Two New Iron Coordination Polymers Based on Fe-pyta ChainsIncorporating Pyridine-2,4,6-tricarboxylate

Reaction of FeCIz＇6H20, pyridine-2,4,6-tricarboxylic acid（H3pyta） and NaOH in the hydrothermal system at 185 ℃ resulted in the formation of 1D coordination polymer[Fe（Hpyta）（H2O）2]（1） based on Fe-Hpyta chains. When the abpt[abpt=-4-amino-3,5-bis（4-pyridyl）-l,2,4-triazole] ligand was employed in the reaction system, a 3D supramolecular porous network （H2bpt）[Fe（pyta）（H2O）2]·4H2O（2） was obtained. The framework was constructed with negative （Fe-pyta） chains and the positive H3bpt^＋ in situ, formed from the abpt reagent, to form 1D channels filled with guest water molecules via hydrogen-bonds. X-Ray diffraction crystal structure analysis shows that complex 1 crystallized in the monoclinic system, space group C2/c, a=1.1490（5） nm, b=0.9008（4） nm, c=1.0058（5） nm, B=107.254（9）°, V=0.9942（8） nm3, Z=4; and complex 2 crystallizes in the triclinic system, space group P1 with a=0.90392（11） nm, b=0.96027（11 ） nm, c=1.55540（18） nm, a=73.558（2）°,B= 86.126（2）°,r= 68.745（2）°, V=1.2059（2） nm^3 and Z=2.     

A Photoluminescent Bimetallic Zinc-pyridinedicarboxylate：Diverse Supramolecular Motifs from Distinct Hydrogen Bonds

A cyclic bimetallic metal-organic complex [Zn（C）（H-fmpdc）（H2O）]2·2H2O （fmpdc = 4-（furan-2-yl）-2,6-dimethylpyridine-3,5-dicarboxylate） was synthesized and characterized by single-crystal X-ray analysis. The compound crystallizes in orthorhombic, space group Pbca with a = 12.905（2）, b = 14.774（3）, c = 16.833（3）A, V= 3029.4（10）A^3 Z = 4, Dc = 1.644 g/cm^3, F（000） = 1616, R = 0.0347 and wR = 0.0956 （I 〉 2σ（I））. There exist diverse supramolecular motifs （1-D, 2-D and 3-D） from distinct hydrogen bonds in the crystal structure of the title compound. The furanyl group has obvious contribution to the red-shift in the photoluminescent spectrum of the H2fmpdc ligand. The title compound 1 shows strong photoluminescence with emission maximum at 2 = 402 nm （λex.max = 367 nm）.     

Synthesis,Characterization, and Properties of Supported Tungstozincate Bridged by Co（Ⅱ） Complex Fragment

[Co^11（phen）3]2[{（ZnW12O40）Co^11（phen）2（H2O）}2Co^11（trien）2（NaH2O）2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{（ZnW12O40）Co（phen）2（H2O）}2Co（C6H18N4）2·（NaH2O）2]^4- in which each supported Keggin anion [（ZnW12O40Co^11（phen）2（H2O）]^4- acts as a ligand to coordinate to central bridging Co^2＋ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction（0=-46.796 K）.     

A Novel 2D Architecture from Bismuth and Flexible Ligand N,N'-Diacetic Acid Imidazolium Chloride

A new compound {[Bi（trans-DAM）（cis-DAM）（H2O）]NO3·H2O}n 1 derived from bismuth and the flexible ligand N,N＇-diacetic acid imidazolium chloride （H2DAMCl） was obtained by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic P21/c space group with a = 9.2298（18）, b = 13.339（3）, c = 17.090（3） , β = 105.38（2）°, V = 2028.7（7）A^3, Z = 4, C14H18N5O13Bi, Mr = 673.31, Dc = 2.204 g/cm^3, F（000） = 1296, μ = 8.772 mm-1, the final R = 0.0472 and wR = 0.1441 for 4129 observed reflections （I 〉 2σ（I））. In 1, the carboxylic groups from DAM- ligands adopt a cheating mode to link bismuth ions to form a 2D sheet network. These sheets are further connected by hydrogen bonding interactions to give an interesting 3D supramolecular framework. 2D correlation analysis of IR of 1 with thermal and magnetic perturbation was introduced to ascertain the characteristic adsorption of the groups overlapped in the 1D IR spectrum. Additionally, compound 1 exhibits fluorescent emission at room temperature.     

