3. The final statistics based on F2 are GOF = 1.007, R1 = 0.0620 and wR2 = 0.1346 for I > 2σ(I). X-ray diffraction analysis revealed that the structure of 1 contains a 1D chain constructed from a monosubstituted tungstophosphate with one pendant conjugated ligand, five silver−bppy groups and two water molecules. The periphery of the Keggin cluster consists of five Ag−bppy groups so that a bicapped trisupporting Keggin structure is obtained. It is rare that a Keggin anion cluster is simultaneously coordinated to five transition metal atoms. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Yuhua Feng, Zhangang Han, Jun Peng, Xiangrong Hao
Journal of Molecular Structure 2005 Volume 734(1–3) pp:171-176
Publication Date(Web):31 January 2005
DOI:10.1016/j.molstruc.2004.09.017
A new organic–inorganic hybrid mixed-valence Cu(I)/Cu(II) complex [Cu4(ophen)4(mtp)] (1) (Hophen=2-hydroxy-1,10′-phenanthroline, mtp=2-methyl-terephthalate acid) has been hydrothermally synthesized and characterized by XPS spectrum, FTIR spectrum and X-ray single-crystal diffraction. Compound 1 belongs to monoclinic system, space group P2(1)/n, a=10.281(2), b=15.188(3), c=15.333(3) Å, β=105.072(3)°, V=2311.8(8) Å3, Z=2, R1=0.0441. Compound 1 consists of two Cu2(ophen)2+ building units linked by mtp ligand to form a dumbbell shape.
Co-reporter:Yanhui Chen, Jun Peng, Hongquan Yu, Zhangang Han, Xiaojun Gu, Zhenyu Shi, Enbo Wang, Ninghai Hu
Inorganica Chimica Acta 2005 Volume 358(Issue 2) pp:403-408
Publication Date(Web):25 January 2005
DOI:10.1016/j.ica.2004.07.038
The compound H3[l/d-Cd(Cl)(H2O)(phen)2][{l/d-Cd(H2O)(phen)2}2{V16O38 (Cl)}] · 3.5H2O (1) was synthesized via hydrothermal techniques from the starting materials of V2O5, CdCl2, phen, H2C2O4 · 2H2O, CH3COONa and H2O. The compound crystallizes in the space group P21/c of the monoclinic system with a = 12.6315 (2) Å, b = 27.2451 (5) Å, c = 27.3999 (6) Å, α = 90 °, β = 92.3870 (10)°, γ = 90°, V = 9421.4 (3) Å3, Z = 4. In the 3-D structure of 1, a novel supramolecular assembly of enantiomers l/d-[Cd(Cl)(H2O)(phen)2]+ and l,l/d,d-dinuclear Cd complex coordinated by phen groups and V16O38(Cl) cluster is formed via strong intermolecular H-bonding and π ⋯ π stacking interactions with chiral chains of [{l/d-Cd(H2O)(phen)2}2{V16O38 (Cl)}]4−, racemic layers and channels. The channels contain enantiomers l/d-[Cd(Cl)(H2O)(phen)2]+ in pairs. The multiple supramolecular interactions strengthen the stability of compound 1.A novel supramolecular assembly of enantiomers l/d-[Cd(Cl)(H2O)(phen)2]+ and l,l/d,d-dinuclear Cd complex coordinated by phen groups and {V16O38(Cl)} cluster is formed via strong intermolecular H-bonding and π ⋯ π stacking interactions with chiral chains of [{l/d-Cd(H2O)(phen)2}2{V16O38 (Cl)}]4−, racemic layers and channels. The channels contain enantiomers l/d-[Cd(Cl)(H2O)(phen)2]+ in pairs.
