摘要
本论文利用水热技术，设计合成了8种以经典Keggin型多酸阴离子以及同多酸阴离子[Mo_8O_(26)]~(4-)为结构导向的铜-柔/刚性多唑类配体的配合物，并通过元素分析、IR、TG、XPRD和X-射线单晶衍射对晶体结构进行了表征，对部分化合物的电化学性质、磁性和光催化性质等进行了初步研究。
1.以双四唑基硫醚为有机配体，以铜离子为中心金属离子，通过引入三种不同的多金属氧酸盐，在水热条件下合成并表征了三个结构新颖的无机有机杂化配合物，并讨论了不同的多阴离子对晶体结构的影响。
[Cu(bmte)(H_2Mo_8O_(26))_(0.5)]·3H_2O (1)
[Cu_3(bmte)_3(HSiMo_(12)O_(40))]· H_2O (2)
[Cu_3(bmte)_3(HGeMo_(12)O_(40))]· H_2O (3)
bmte=1,2-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)ethane
在化合物1中，两个bmte配体通过三个N原子螯合了两个CuI离子，进而形成了一个双核的纳米尺寸的亚单元[Cu2(bmte)2]2+，然后双核的[Cu2(bmte)2]2+单元由[Mo8O26]~(4-)多阴离子连接形成一个一维链。在化合物2中，由三个CuI离子和三个bmte配体形成了纳米尺寸的三核[Cu3(bmte)3]3+金属簇，相邻的三核簇单元通过[SiMo_(12)O_(40)]~(4-)多阴离子连接形成了一个“Z”字型的一维链。相邻的一维链通过bmte和多阴离子的氢键作用进而形成了二维层状化合物。化合物3中因[GeMo_(12)O_(40)]~(4-)和化合物2中的[SiMo_(12)O_(40)]~(4-)带有相同的电荷和相似的尺寸，而形成了与化合物2相同的结构。
2.以Keggin型多酸SiMo_(12)O_(40)4-和SiW12O404-为结构导向剂，通过引入刚性的苯并三氮唑有机胺配体，设计、合成并表征了2个新的金属铜的多酸基多核配合物：
[CuI8(BTA)4(HBTA)8(SiMo_(12)O_(40))]·2H_2O (4)
[CuⅡ6(OH)4(BTA)4(SiW12O40)(H_2O)6]·6H_2O (5)
HBTA=1-H-1,2,3-benzotriazole
在化合物4中，八个CuI通过十二个HBTA/BTA连接形成一个八核的CuI铜簇，这个金属簇由SiMo_(12)O_(40)4-上两个端氧和两个桥氧连接形成一个一维具有波浪形结构的化合物。这个八核的铜单元在多金属氧酸盐(POM)体系中代表了仅由含氮配体和金属构筑的最大数目的金属簇。在化合物5中，四个BTA配体连接了五个CuⅡ离子形成了一个史无前例的类似“卟啉”状的结构单元，这个单元通过另外的一个CuⅡ离子连接，形成一个一维的金属有机带。SiW_(12)O_(40)~(4-)阴离子作为四齿无机连接剂，将这个一维带拓展成具有(83)2(85·10)拓扑结构的二维网络。据我们所知，这两个化合物代表了多酸领域中首例由金属-HBTA和多金属氧酸盐构筑的无机有机多核金属杂化物。
3.以Keggin型多酸为结构导向剂，通过引入刚性的苯并咪唑和5,6-二甲基苯并咪唑配体，设计、合成并表征了3个新的金属铜配合物：
[CuⅡ2(biz)_8(PMoVI11MoVO40)(H_2O)_2]· H_2O (6)[CuI_4(biz)_8(SiW_(12)O_(40))]· H_2O (7)
biz=benzimidazole
[CuI_2(dmbiz)_4(Hdmbiz)(HSiW_(12)O_(40))](8)
dmbiz=5,6-dimethyl benzimidazole
在化合物6中，两个含有CuⅡ的金属有机单元通过氢键作用分别与四个多阴离子PMo_(12)O_(40)3-相连，并且每个多阴离子都通过氢键作用连接了八个金属有机单元，最终形成了一个由氢键连接的(4,8)-连接的三维超分子网络。在化合物7中，采用了SiW_(12)O_(40)4-作为无机阴离子配体，该化合物中存在着弱的Cu···O键和氢键作用，进而形成6-连接的三维超分子网络。与化合物6和7相比，在化合物8中，我们采用了dmbiz作为含氮配体，最终我们得到了一个具有NaCl拓扑结构的三维超分子化合物。
4.在本工作中，我们实现了在水热体系中定向组装多酸基有机胺功能配合物，并探索了该体系组装过程的影响因素，包括：pH、温度、反应时间、多阴离子类型以及填料的配比等。此外，我们研究了部分化合物的电化学性质、磁性以及光催化降解亚甲基蓝的性能，结果表明部分化合物展现出很好的性能，成为潜在的无机功能材料。
In this paper, eight new functional complexes based on copper-flexible/rigid organonitrogenligands and structure-oriented by classical Keggin-type polyanions and [MO_8O_26]~(4-)anion, havebeen synthesized under hydrothermal conditions and structurally characterized by elementalanalyses, IR, TG, XPRD, and single crystal X-ray diffractions. The electrochemical properties,the magnetic properties and photocatalytic properties of these compounds have been studied.