两个N-己酰基水杨酰肼合镍(Ⅱ)配合物的合成、结构及抗菌活性的研究

The two trinuclear nickel（Ⅱ） complexes, Ni3（C13H15N2O3）2（C5H5N）4 （1） and Ni3（C13H15N2O3）2（C5H5N）2- （C3H7NO）2 （2）, were prepared by the reaction of Ni（OAc）2·4H2O with N-hexanoylsalicylhydrazide. The crystal structures of complexes were determined by X-ray diffraction analysis. Complex 1 takes triclinic symmetry with space group P-1 and cell dimensions of a=0.92377（2） nm, b= 1.08786（6） nm, c= 1.29391（3） nm, α=76.395（4）°, β=78.418（3）°, γ=67.378（4）°, V= 1.15772（7） nm^3, Z= 1,μ= 12.63 cm^-1. Complex 2 belongs to triclinic system and P2（1） space group and the crystallographic data： a= 1.4889（2） nm, b= 1.0389（1） nm, c= 1.4994（2） nm, β= 96.174（4）°, V=2.3058（5） nm^3, Z=2,μ= 12.70 cm^-1. The structures of the two molecules are similar. The three nickel atoms in each molecule of the two title complexes arrange in a strictly linear structure. The central nickel atom of the molecule adopts octahedral configuration, while the two nickel atoms on the two sides adopt square-planar configuration in each molecule. But the central nickel atoms of the two complexes have different axial ligands, which cause a slight difference in the bond distances of the octahedron. The antibacterial activity of compound 1 against seven common bacteria was investigated.     

Synthesis and Crystal Structure of a New Cadmium（Ⅱ） Supramolecular Network Containing Chelating Imidazole-4-carboxylate Ligand

A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.     

New Inorganic-organic Hybrid Compound Containing One Dimensional Keggin Polyoxometalate[SiW11O39Co]6- Chains:Preparation,Characterization and Application in Chemically Bulk-modified Electrode

A new inorganic-organic hybrid compound based on polyoxometalate and organic ligand formulated as （H2bpp）3[SiWlIO39Co]-2H20（1）[bpp=l,3-bis（4-pyridyl）propane] was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR, TG, and cyclic voltammetry. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of interesting cobalt-monosubstituted POMs one dimensional chain together with protonated bpp ligands. Additionally, the polyoxoanions combined with the discrete organic substrates by hydrogen bond interactions to afford a supramolecular 3D network structure. The hybrid compound 1 was used as a bulk modifier to fabricate a three-dimensional chemically modified carbon paste electrode（1-CPE） by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE were studied in detail. The results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite or bromate in 1 mol/L 1-12SO4 aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the insolubility of compound 1 and the supramolecular interactions existed between 1D POM anion chains and organic ligand bpp, which is very important for practical applications in electrode modification.     

The First Example of a Supramolecular Structure Containing [2-（1H-Pyrazol-3-yl）-pyridine] Complex and both α- and β-Octamolybdates

The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.     

Synthesis,Crystal structure and Luminescent Property of a New 3D Supramolecular Compound （C6H6NO2）3（C6H5NO2）（PW12O40）·2H2O

A supramolecular compound （C6H6NO2）3（C6H5NO2）（PW12O40）·2H2O including the Keggin-type [PW1O40]3- polyanion, [HC6H5NO2]＋ （protonated pyridine-4-carboxylic acid molecule）, C6H5NO2 （pyridine-4-carboxylic acid molecule） and two free H20 molecules has been synthesized by the hydrothermal method and characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction and powder X-ray diffraction. The crystal belongs to orthorhombic, space group Pnnm with a = 1.0483（3）, b = 1.4368（6）, c = 2.0526（7） nm, V= 3.0918（18） nm3,Z = 2, F（000） = 3004, Mr= 3406.07, Dc= 1.757 g.m-3,μ = 41.241 mm-1, the final R = 0.0387 and wR = 0.1089 for 2091 observed reflections withI〉 2σ（I）. A total of 30431 reflections were collected, of which 3083 were independent （Rint = 0.0605）. S is 1.182. The title compound presents a 3-D structure via intermolecular hydrogen bonds among [PW12O40]3- polyanions and pyridine-4-carboxylic acid ligands. The ultraviolet and luminescence spectra have been studied at room temperature, of which the purple fluorescent emission is located at 363 nm when excited at 264 nm. Fluorescent emission of the compound derives from the π-π＊ transitions in the pyridine-4-carboxylic acid ligands.     