Co-reporter:Zhangang Han, Yulong Zhao, Jun Peng, Aixiang Tian, Yuhua Feng, Qun Liu
Journal of Solid State Chemistry 2005 Volume 178(Issue 5) pp:1386-1394
Publication Date(Web):May 2005
DOI:10.1016/j.jssc.2005.02.006
The solid hybrid material (H3/4pbpy)4[PMo12O40]·1.25H2O (1) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) has been prepared and characterized. A structural feature of compound 1 is that the polyoxometalate anions exhibit a one-dimensional inorganic double chain-like structure via weak interactions of O…O. The organic moiety exhibits regular packing with offset aromatic–aromatic interactions between the pbpys, leading to a compact supramolecular framework structure to accommodate the inorganic chains. Compound 1 was employed to fabricate the three-dimensional bulk-modified carbon paste electrode (1-CPE) to research on its electrochemistry properties. The results indicate that 1 retained Keggin molybdate anion electrocatalytic activities toward the reduction of chlorate, hydrogen peroxide and nitrite.A view showing the weak interaction of N…O occurred between organic cations and inorganic anion in compound.
Co-reporter:Xiaojun Gu, Jun Peng, Zhenyu Shi, Yanhui Chen, Zhangang Han, Enbo Wang, Jianfang Ma, Ninghai Hu
Inorganica Chimica Acta 2005 Volume 358(Issue 13) pp:3701-3710
Publication Date(Web):1 September 2005
DOI:10.1016/j.ica.2005.06.002
By the approach of target synthesis, three infinitely extended hybrid compounds based on the saturated Keggin polyoxoanions have been synthesized under hydrothermal conditions: {[Co(phen)2]2[SiMo8VIMo4VO40(VIVO)2]}{[Co(phen)2(H2O)]2[SiMo8VIMo4VO40(VIVO)2]}·3H2O(1), {[Co(phen)2]2[GeMo8VIMo4VO40(VIVO)2]}{[Co(phen)2(H2O)]2[GeMo8VIMo4VO40(VIVO)2]}·4.8H2O(2)and [Ni(phen)2][SiMo10VIMo2VO40(VIVO)2]·2trea·2H2O(3) (phen = 1,10-phenanthroline, trea = triethylamine). The isostructural compounds 1 and 2 belong to the monoclinic space group P21/c and both contain neutral 2D layers and discrete polyoxometalate clusters decorated by transitional metal complexes. They represent an important example of the family of intercalated solids, in which both the 2D layers and the intercalated molecules are polyoxometalates with covalently linked transitional metal complex fragments. Compound 3, crystallizing in the monoclinic space group C2/c , consists of 1D zigzag chains constructed from alternating [SiMo10VIMo2VO40(VIVO)2]2- polyoxoanions and [Ni(phen)2]2+ fragments. More interestingly, these three compounds are constructed directly from saturated polyoxometalates, in which the intact skeletons of Keggin clusters are maintained under hydrothermal conditions. Variable-temperature magnetic susceptibility measurements of compounds 1 and 2 reveal the feature of antiferromagnetic exchange interaction in these compounds.By the approach of target synthesis, three infinitely extended Keggin-based hybrid compounds have been hydrothermally synthesized. The isostructural compounds 1 and 2 contain neutral 2D layers and discrete polyoxometalate clusters decorated by transitional metal complexes. Compound 3 consists of 1D zigzag chains constructed from alternating [SiMo10VIMo2VO40(VIVO)2]2- polyoxoanions and [Ni(phen)2]2+ fragments.
Co-reporter:Huiyuan Ma, Jun Peng, Zhangang Han, Xia Yu, Baoxia Dong
Journal of Solid State Chemistry 2005 Volume 178(Issue 12) pp:3735-3739
Publication Date(Web):December 2005
DOI:10.1016/j.jssc.2005.09.031
A novel nanosized biological active multilayer film composed of polyoxometalate (POM) anion α-[SiW11O39Co(H2PO4)]7−(abbr. SiW11Co–PO4) and poly(diallyldi methylammonium chloride) (abbr. PDDA) was fabricated by layer-by-layer self-assembly (LBL). The composition and growth processes of the films have been determined by X-ray photoelectron spectra (XPS) and ultraviolet-visible absorption spectra (UV). The composite film was formed by the alternate adsorption of SiW11Co–PO4 and PDDA, and the deposition process was quantitative and highly reproducible from layer to layer. The morphology of the film was studied by atomic force microscopy (AFM), which showed that the film was relatively uniform and smooth, and POM anions aggregated into nanoclusters distributing on the surface uniformly. The film exhibited favorable electrochemical behavior of POM indicated by cyclic voltammetry (CV). The film can immobilize the DNA molecules via Mg2+-bridging medium.A novel nanosized biological active multilayer film based on POM anion α-[SiW11O39Co(H2PO4)]7− (abbr. SiW11Co–PO4) and poly(diallyldimethyl ammonium chloride) (PDDA) was fabricated by layer-by-layer self-assembly (LBL). The composite film was formed by the alternate adsorption of SiW11Co–PO4 and PDDA, and the deposition process was quantitative and highly reproducible from layer to layer. The film can immobilize the DNA molecules via Mg2+-bridging medium, which possesses potential biological activity.