1. Three new inorganic-organic hybrid complexes structure-oriented by three kinds ofpolyoxometalate anions have been hydrothermally synthesized by using the flexible bis(tetrazole)as organic ligands and copper ions as central metal ions. The influence of different kinds ofpolyoxometalates on crystal structures has been discussed:
[Cu(bmte)(H_2MO_8O_26)0.5]·3H_2O (1)
[Cu_3(bmte)_3(HSiMo_(12)O_(40))]· H_2O (2)
[Cu_3(bmte)_3(HGeMo_(12)O_(40))]· H_2O (3)bmte=1,2-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)ethane
In compound1, two bmte ligands chelate two CuIions with three N atoms to form a binuclearnano-scale subunit [Cu_2(bmte)_2]~(2+), then the binuclear [Cu_2(bmte)_2]~(2+)subunits are connected by[MO_8O_26]~(4-)anions to build a one dimensional (1D) chain. In compound2, a trinuclear nano-scalesubunit [Cu_3(bmte)_3]3+constructed from three CuIions and three bmte ligands has been obtained,and the adjacent trinuclear subunits are linked by [SiMo_(12)O_(40)]~(4-)anions to form a “zipper”1Dchain. The adjacent chains of the title compounds are ultimately extended into2D layers byhydrogen bonds between bmte and [SiMo_(12)O_(40)]~(4-)anions. In compound3, because the GeMo12polyanion has the similar size and charge to SiMo12anion, compounds3and2are isostructural.The structural difference of the three compounds indicates that the POMs play an importantstructure-directed role in the construction of the final networks.
2. Two new copper complexes structure-oriented by Keggin-type SiMo_(12)O_(40)4-andSiW_(12)O_(40)~(4-)anions have been hydrothermally synthesized on the basis of the rigid benzotriazole ligand:
[CuI_8(BTA)_4(HBTA)_8(SiMo_(12)O_(40))]·2H_2O (4)
[CuⅡ_6(OH)_4(BTA)_4(SiW_(12)O_(40))(H2O)_6]·6H_2O (5)HBTA=1-H-1,2,3-benzotriazole
In compound4, eight CuIions were linked by twelve HBTA/BTA ligands to form anoctanuclear CuIcluster, which is connected by SiMo12O404-anion with two bridging O atoms andtwo terminal O atoms to construct a one-dimensional (1D) wave-like chain. The octanuclearcopper unit represents the maximum subunit linked just by amine ligands in POMs system. In5,four BTA ligands linked five CuⅡions constructing a pentanuclear “porphyrin-like” subunit,which is connected by another CuⅡion to form a1D metal-organic band. The SiW_(12)O_(40)_4-polyanions as tetradentate inorganic linkages extend the1D band into a two-dimensional (2D)network with (83)2(85·10) topology. To the best of our knowledge, compounds4and5representthe first examples of inorganic-organic hybrids based on metal-HBTA multinuclear subunits andpolyoxometalates.
3. Three new metal-organic complexes structure-oriented by Keggin-type anions have beenhydrothermally synthesized by introducing rigid benzimidazole and its derivative ligands into thesystem:
[CuⅡ2(biz)_8(PMoVI_(11)MoVO_(40))(H_2O)_2]· H_2O (6)
[CuI_4(biz)_8(SiW_(12)O_(40))]· H_2O (7)biz=benzimidazole
[CuI_2(dmbiz)_4(Hdmbiz)(HSiW_(12)O_(40))](8)dmbiz=5,6-dimethyl benzimidazole
In compound6, two kinds of metal-organic CuⅡunits linked with four PMo12O403-and eachPMo12O403-anion connected with eight metal-organic unit through hydrogen bondinginteraction, leading to the formation of (4,8)-connected3D supermolecular framework. Incompound7, we selected SiW_(12)O_(40)_4-as inorganic ligand, and the final structure is6-connected3D superamolecular network, which was linked not noly by hydrogen bonds interactions butalso by weak Cu···O interaction. Compound8is a3D superamolecular framework with NaCltype structure, in which dmbiz was used as organic amine ligand instead of biz.
4. In this thesis, the directional assembly of such functional complexes oriented by polyoxometalates under hydrothermal conditions has been realized. The influence of systemfactors of the assembly processes, including the pH value, temperature, reaction time of thesystem, the type of polyoxometalate and the reactant ratio etc., on the construction of targetcomplexes has been explored. In addition, the electrochemical behavior, magnetic property andpotocatalytic degradation methylene blue performance of some title compounds have beeninvestagated. The results indicate that some compounds show good property and will become thepotential inorganic functional materials.
引文
[1]王恩波,胡长文,许林.多酸化学导论[M].北京:化学工业出版社.1998,1.
[2] Wang, E.B., Hu, C.W., Xu, L., Concise of polyoxometalate Chemistry, Chemiealhidustrial PublishingComPany，Beijing，1998，4.
[3] M.T. Pope著,王恩波等译,杂多和同多金属氧酸盐.长春:吉林大学出版社,1991.
[4] Berzelius J., Pogg. Ann.,？Phys. Chem.1826,6,369-371.
[5] Pauling L, The molecular strcture of the tungstosilicates and related compounds, J. Am. Chem. Soc.,1929,51,2868-2880.
[6] Keggin, J. F., The Structure and Formula of12-Phosphotungstic Acid. Proc. R. Soc.,1934,144A,75.
[7] Anderson, J. S., Constitution of the polyacids. Nature,1937,140,850.
[8] Dawson B., The structure of the9(18)-heteropoly anion in potassium9(18)-tungstophosphate,K6(P2W18O62).14H2O, Acta Crystallogr,1953,6,113-126.