{Na2[μ2-(C6H4O2)2](C6H4OOH)2}4-的结构及其在固态合溶液中的NMR比较

The new compound （NH3CH2CH2NH3）2{Na2[μ2-（C6H4O2）2]（C6H4OOH）2} has been synthesized and characterized by elemental analysis, IR, UV, NMR and single crystal X-ray diffraction. The yellow crystals crystallized in the triclinic system with space group P-1 and a=0.6091（2） nm, b= 1.0274（3） nm, c= 1.2466（4） nm, α=89.073（6）°, β=89.376（6）°, γ=78.873（5）°, V=0.7653（4） nm^3, Z= 1, R1=0.0568, wR2=0.1198. Every sodium ion coordinates in trigonal prismatic fashion with two O atoms from a terminal chelating catecholato ligand and four O atoms from bridging P2 catecholato ligands, Two neighboring NaO6 trigonal prisms are face-shared and centrosymmetric with regard to the inversion center consisting of four tri-bridging O atoms to form a binuclear cluster {Na2[μ2-（C6H4O2）2]}^2- anion. The comparison of ^13C NMR spectrum of tlie complex in solid state with that in solution indicated that the rapid exchange between the bridging [μ2-（C6H4O2]^2- and terminal [C6H4OOH]^- ligands was present in solution.     

Solvothermal Synthesis, Structural Characterization and Properties of Two New Layered Lanthanide Sulfates

Two new layered lanthanide sulfates,[C₁₀H₁₀N₂][Pr₂(SO₄)₄(H₂O)₂](1)and[H₅O₂][Sm(SO₄)₂(H₂O)₃](2)were synthesized via solvothermal reaction and structurally characterized by single-crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Crystal data for compound 1, triclinic, P space group, a=0.8052(4) nm, b=0.9438(4) nm, c=1.4990(7) nm, α=79.450(5)°, β= 83.703(5)°, γ=74.048(5)°, V=1.0746(9) nm³, Z=2; for compound 2, monoclinic, P2₁/c space group, a=0.6599(11) nm, b=1.8940(3) nm, c=0.8765(14) nm, β=96.596(2)°, V=1.0883(3) nm³, Z=4. Structure analysis indicates that both the compounds exhibit a 2D corrugated layer structure, with protonated 4,4'-bipyridine cations and water dimmers (H₅O₂)⁺ located between the inorganic layers of compounds 1 and 2, respectively. Luminescent properties of compounds 1 and 2 were further investigated.     

A Novel Hydrogen-bonded Three-dimensional Network Complex Containing Nickel

A novel complex, (H3O)2[Ni(2,6-pydc)2] · 2H2O was synthesized in an aqueous solution and characterized by means of single-crystal X-ray diffraction, elemental analyses and IR spectra. The X-ray structural analysis revealed that the novel compound forms three-dimensional(3D) networks by both π-π stacking and hydrogen-bonding interactions. The crystal data for the complex are a = 13. 853 (3) nm, b= 9. 6892 (19) nm,c=13.732(3) nm, α=90. 00°, β=115.52(3)°, γ=90.00°, Z=3, R1=0. 0786, wR2=0.1522.     