Co-reporter:Huiyuan Ma, Jun Peng, Baibin Zhou, Zhangang Han, Yuhua Feng
Applied Surface Science 2004 Volume 233(1–4) pp:14-19
Publication Date(Web):30 June 2004
DOI:10.1016/j.apsusc.2004.03.219
Abstract
A luminescent multilayer film has been fabricated from mixed-addenda polyoxometalate anion [Eu(SiW4Mo7O39)2]13− (EuSiWMo) and polyethyleneimine (PEI) through electrostatic layer-by-layer self-assembly (LBL). The fabrication processes of the film have been monitored by UV-Vis absorption spectra. The results indicated that the composite film was formed by the alternate adsorption of EuSiWMo and PEI, and the layer growth was linear and highly reproducible from layer-to-layer. The elemental composition of the film was obtained from X-ray photoelectron spectrum (XPS). The data of XPS confirmed the presence of the expected elements. The film was smooth and homogeneous as indicated by atomic force microscopy images (AFM). The close-packed nanoclusters of the conglomeration of EuSiWV anions, with a mean grain size of ca. 60 nm, are distributed on the surface uniformly. The mean interface roughness estimated by AFM is about 3.8 nm in an area of 2.0×2.0 μm2. The film exhibited characteristic emission bands of rare-earth ions, consisting with those of the solid sample. In addition, the electrochemical behavior of the film was investigated by cyclic voltammetry, indicating that the electrochemical property of EuSiWMo was fully maintained in the LBL film.
Co-reporter:Xiaojun Gu, Zhenyu Shi, Jun Peng, Yanhui Chen, Enbo Wang, Ninghai Hu
Journal of Molecular Structure 2004 Volume 694(1–3) pp:219-222
Publication Date(Web):June 2004
DOI:10.1016/j.molstruc.2004.03.036
A simultaneous reduction of SO42− to S2− by 2,5-pyridinedicarboxylate under hydrothermal conditions produced a new binuclear copper(II) coordination polymer [CuS(4,4′-bipy)]n (4,4′-bipy=4,4′-bipyridine) (1). Single crystal X-ray analysis revealed that compound 1 consisted of sulfur-bridged binuclear copper(II) units with Cu–Cu bonding which were combined with 4,4′-bipy to generate a three-dimensional network constructed from mutual interpenetration of two-dimensional (6,3) nets. Crystal data for 1: C10H8CuN2S, tetragonal I41/acd, a=14.0686(5) Å, b=14.0686(5) Å, c=38.759(2) Å, Z=32. Other characterizations by elemental analysis, IR, EPR and TGA analysis were also described in this paper.
Co-reporter:Zhangang Han, Yulong Zhao, Jun Peng, Huiyuan Ma, Qun Liu, Enbo Wang, Ninghai Hu
Journal of Solid State Chemistry 2004 Volume 177(Issue 11) pp:4325-4331
Publication Date(Web):November 2004
DOI:10.1016/j.jssc.2004.05.025
Two novel supramolecular assemblies of organic bicapped Keggin polyoxometalates (pbpy)8H3[PW12O40]·2H2O (1) and (pbpy)4H[PMo12O40(VO)] (2) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Crystallographic data for compound (1), C128H103N16O42PW12, triclinic, space group : a=13.4759(8) Å, b=14.6395(11) Å, c=16.5743(10) Å, α=95.764(2)°, β=102.166(2)°, γ=92.9870(10)°, Z=1, V=3171.1(4) Å3; for compound (2), C64H49N8O41PMo12V, triclinic, space group : a=11.5377(11) Å, b=12.7552(8) Å, c=14.9599(10) Å, α=72.270(4)°, β=88.916(2)°, γ=67.865(4)°, Z=1, V=1931.0(3) Å3. X-ray analyses show that both 1 and 2 represent rare organic bicapped Keggin structures and are supported by supramolecular interactions to extend into a 3D framework. In particular, the unusual structure feature of compound 2 contains a simultaneously organic and inorganic capped structure.