[9] Waugh, J. C. T., Schoemaker, D. P.,L. Pauling, On the structure of the heteropoly anion in ammonium9-molybdomanganate,(NH4)6MnMo9O32.82O, Acta Crystallogr,1954,7,438-441.
[10] Tsay Y. H., Silverton J. V, Z. Kristallogr,1973,137,256-279.
[11] Lindqvist I., Ark. Kemi.1950,2,325-349.
[12] Mizumo N, Misono M, Heterogeneous catalysis. Chem.Rev,1998,98,199-218.
[13] Harrup M, Hill C L, Triniobium polytungstophosphates, suntheses, structures, clarification of isomerismand reactivity in the presence of H2O2. Inorg.Chem,1998,37,5550-5556.
[14]刘术侠，刘彦勇，王恩波等, Keggin结构钨磷酸稀土镨盐杂多蓝的合成及抗艾滋病毒（HIV-1）活性的研究.高等学校化学学报,1996,17,1188-1190.
[15]Yamase T,Fujita H, Fukushima K, Medical chemistry of polyoxometalates part1. potent antitumor activityof polyoxomolybdates on animal transplantable tumors and human cancer xenograft. Inorg Chim Acta,1988,152,9-15.
[16] Baker L C W, Glick D C, Present general status of understanding of heteropoly electrolytes and tracing ofsome major highlights in the history of their elucidations. Chem. Rev.,1998,98,3-50.
[17]周云山，多酸型超分子功能化合物、表征与三阶非线性光学性质研究，东北师大博士论文，(1998).
[18] Sessler J. L., Andrievsky A., Gale P. A., Lynch V., Anion Binding: Self-Assembly of PolypyrrolicMacrocycles, Angew. Chem., Int. Ed. Engl.,1996,35,2782-2785.
[19] Nobler C. B., Hawthorne M.F.,[12]Mercuracarborand-4, the First Representative of a New Class ofRigid Macrocyclic Electrophiles: The Chloride Ion Complex of a Charge-Reversed Analogue of
[12]Crown-4, Angew. Chem., Int. Ed. Engl.,1991,30,1507-1508.
[20] Hagrman, D. Hagrman, P. Zubieta, J. Solid-State Coordination Chemistry: The Self-Assembly ofMicroporous Organic-Inorganic Hybrid Frameworks Constructed from Tetrapyridylporphyrin andBimetallic Oxide Chains or Oxide Clusters, Angew. Chem., Int. Ed.1999,38,3165-3168.
[21] Wang X.L., Guo Y.Q., Li Y.G., Wang E.B., Hu C.W., Hu N.H., Novel Polyoxometalate-Templated,3-DSupramolecular Networks Based on Lanthanide Dimers: Synthesis, Structure, and Fluorescent Propertiesof [Ln2(DNBA)4(DMF)8][Mo6O19](DNBA=3,5-Dinitrobenzoate), Inorg. Chem.2003,42,4135-4140.
[22] Jin H., Qi Y.F., Wang E.B., Li Y.G., Qin C., Wang X.L., Chang S., A Novel Copper(I) Halide FrameworkTemplated by Organic–Inorganic Hybrid Polyoxometalate Chains Formed In Situ: A New Route for theDesign and Synthesis of Porous Framework. Eur. J. Inorg. Chem.2006,22,4541-4545.
[23] Zang H.Y., Lan Y.Q., Su Z.M., Yang G.S., Xu G.J., Du D.Y., Chen L., Yan L.K., Construction of a series of0D,2D and3D inorganic–organic hybridcoordination polymers based on octamolybdate and2-(2-pyridyl)imidazoleand its derivative, Inorg. Chim. Acta,2010,363,118-126.
[24] Sha J.Q., Huang L., Peng J., Pang H.J., Tian A.X., Zhang P.P., Chen Y., Zhu M, Assembly of two novelLindqvist polyoxoanion-templated coordination polymers with standard honeycomb cavities, Solid StateSci.,2009,11,417-421.
[25] Zheng L. M., Wang Y. S., Wang X. Q., Korp J. D., Jacobson A. J., Anion-Directed Crystallization ofCoordination Polymers: Syntheses and Characterization of Cu4(2-pzc)4(H2O)8(Mo8O26)·2H2O andCu3(2-pzc)4(H2O)2(V10O28H4)·6.5H2O (2-pzc=2-Pyrazinecarboxylate), Inorg. Chem.,2001,40,1380-1385.
[24] Inman C., Knaust J. M., Keller S. W., A polyoxometallate-templated coordination polymer: synthesis andcrystal structure of [Cu3(4,4-bipy)5(MeCN)2]PW12O40·2C6H5CN, Chem. Commun.,2002,156.
[25] Knaust J. M., Inman C., Keller S. W., A host–guest complex between a metal–organic cyclotriveratryleneanalog and a polyoxometalate:[Cu6(4,7-phenanthroline)8(MeCN)4]2PM12O40(M=Mo or W), Chem.Commun.,2004,492.
[26] Wei M.L., He C., Hua W.J., Duan C.Y., Li S.H., Meng Q.J., A Large Protonated Water Cluster H+(H2O)27in a3D Metal Organic Framework, J. Am. Chem. Soc.,2006,128,13318-13319.
[27] Duan C. Y., Wei M. L., Guo D., He C., Meng Q. J., Crystal Structures and Properties ofLarge Protonated Water Clusters Encapsulated by Metal Organic Frameworks,J. Am. Chem. Soc.,2010,132,3321-3330.