基于一维[H_2Mo_4O_(14)]_n~(2n-)链和双吡啶双酰胺配体的三维锌配合物的合成、结构与性能

选择柔性的双吡啶双酰胺配体N,N'-双(3-吡啶甲酰胺基)-1,2-乙烷(3-bpye)、钼酸铵和氯化锌在水热条件下自组装制备了一个基于一维[H_2Mo_4O_(14)]_n~(2n-)链的三维锌配合物[Zn(3-bpye)(H_2Mo_4O_(14))(H_2O)_2],并通过元素分析、红外光谱、热重分析等技术手段研究了配合物的结构,并利用X射线单晶衍射分析进行了晶体结构表征。结构解析揭示标题配合物是三斜晶系,P-1空间群,晶胞参数a=0.61310(3)nm,b=1.04750(6)nm,c=1.06540(6)nm,α=78.5540(10)°,β=77.5350(10)°,γ=89.9050(10)°,V=0.65420(6)nm~3,M_r=981.47,D_c=2.491 g/cm~3,Z=1,F(000)=468,R_1=0.0290,ωR_2=0.1068。标题配合物中,金属锌离子连接一维[H_2Mo_4O_(14)]_n~(2n-)链形成一种二维无机双金属层[Zn(H_2Mo_4O_(14))]_n,相邻的层间又通过双齿配体3-bpye连接形成三维CdSO_4拓扑的骨架结构。配合物表现出强的荧光发射特性,而且其在紫外光照下对亚甲基蓝和罗丹明B均有明显的催化降解活性。     

A Novel Dimer--Heteropolytungstate with a Vanadium Atom as the Centre--Synthesis and Structural Characterization of (H3O)4[VW12O40Na(H2O)4]2

A novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,βA novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,β=93.17(3)°,γ=117.47(3)°,V=2.2106(8) nm3,Z=1,Dc=4.552 g.cm-3,λ(Mo Kα)=0.071073 nm,μ=31.402 mm-1,F(000)=2648,R=0.0780.The title compound consists of two Keggin structure units linked together with two hydrated sodium cations to form a dimer with a porous structure with the pore dimension of 0.766 nm×0.7785 nm.     

萘磺酸型离子配合物的合成及其分子识别性能

常温反应条件下制备了4个基于乙二胺和1,5-萘二磺酸的配位化合物[M(en)(H_2O)_4]·1,5-nds·(H_2O)_2(M=Ni(1),Co(2),Cd(3),Cu(4),nds=1,5-萘二磺酸;en=乙二胺),并通过红外光谱、元素分析、X射线单晶衍射、X射线粉末衍射和热重分析等技术手段确定了其晶体结构。结构分析表明,该系列配合物属于同构体系,单斜晶系,C2/c空间群。以配合物1为例,其晶胞参数为a=1.69026(19)nm,b=1.01373(11)nm,c=1.3448(3)nm,α=90°,β=120.2650°,γ=90°,V=1.9901(5)nm~3,Z=4,Dc=1.713 g/cm~3,F(000)=1072,R_1=0.0326,wR_2=0.0867。该系列配合物的中心金属为六配位模式,与来自乙二胺的2个N原子和4个H_2O中的氧原子配位。游离水与磺酸氧和配位水之间存在着丰富的氢键作用,构筑成三维的网络结构。测定了以Cd为中心金属配合物3的荧光光谱,发现其在对于甲醇的小分子识别性能方面具有应用前景。     

Multi-component Hydrogen-bonding Organic Salts Formed from 1-Methylpiperazine with Aromatic Carboxylic Acids: Synthons Cooperation and Crystal Structures

1-Methylpiperazine was employed to crystallize with 2,4-dihydroxybenzoic acid and 1,8-naphthalene acid, affording two multi-component hydrogen-bonding salts [(C₅H₁₄N₂)²⁺·(C₇H₅O₄)_2-·H₂O](1) and [(C₅H₁₄N₂)²⁺(C₁₂H₆O₄)²ˉ·2H₂O](2). These two forms of salts are both monoclinic systems with space group P2₁/c(14). The lattice parameters of salts 1 and 2 are a=1.32666(10) nm, b=0.90527(7) nm, c=1.67107(13) nm, β=103.125(1)° and a=1.4950(2) nm, b=0.75242(15) nm, c=1.6563(3) nm, β=92.834(2)°, respectively. Expected classical hydrogen bonds N―H…O and O―H…O appear in the chargetransfer salts, and asymmetric units of these two forms both contain water molecules which play a significant role in building novel supramolecular architectures. Robust hydrogen-bond interactions between 1-methylpiperazine and aromatic acid provide sufficient driving force to direct the two crystals to three-dimensional structures. Weak interactions C―H…O emerging in salts 1 and 2 further enhance their crystal structures. As a consequence, hydrogen-bonding interactions in these compounds afford diverse 3D net supramolecular architectures. Thermal stability of these compounds was investigated by thermogravimetric analysis(TGA).     