Co-reporter:Huiyuan Ma, Jun Peng, Yanhui Chen, Yuhua Feng, Enbo Wang
Journal of Solid State Chemistry 2004 Volume 177(Issue 10) pp:3333-3338
Publication Date(Web):October 2004
DOI:10.1016/j.jssc.2004.05.054
A photoluminescent multilayer film based on Keggin-type polyoxometalate PMo12O403− (PMo12) and transition metal complex tris(2,2-bipyridine) ruthenium [Ru(bpy)3]2+ (Ru(bpy)) was prepared by using layer-by-layer assembly(LBL). The formation of multilayer film was monitored by ultraviolet absorption spectra. The absorption intensity of characteristic peaks increase with a four-layer cycle, indicating that the LBL assembly film grow linearly and reproducibly from layer to layer. The composition of the film was measured by X-ray photoelectron spectrum (XPS). The data of XPS confirmed the presence of the expected elements. The film exhibited photoluminescence arising from π*−t2g ligand-to-metal transition of Ru(bpy) and redox activity attributing to molybdenum-centered redox processes of PMo12. The surface morphology of multilayer film was characterized by atomic force microscopy (AFM). The result shows that the film had a smooth surface with root-mean-square (rms) roughness ca. 1.363 nm for {PEI/(PSS/PEI/PMo12/Ru(bpy))3}. The grains are homogeneously dispersed in the substrate and have a rather narrow diameter size distribution.
Co-reporter:Xiaojun Gu, Yanhui Chen, Jun Peng, Zhenyu Shi, Enbo Wang, Ninghai Hu
Journal of Molecular Structure 2004 Volume 697(1–3) pp:231-235
Publication Date(Web):16 July 2004
DOI:10.1016/j.molstruc.2004.04.015
A new coordination polymer [Cd2(1,10′-phen)2(betc)(H2O)]n (1) (betc=benzene-1,2,4,5-tetracarboxylate, 1,10′-phen=1,10′-phenanthroline) was hydrothermally synthesized from CdCl2·2.5H2O, H4betc and 1,10′-phen at 160 °C. It was characterized by IR, XPS, TG and single-crystal X-ray diffraction. Compound 1 possesses infinite chair-like chains which construct 3D framework through π–π interactions and the hydrogen bond interactions. The fluorescent spectrum study shows that compound 1 exhibits blue fluorescent emission in the solid at room temperature.
Co-reporter:Huiyuan Ma, Jun Peng, Zhangang Han, Yuhua Feng, Enbo Wang
Thin Solid Films 2004 Volume 446(Issue 2) pp:161-166
Publication Date(Web):15 January 2004
DOI:10.1016/j.tsf.2003.09.040
A nanosized composite film based on polyoxometalate anion [Eu(SiW10VO39)2]15− (EuSiWV) and polyethyleneimine (PEI) has been synthesized by layer-by-layer (LBL) self-assembly. The components and growth processes of the film have been determined by X-ray photoelectron spectra and ultraviolet–visible absorption spectra. The results showed that the composite film was formed by the alternate adsorption of EuSiWV and PEI, and the deposition process was quantitative and highly reproducible from layer to layer. Atomic force microscopy images indicated that the surface of the film was relatively uniform and smooth. The EuSiWV salt aggregated into nanoclusters with approximately 10 nm mean grain size, distributing on the surface uniformly. The surface roughness was approximately 2.4 nm. Fluorescence properties of the film were consistent with those of the solid sample, exhibiting obvious activity of fluorescence and incarnating the characteristic luminescence of Eu3+. In addition, the electrochemical behavior of the film has also been investigated, demonstrating that the electrochemical property of EuSiW10V was fully maintained in the LBL film.