[28] Sun C. Y., Liu S. X, Liang D. D., Shao K. Z., Ren Y. H., Su Z. M.. Highly Stable Crystalline CatalystsBased on a Microporous Metal Organic Framework and Polyoxometalates, J. Am. Chem. Soc.,2009,131,1883-1888.
[29] Feng-Ji Ma, Shu-Xia Liu, Chun-Yan Sun, Da-Dong Liang, Guo-Jian Ren, Feng Wei, Ya-Guang Chen,and Zhong-Min Su A Sodalite-Type Porous Metal-Organic Framework with Polyoxometalate Templates:Adsorption and Decomposition of Dimethyl Methylphosphonate J. Am. Chem. Soc.
[30] Li Y.G., Dai L.M., Wang Y.H., Wang X.L., Wang E.B., Su Z. M., Xu L., A new molybdenum-oxide-basedorganic–inorganic hybrid framework templated by double-Keggin anions, Chem. Commun.,2007,2593.
[31] Hao X.L., Luo M.F., Yao W. Li Y.G., Wang Y.H. and Wang E.B., Polyoxometalate-templatedlanthanide–organic hybrid layers based on63-honeycomb-like2D nets,Dalton Transactions, DaltonTrans.,2011,40,5971-5976.
[32] Li C.H., Huang K.L., Chi Y.N., Liu X., Han Z.G., Shen L., Hu C.W., Lanthanide Organic CationFrameworks with Zeolite Gismondine Topology and Large Cavities from Intersected Channels Templatedby Polyoxometalate Counterions, Inorg. Chem.,2009,48,2010-2017.
[33] Liu X.Y., Jia Y.Y., Zhang Y.F., Huang R.D., Construction of a Hybrid Family Based onLanthanide–Organic Framework Hosts and Polyoxometalate Guests, Eur. J. Inorg. Chem.,2010,25,4027-4033.
[34] Zhai Q.G., Wu X.Y., Chen S.M., Zhao Z.G., Lu C.Z., Construction ofAg/1,2,4-Triazole/Polyoxometalates Hybrid Family Varying from Diverse Supramolecular Assemblies to3-D Rod-Packing Framework, Inorg. Chem.,2007,46,5046-5058.
[35] Kong X.F., Ren Y.P., Zheng P.Q., Long Y.X., Long L.S.， Surface modification of polyoxometalatehost–guest supramolecular architectures: from metal–organic pseudorotaxane framework to molecularbox，ChemComm.,2011,47,4150-4152.
[36] Wang X.L., Bi Y.F., Chen B.K., Lin H.Y., Liu G.C., Self-Assembly of Organic–Inorganic Hybrid MaterialsConstructed from Eight-Connected Coordination Polymer Hosts with Nanotube Channels andPolyoxometalate Guests As Templates, Inorg. Chem.,2008,47,2442-2448.
[37] Wang X.L., Hu H.L., Tian A.X., Lin H.Y., Li J., Application of Tetrazole-Functionalized Thioethers withDifferent Spacer Lengths in the Self-Assembly of Polyoxometalate-Based Hybrid Compounds, Inorg.Chem.,2010,22,10299–10306.
[38] Wang X.L., Li J., Tian A.X., Zhao D., Liu G.C., Lin H.Y.，Assembly of Three NiII—Bis(triazole)Complexes by Exerting theLinkage and Template Roles of Keggin AnionsCryst. Growth Des.2011,11,3456–3462.
[39] Zhao X.Y., Liang D.D., Liu S.X., Sun C.Y., Cao R. G., Gao C.Y., Ren Y.Y., Su Z.M., TwoDawson-Templated Three-Dimensional Metal Organic Frameworks Based on Oxalate-Bridged BinuclearCobalt(II)/Nickel(II) SBUs and Bpy Linkers, Inorg. Chem.,2008,47,7133-7138.
[40] Wang X.L., Hu H.L., Tian A.X., Lin H.Y., Li J., Shi L.M., A new bitrack sinusoidal-like chain templatedby Wells-Dawson POMs, Inorg. Chem. Commun.2010,13,745-748.
[41]王恩波，李阳光，鹿颖，王新龙.多酸化学概论[M].长春：东北师范大学出版社
[42] Zheng P.Q., Ren Y.P., Long L.S., Huang R.B., Zheng L.S., pH-Dependent Assembly of Keggin-BasedSupramolecular Architecture, Inorg. Chem.,2005,44,1190-1192.
[43] Ren Y.P., Kong X.J., Hu X.Y., Sun M., Long L.S., Huang R.B., Zheng L.S., Influence of Steric Hindranceof Organic Ligand on the Structure of Keggin-Based Coordination Polymer, Inorg. Chem,2006,45,4016-4023.
[44] Ren Y.P., Kong X.J., Hu X.Y., Sun M., Long L.S.,. Huang R.B., Zheng L.S., Anion-Dependent Assemblyof Cyclic Structure, Cryst. Growth Des.,2006,6,572-576.
[45] Kong X.J., Ren Y.P., Zheng P.Q., Long Y.X., Long L.S., Huang R.B., Zheng L.S., Construction ofPolyoxometalates-Based Coordination Polymers through Direct Incorporation between Polyoxometalatesand the Voids in a2D Network, Inorg. Chem.,2006,45,10702-10711.
[46] An H.Y., Xiao D.R., Wang E.B., Li Y.G., Su Z.M., Xu L., Chiral3D Architectures with Helical ChannelsConstructed from Polyoxometalate Clusters and Copper-Amino Acid Complexes, Angew. Chem., Int. Ed.,2006,45,904-908.