A Novel Layered Complex with Rhomboidal Channels： Hydrothermal Synthesis, Crystal Structure, and Properties of Cu （4,4′-bipy）2（H2PO4）2（H2O）2（bipy=bipyridine）

The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)₂(H₂PO₄)₂(H₂O)₂. The crystal structure comprises discrete neutral Cu(4,4′-bipy)₂(H₂PO₄)₂(H₂O)₂ units. The copper atom, located on the crystallographic twofold axis, is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions, and two dihydrogen phosphate oxygen atoms at the axial positions, forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca. 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm, respectively. The two-dimensional networks are stacked parallelly on each other along c-axis to give an extended three-dimensional channel network with an interlayer distance of ca. 0.5030 nm. Crystal data: triclinic, space group P1, a=1.0253(2) nm, b=1.4501(3) nm, c=0.79715(16) nm, α=97.91(3)°, β=90.99(3)°, γ=85.54(3)°, V=1.1703(4) nm³, Z=2, R=0.0892, wR=0.2451.     

Two New Piperazine Templated Lanthanide Sulfates with 2D Corrugated Layered Crystal Structures

Two new piperazine templated lanthanide sulfates (C₄N₂H₁₂)_1.5[Ln(SO₄)₃(H₂O)]·H₂O[Ln=Gd(1), Tb(2)] have been synthesized solvothermally and structurally characterized by single crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Single crystal X-ray diffraction reveals that both compounds 1 and 2 crystallized in the monoclinic crystal system, with space group P2₁/c and cell dimensions: a=0.64468(19) nm, b=2.9979(9) nm, c=0.9818(3) nm, β=101.271(4)°, V=1.8608(10) nm³, Z=4 for compound 1; a=0.64259(19) nm, b=3.0010(9) nm, c=0.9812(3) nm, β=101.229(4)°, V=1.8560(10) nm³, Z=4 for compound 2. Compounds 1 and 2 are isomorphous and have similar 2D corrugated inorganic frameworks fabricated via the connection of single chains and S2O₄ groups, while fully protonated piperazine cations and water molecules are located between the inorganic layers. The solid state luminescent properties of compound 2 were investigated and it displayed a typical luminescent property of Tb³⁺ with excitation wavelength at 371 nm.     

双核锌配合物[Zn(dna)(phen)(H_2O)]的合成、结构及性质

以5,5'-二硫代双(2-硝基苯甲酸)(H2dna)和1,10-邻菲啰啉(phen)为配体在水热条件下合成了标题配合物,并利用元素分析、傅里叶变换红外光谱、X射线单晶衍射、X射线粉末衍射以及热重分析等技术手段对该配合物进行了结构和性质表征。晶体结构分析表明:配合物为单斜晶系,P2_1/n空间群,a=1.5312(3)nm,b=1.16054(18)nm,c=1.5609(3)nm,β=110.451(2)°,V=2.5990(7)nm~3,Z=4。该配合物为环状双核结构。基于氢键作用邻近的双核分子相连形成一维超分子链。而邻近超分子链又基于S幆O和CH幆π的弱相互作用扩展形成三维超分子网结构。该配合物失水后的产物保持相对稳定,直到245~450℃配体才开始分解,表现出良好的热稳定性。配合物在波长为280 nm的光源激发下,在440 nm有较强的荧光发射峰,且发射峰的形状与H2dna配体相似,但配合物的荧光强度相比H2dna配体有了明显的增强。     

Synthesis,Electrocatalytic Properties and Crystal Structure of a New Organic—Inorganic Hybrid Constructed from Dodecamolybdophosphoric Acid and Benzotriazole

IntroductionIn the last few years there has been a rapidlygrowing number of reports in the literature ad-dressing the use of polyoxometalate- based hybridmaterials as catalysts,non- linear optical materialsand anti- virus drugs[1— 5] . In all the cases men-tioned above,the size,the shape and the chargesof the inorganic counter anions strongly affect theproperties of the materials. Polyoxometalates arelarge in size and high in electron accepting abili-ty[6] .They can form novel compounds with …