Co-reporter:Jun Peng, Hui-Yuan Ma, Zhan-Gang Han, Bao-Xia Dong, Wen-Zhuo Li, Jun Lu and En-Bo Wang
Dalton Transactions 2003 (Issue 20) pp:3850-3855
Publication Date(Web):17 Sep 2003
DOI:10.1039/B307947N
A novel series of Keggin species with a covalently bonding support-ligand, formulated α-[SiW11O39M(H2PO4)]n−
(M = CoII, MnII, NiII or CrIII), have been synthesized and characterized by elemental analyses, IR, CV, NMR and X-ray powder diffraction measurements. The structure is reminiscent of an ancient Chinese three-legged wine vessel, and is a possible model for POM–nucleotide interaction. An interesting property is the different thermal behaviors for this series in comparison with those for corresponding 3d metal monosubstituted Keggin polyoxometalates. This can be attributed largely to the pendant surface ligand and H bonding interaction. Compared with α-PW11M, the orders of line broadening of 31P NMR signals are the same for the two series of complexes α-PW11M and α-SiW11M–PO4, but both contact and dipolar interactions might make a significant contribution to the chemical shift for phosphorus for the latter.
Co-reporter:Jun Peng, Wenzhuo Li, Enbo Wang and Qinglong Bai
Dalton Transactions 2001 (Issue 24) pp:3668-3671
Publication Date(Web):27 Nov 2001
DOI:10.1039/B104132K
Novel Keggin anions with covalently bonding pendant surface ligands, formulated as [SiW11O39M(H3P2O7)]7−, (M = MnII, CoII, NiII and ZnII), were synthesized, and characterized by elemental analyses and IR, CV and NMR physical measurements. The novel complexes are expected to have the ability to anchor the clusters on supports via terminal phosphato group–support linkages.
Co-reporter:Jing Chen, Jing-quan Sha, Jun Peng, Zhen-yu Shi, Bao-xia Dong, Ai-xiang Tian
Journal of Molecular Structure (26 November 2007) Volume 846(Issues 1–3) pp:
Publication Date(Web):26 November 2007
DOI:10.1016/j.molstruc.2007.01.044
Two novel organic–inorganic hybrid polyoxometalates, [Cu(2,2′-bpy)2]2[HmXMo10VIMo2VO40]·2H2O (X = P, m = 1 1; X = Si, m = 2 2; 2,2′-bpy = 2,2′-bpyridine), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. They are isostructural, possessing orthorhombic, and the parameters of unit cells for compound 1 are space group Pbca, a = 17.317(4) Å, b = 17.092(3) Å, c = 20.587(4) Å, V = 6445(2) Å3, Z = 4; for compound 2 are space group Pcab, a = 17.181(3) Å, b = 18.198(4) Å, c = 20.672(4) Å, V = 6463(2) Å3, Z = 4. The two compounds show a layer framework constructed from Keggin-polyoxoanion clusters and [Cu (2, 2′-bpy)2]2+ coordination polymer fragments via weak covalent interactions, resulting in a 3D network via supramolecular interactions. Their electrochemical properties are studied in detail.
Co-reporter:Yan Shen, Jun Peng, Huanqiu Zhang, Changyun Chen, Fang Zhang and Alan M. Bond
Journal of Materials Chemistry A 2011 - vol. 21(Issue 19) pp:NaN6998-6998
Publication Date(Web):2011/04/06
DOI:10.1039/C1JM10114E
Silver nanoparticles (NPs)-deposited tungstosilicate (Ag/SiW12/Ag) microtubes were obtained by a redox reaction between the heteropoly blue microtubes and Ag+ ions. The Ag/SiW12/Ag microtubes were characterized by FT-IR and XPS spectroscopy. Their morphology was examined by ESEM-FEG, showing that the microtubes kept their original microtubular morphology well after reacting with Ag+ ions and the silver NPs exhibited regular spherical morphology. The current–voltage properties of the Ag/SiW12/Ag microtubes were also briefly investigated.