[47] Wang X.L., Qin C., Wang E.B., Su Z.M., Li Y.G.; Xu L. Self-Assembly of Nanometer-Scale[Cu224I10L1]14+Cages and Ball-Shaped Keggin Clusters into a (4,12)-Connected3D Framework withPhotoluminescent and Electrochemical Properties, Angew. Chem., Int.Ed.,2006,45,7411-7414.
[48] Jin H., Qi Y.F., Wang E.B., Li Y.G., Qin C., Wang X.L., Chang S., A Novel Copper(I) Halide FrameworkTemplated by Organic-Inorganic Hybrid Polyoxometalate Chains Formed In Situ: A New Route for theDesign and Synthesis of Porous Frameworks, Eur. J. Inorg. Chem.,2006,22,4541-4545.
[49] Qi Y.F., Li Y.G., Qin C., Wang E.B., Jin H., Xiao D.R., Wang X.L., Chang S., From Chain to Network:Design and Analysis of Novel Organic Inorganic Assemblies from Organically FunctionalizedZinc-Substituted Polyoxovanadates and Zinc Organoamine Subunits, Inorg. Chem.,2007,46,3217-3230.
[50] You W.S., Wang E.B., Xu Y., An Alkali Metal Crown Ether Complex Supported by a Keggin Anionthrough the Three Terminal Oxygen Atoms in a Single M3O13Triplet: Synthesis and Characterization of
[{Na(dibenzo-18-crown-6)(MeCN)}3{PMo12O40}], Inorg. Chem.,2001,40,5468-5471.
[51] Tan H.Q., Li Y.G., Zhang Z.M.,et al. Chiral Polyoxometalate-Induced Enantiomerically3D Architectures:A New Route for Synthesis of High-Dimensional Chiral Compounds, J. Am. Chem. Soc.,2007,129,10066-10067.
[52] Qin C., Wang X.L., Wang E.B., Su Z.M., Catenation of Loop-Containing2D Layers with a3D pcuSkeleton into a New Type of Entangled Framework Having Polyrotaxane and Polycatenane Character,Inorg. Chem,2008,47,5555-5557.
[53] Li S.L., Lan Y.Q., Ma J.F., Yang J., Liu J., Mei Y.M., Su Z.M., Inorganic–organic hybrid materials withdifferent dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanionclusters, Dalton Trans,2008,2015.
[54] Li S.L., Lan Y.Q., Ma J.F., Yang J., Wang X.H., Su Z.M., Syntheses and Structures of Organic InorganicHybrid Compounds Based on Metal Fluconazole Coordination Polymers and the β-Mo8O26Anion, Inorg.Chem.,2007,46,8283.
[55] Sha J.Q., Peng J., Liu H.S., Chen J., Tian A.X., Zhang P.P., Asymmetrical Polar Modification of aBivanadium-Capped Keggin POM by Multiple Cu N Coordination Polymeric Chains, Inorg. Chem.2007;46,11183-11189.
[56] Sha J.Q., Peng J., Liu H.S., Chen J.,Dong B.X., Tian A.X., Su Z.M., Keggin POMs Modified by Bondingto Multitrack Cu(bipy) Chains through Linearly Arrayed Terminal and Bridging Oxygen Atoms of theM3O13Triad,Eur.J.Inorg.Chem.,2007,1268-1274.
[57] Tian A.X., Ying J., Peng J., Sha J. Q., Pang H. J., Zhang P. P., Chen Y., Zhu M., Su Z. M.，Tuning theDimensionality of the Coordination Polymer Based on Polyoxometalate by Changing the Spacer Lengthof Ligands，Cryst. Growth Des.,2008,8,3717-3724.
[58] Dong B.X.,Peng J.,Zhang P. P.,Tian A.X.,Chen J.,Xue B., Hydrothermal synthesis and crystal structure ofa novel Keggin polyoxoanion-templated multichain coordination polymer with a flexible bis(imidazole)ligand, Inorg. Chem. Commun.2007,10,839-842.
[59] Sha J.Q., Peng J., Tian A.X., Liu H., Chen J., Zhang P.P., Su Z.M., Assembly of Multitrack Cu NCoordination Polymeric Chain-Modified Polyoxometalates Influenced by Polyoxoanion Cluster andLigand, Cryst. Growth Des.2007,7,2535-2541.
[60] Tian A.X., Ying J., Peng J., Sha J.Q., Pang H.J., Zhang P.P., Chen J., Zhu M., Su Z.M., Assembly ofMultitrack Cu N Coordination Polymeric Chain-Modified Polyoxometalates Influenced by PolyoxoanionCluster and Ligand, Cryst. Growth Des.,2007,7,2535-2541.
[61] Liu H.Y., Wu H., Yang J., Liu Y.Y., Ma J.F., Bai H.Y., Solvothermal Assembly of a Series ofOrganic_Inorganic Hybrid Materials Constructed from Keggin Polyoxometalate Clusters and Copper(I)Organic Frameworks Cryst. Growth Des.,2011,11,1786-1797.
[62] Lan Y.Q., Li S.L., Li Y.G., Su Z.M., Shao K.Z. and Wang X.L.，A novel (4,8)-connected3Dpolyoxometalate-based metal–organic framework containing an in situ ligand，CrystEngComm.,2008,10,1129-1131.
[63] Hou G.F., Bi L.H., Li B., Wu L.X., Reaction Controlled Assemblies of Polyoxotungstates (-molybdates)and Coordination Polymers, Inorg. Chem.2010,49,6474-6483.