Co-reporter:Zhe-Yu Zhang, Jun Peng, Zhen-Yu Shi, Wan-Li Zhou, Shifa Ullah Khan and Hong-Sheng Liu
Chemical Communications 2015 - vol. 51(Issue 15) pp:NaN3093-3093
Publication Date(Web):2015/01/02
DOI:10.1039/C4CC09612F
Nine new Sb-bicapped α-Keggin-type heteropolyoxoniobates (HPNb) were synthesized under hydrothermal conditions. Among them, the As-centered HPNb was never reported before, and the two dimer compounds are the biggest isolated HPNbs at present.
Co-reporter:Huanqiu Zhang, Jun Peng, Yan Shen, Xia Yu, Fang Zhang, Jilan Mei, Bin Li and Liming Zhang
Chemical Communications 2012 - vol. 48(Issue 37) pp:NaN4464-4464
Publication Date(Web):2012/03/15
DOI:10.1039/C2CC00132B
Fluorescent microtubes based on α-Keggin tungstosilicate and fluorescein (SiW12-F) have been obtained by using a simple method, which present tunable photoluminescence from sky blue to green to red by variation of excitation light. The SiW12 component can inhibit photobleaching of fluorescein.
Co-reporter:Hai-jun Pang, Jun Peng, Chun-jing Zhang, Yang-guang Li, Peng-peng Zhang, Hui-yuan Ma and Zhong-min Su
Chemical Communications 2010 - vol. 46(Issue 28) pp:NaN5099-5099
Publication Date(Web):2010/06/15
DOI:10.1039/C003048A
A novel compound, [Cu(bimb)]2(HPW12O40)·3H2O (bimb = 1,4-bis(imidazol-1-ylmethyl)biphenyl) with a polyoxometalate-encapsulated 3D metal–organic pseudo-rotaxane framework that can be described as a 2-fold dianet topology showing well-defined 1D nano-scale tunnels, has been synthesized hydrothermally, and its de-/rehydration behavior has been investigated.
Co-reporter:Haijun Pang, Carlos J. Gómez-García, Jun Peng, Huiyuan Ma, Chunjing Zhang and Qingyin Wu
Dalton Transactions 2013 - vol. 42(Issue 47) pp:NaN16601-16601
Publication Date(Web):2013/09/10
DOI:10.1039/C3DT51899J
The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d–4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2]·nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. A structural feature in 1 and 2 is that each [SiW11O39]8− cluster (SiW11) is connected to ten metals (five Ag+ and five Ln3+ cations), representing the highest number of connected metal atoms to any mono-lacunary Keggin anion to date. This large connectivity leads to a structure with a purely inorganic 3D framework with two kinds of channels along the [100] and [010] directions. The magnetic properties of both compounds show the expected magnetic moments (0.8 and 1.6 amu K mol−1 per Ce3+ and Pr3+ ion, respectively) and confirm the presence of isolated Ce3+ and Pr3+ ions.
Co-reporter:Hongsheng Liu, Carlos J. Gómez-García, Jun Peng, Jingquan Sha, Yangguang Li and Yechao Yan
Dalton Transactions 2008(Issue 44) pp:NaN6218-6218
Publication Date(Web):2008/09/25
DOI:10.1039/B805714A
Three new organic–inorganic hybrid complexes based on 3d-transition metal monosubstituted Keggin polyoxometalates (POMs) with imidazole (Im) as pendant ligands, formulated as (HIm)6[SiW11O39NiIm]0.8[SiW11O39Ni(H2O)]0.2·7H2O (1), (Im)4Na6[SiW11O39MnIm]0.69[SiW11O39Mn(H2O)]0.31·7.5H2O (2) and (HIm)6[SiW11O39CoIm]0.63[SiW11O39Co(H2O)]0.37·7H2O (3), have been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy, elemental analysis, TG analysis, cyclic voltammetry, magnetic properties, EPR and single-crystal/powder X-ray diffraction. The structural analyses indicate that the 3d metal atoms are incorporated into the vacancy of the α-[SiW11O39]8− (SiW11). Complexes 1–3 are the first examples of crystallographically characterized 3d-transition metal mono-substituted POMs with an antenna organic ligand synthesized under normal bench conditions.