[64] Hou G.F., Bi L.H.,Li B.,Wang B., Wu L.X., Polyoxometalate charge directed coordination assemblies:Macrocycles and polymer chains, CrystEngComm.,2011,13,3526-3535.
[65] Wang X.L., Hu H.L., Liu G.C., Lin H.Y., Tian A.X., Self-assembly of nanometre-scalemetallacalix[4]arene building blocks and Keggin units to a novel (3,4)-connected3D self-penetratingframework, Chem. Commun.,2010,46,6485-6487.
[66] Wang X.L., Hu H.L., Tian A.X., Lin H.Y., Li J., Application of Tetrazole-Functionalized Thioethers withDifferent Spacer Lengths in the Self-Assembly of Polyoxometalate-Based Hybrid Compounds Inorg.Chem.,2010,22,10299–10306.
[67] Wang X.L., Wang Y.F., Liu G.C., Tian A.X., Zhang J.W., Lin H.Y., Novel inorganic–organic hybridsconstructed from multinuclear copper cluster and Keggin polyanions: from1D wave-like chain to2Dnetwork, Dalton Trans.,2011,40,9299–9305.
[68] Yan B.B., Xu Y., Bu X.H., Goh N.K., Chia L.S., Stucky G.D., Hydrothermal syntheses and structures ofthree one-dimensional heteropolytungstates formed by Dawson or Keggin cluster units, DaltonTrans.2001,13,2009.
[69] Soumahoro T., Burkholder E., Ouellette W., Zubieta J., Organic–inorganic hybrid materials constructedfrom copper-organoimine subunits and molybdoarsonate clusters,Inorg.Chem.Acta2005,358,606-616.
[70] Tian A.X., Z.G. Han, J. Peng, B.X. Dong, J.Q. Sha, B. Li, Two novel hybrid inorganic–organiccompounds based on Wells-Dawson polyanion and transition metal (TM) complex with one-dimensionalstructure: Hydrothermal synthesis and characterization, J.Mol.Struct.2007,832,117-123.
[71] J.Y. Niu, D.J. Guo, J.P. Wang, J.W. Zhao,1D Polyoxometalate-Based Composite Compounds Derivedfrom the Wells Dawson Subunit: Synthesis and Crystal Structure of
[{Ce(DMF)4(H2O)3}{Ce(DMF)4(H2O)4}(P2W18O62)]·H2O and
[{La(DMF)6(H2O)}{La(DMF)4.5(H2O)2.5}(P2W18O62)], Cryst.Growth. Des.2004，4,241-247.
[72] Jin H., Qi Y.F., Xiao D.R., Wang X.L., Chang S., Wang E.B., Two novel inorganic–organic hybrids basedon saturated Wells–Dawson polyoxoanion and copper–organonitrogen coordination polymer, J.Mol.Struct.2007,837,23-29.
[73] Fu H.,Li Y. G., Lu Y.,Chen W.L.,Wu Q.,Meng J. X., Wang X.L.,Zhang Z.M., andWang E.B.,Solvothermal Assembly of a Series of Organic_Inorganic Hybrid Materials Constructed from KegginPolyoxometalate Clusters and Copper(I) Organic Frameworks Cryst. Growth Des.2011,11,458-465.
[74] Zhao J.W., Zheng S.T., Liu W., Yang G.Y., Hydrothermal synthesis and structural characterization of two1-D and2-D Dawson-based phosphotungstates. J. Solid State Chem.2008,181,637–645.
[75] Lin B.Z., He L.W., Xu B.H., Li X.L., Li Z., Liu P.D., Two Polyoxophosphotungstates Formed byWells-Dawson Cores Linked through W-O-W Linkages. Cryst.GrowthDes.2009，9(1),273-281.
[76] Tian A.X., Ying J., Peng J., Sha J.Q., Han Z.G., Ma J.F., Su Z.M., Hu N.H., Jia H.Q., Assembly of theHighest Connectivity Wells-Dawson Polyoxometalate Coordination Polymer: the Use of Organic LigandFlexibility, Inorg. Chem.,2008,47,3274-3283.
[77] Tian A.X., Ying J., Peng J., Sha J.Q., Zhu D.X., Pang H.J., Zhang P.P., Chen Y., Zhu M., Assembly of anew Wells–Dawson polyoxometalate-templated compound based on Fe-btb complex, Inorg. Chem.Commun.,2008,11,1132-1135.
[78] Sha J.Q., Peng J., Li Y.G., Zhang P.P., Pang H.J., Synthesis and characterization of the highest connected3D Wells-Dawson POM/TMC hybrid, Inorg. Chem. Commun,2008,11,907-910.
[79] Dong B.X., Peng J., Chen Y.H., Zhang P.P., Tian A.X., Chen J., A novel wavelike chain constructed fromWells–Dawson type polyoxoanions and mixed-ligand decorated transition metal complex cations[Ni(phen)(bbi)2+2], J. Mole. Struc,2008,875,75-79.
[80] Sha J.Q., Wang C., Peng J., Chen J., Tian A.X., Zhang P.P.,[Cu(4,4′-bipy)]2[H4P2W18O62]·2H2O: Thefirst three-dimensional framework based on saturated Wells–Dawson POMs modified by multi-trackCu–N coordination polymeric chains, Inorg. Chem. Commun.,2007,10,1321-1324.
[81] Sha J.Q., Peng J., Lan Y.Q., Su Z.M., Pang H.J., Tian A.X., Zhang P.P., Zhu M., pH-Dependent Assemblyof Hybrids Based on Wells-Dawson POM/Ag Chemistry, Inorg. Chem.,2008,47,5145-5153.
[82] Zhang P.P., Peng J., Pang H.J., Sha J.Q., Zhu M., WangD.D., Liu M.G.，The factors affecting on theassembly of Ag–H2biim system: size, charge orshape of polyanions?, CrystEngComm.,2011,13,3832-3841.
[83] Zhu M., Peng J., Pang H.J., Zhang P.P., Chen Y., Wang D.D., Liu M.G., Wang Y.H., A new3Dtransition-metal complex-templated framework based on Wells–Dawson polyoxometalate andcopper(I)–pyrazine moieties, Inorg. Chim. Acta,2011,370,260-264.
[84] Shivaiah V., Nagaraju M., Das S.K., Formation of a Spiral-Shaped Inorganic Organic Hybrid Chain,[CuII(2,2′-bipy)(H2O)2Al(OH)6Mo6O18]n-n: Influence of Intra-and Interchain Supramolecular Interactions,Inorg. Chem.,2003,42,6604-6606.
[85] Yan A.H., Li Y.G., Xiao D.R., Wang E.B., Sun C.Y., Self-Assembly of Extended High-DimensionalArchitectures from Anderson-type Polyoxometalate Clusters, Cryst. Growth Des.,2006,6,1107-1112.
[86] An H. Y., Li Y. G., Wang E.B., Self-Assembly of a Series of Extended Architectures Based onPolyoxometalate Clusters and Silver Coordination Complexes, Inorg. Chem.,2005,44,6062-6070.
[87] An H.Y., Xiao D.R., Wang E.B., Li Y.G., Wang X.L., Xu L., Open-Framework Polar Compounds:Synthesis and Characterization of Rare-Earth Polyoxometalates(C6NO2H5)2[Ln(H2O)5(CrMo6H6O24)]·0.5H2O (Ln=Ce and La), Eur. J. Inorg. Chem.,2005,854-859.
[88] An H.Y., Lan Y., Li Y.G., Wang E.B., Hao N., Xiao D.R., Duan L.Y., Xu L., A novel chain-like polymerconstructed from heteropolyanions covalently linked by lanthanide cations:(C5H9NO2)2[La(H2O)7CrMo6H6O24]·11H2O (Proline=C5H9NO2), Inorg. Chem. Commun.,2004,7,356-358.
[89] An H.Y., Xiao D.R., Wang E.B., Li Y.G., Xu L., A series of new polyoxoanion-based inorganic-organichybrids:(C6NO2H5)[(H2O)4(C6NO2H5)Ln(CrMo6H6O24)].4H2O (Ln=Ce, Pr, La and Nd) with a chirallayer structure. New. J. Chem.,2001,40,667-672.
[90]Cao R.G.,Liu S.X.,Xie L.H.,Pan Y.B.,Cao J.F.,Ren Y.H.,Xu L., Organic Inorganic Hybrids Constructed ofAnderson-Type Polyoxoanions and Oxalato-Bridged Dinuclear Copper Complexes, Inorg Chem,2007,46,3541–3547.
[91] Li S.Z.,Ma P.T.,Wang J.P.,Guo Y.Y.,Niu H.Z.,Zhao J.W.,Niu J.Y., J.W. Zhao, J.Y. Niu, A3Dorganic–inorganic network constructed from an Anderson-type polyoxometalate anion, a copper complexand a tetrameric [Na4(H2O)+14]4cluster CrystEngComm,2010,12,1718-1721.
[92] Lan Y.Q., Li S.L.,Wang X.L.,Shao K.Z.,Du D.Y., Zang H.Y., Su Z.M., Self-Assembly ofPolyoxometalate-Based Metal Organic Frameworks Based on Octamolybdates and Copper-Organic Units:from CuII, CuI,IIto CuI via Changing Organic Amine. Inorg. Chem.,2008,47,8179-8187.
[93] Zang H.Y.,Lan Y.Q.,Li S.L.,Yang G.S.,Shao K.Z., Wang X.L.,Yan L.K. and Su Z.M., Step-wisesynthesis of inorganic–organic hybrid based on γ-octamolybdate-based tectons Dalton Trans.,2011,40,3176-3182.
[94] Lu J., Shen E.H.,Li Y.G., Xiao D.R., Wang E.B., Xu L., A Novel Pillar-Layered Organic-InorganicHybrid Based on Lanthanide Polymer and Polyomolybdate Clusters: New Opportunity toward the Designand Synthesis of Porous Framework, Cryst. Growth Des.,2005,5,65-67.
[95] Wu X.Y., Dong P.,Yu R.M., Zhang Q.K., Kuang X.F., Chen S.C., Lin Q.P., Lu C.Z.，A2Dpolyoxometalate-based complex: spin-canting and metamagnetism CrystEngComm.,2011,13,3686-3688.
[96] Haushalter R C, Mundi L A. Reduced molybdenum phosphates: octahedral-tetrahedral framework solidswith tunnels, cages, and micropores. Chem Mater1992,4,31-48.
[97] Meyer L A, Haushalter R C. Hydrothermal synthesis, structure, and sorption properties of the newmicroporous ferric molybdenum phosphates [(CH3)4N]2(NH4)2[Fe2Mo12O30(H2PO4)6(HPO4)2]·nH2O, and
[(CH3)4N]2Na4[Fe3Mo12O30(HxPO4)8]·nH2O. Inorg Chem,1993,32,1579-1586.
[98] Xu L, Sun Y Q, Wang E B, Shen E.H, Liu Z.R, Hu C.W,Xing Y, Lin Y.H, Jia H.Q. A manganesemolybdenum phosphate with a tunnel: hydrothermal synthesis, structure and catalytic properties of(NH3CH2CH2NH3)10(H3O)3(H5O2)Na2[MnMo12O24(OH)6(PO4)4(PO3OH)4][MnMo12O24(OH)6(PO4)6(PO3OH)2]·9H2O [J]. New J Chem,1999,23,1041-1044.
[99] Ma Y, Li Y.G, Wang E.B, Lu Y, Wang X.L, Xu X.X. Self-assembly of four new extended architecturesbased on reduced polyoxometalate clusters and cadmium complexes. Solid State Chem.,2006,179,2367–2375.
[100] Ma Y, Li Y.G, Wang E.B, Lu Y, Wang X.L, Xiao D.R, Xu X.X. Self-assembly of fourthree-dimensional reduced molybdenum (V) phosphates decorated with transitional metal complexes.Inorg. Chimi. Acta.2007,2,421–430
[101] Ma Y, Li Y.G, Wang E.B, Lu Y, Qin C, Xu X.X. Syntheses, structure characterizations andfluorescent properties of two reduced molybdenum (V) phosphates functionalized by zinc coordinationcomplexes. J. Clust. Sci.,2006,1,167-181.
[102] Lin B.Z, Han G.H, Xu B.H, Bai L, Feng Y.L, Su H. Hydrothermal Synthesis and CharacterizationofTwo New Phosphatomolybdates(V) ContainingSandwich-Shaped [M(Mo6P4)2] Clusters (M=Co, Ni), J.Clust. Sci.,2008,19,379–390.
[103] Yu K, Chen W.L, Zhou B.B, Li Y.G, Yu Y, Su Z.H, Gao S, Chen Y. New extendedpoly(oxomolybdophosphates) based on strontium(II) linkers, CrystEngComm,2011,13,3417-3424.
[104] Long D.L, Tsunashima R, Cronin L., Angew. Polyoxometalates: Building Blocks forFunctionalNanoscale Systems, Chem. Int. Ed.,2010,49,1736-1758.
[105] Kortz U., Müller A., Slageren J.V., Schnacke J., Dalalf N. S., Dressel M., Polyoxometalates: Fascinatingstructures, unique magnetic properties, Coord. Chem. Rev.,2009,253,2315-2327.
[106] Rhule J.T., Neiwert W.A., K. Hardcastle I..B., Do T., Hill C. L., Ag5PV2Mo10O40, a HeterogeneousCatalyst for Air-Based Selective Oxidation at Ambient Temperature J. Am. Chem. Soc.,2001,123,12101-12102.
[107] Yamase T., Pope M.T., Polyoxometalate Chemistry for Nano-Composite Design, Kluwer: Dordrecht, theNetherlands,2002.
[108] H.J. Pang, Peng J., Zhang C.J., Y.G. Li, Zhang P.P., Ma H.Y., Z.M. Su, A polyoxometalate-encapsulated3D porous metal–organic pseudo-rotaxane frameworkw, Chem. Commun.,2010,46,5097–5099.
[109] Xiao L.N., Wang Y., Pan C.L., Xu J.N., Wang T.G., Ding H., Gao Z.M., Zheng D.F., Cui X.B., Xu J.Q.,Three novel supramolecular hybrid compounds based on keggin polytungstates, CrystEngComm,2011,13,4878-4885.
[110] Wang Y., Peng Y., Xiao L.N., Y.Y. Hu, Wang L.M., Gao Z.M., Wang T.G., Wu F.Q., Cui X.B., Xu J.Q.,New compounds constructed from polyoxometalates and transition metal coordination complexes withlower positive charge, CrystEngComm,2012,14,1049-1056.
[111] Khenkin A. M., Weiner L., Wang Y., Neumann R., Electron and Oxygen Transfer in Polyoxometalate,H5PV2Mo10O40, Catalyzed Oxidation of Aromatic and Alkyl Aromatic Compounds: Evidence for AerobicMars van Krevelen-Type Reactions in the Liquid Homogeneous Phase, J. Am. Chem. Soc.2001,123,8531-8542.
[112] Müller A., Shah S. Q.N., B gge H., Schmidtmann M., Molecular growth from a Mo176to a Mo248cluster,Nature.1999,397,48-50.
[113] Yaghi O. M., O'Keeffe M., Ockwig N. W., Chae H. K., Eddaoudi M., Kim J., Reticular synthesis and thedesign of new materials, Nature,2003,423,705-714.
[114] Hussain F., Kortz U., Ketia B., Nadjo L., M. Pope T., Tetrakis(dimethyltin)-ContainingTungstophosphate [{Sn(CH23)2}4(H2P4W24O92)2]8-: First Evidence for a Lacunary Preyssler Ion, Inorg.Chem.,2006,45,761-766.
[115] Khan M. I., Yohannes E., Nome R., Ayesh S., Golub V. O., O’Connor C. J., Doedens R. J.,Inorganic Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, andMagnetic Properties of the Open Framework Solids [{Co(4,4‘-Bipy)}V2O6] and
[{Co2(4,4‘-Bipy)3(H2O)2}V4O12]·2H2O, Chem. Mater.,2004,16,5273-5279.
[116] K gerler P., Cronin L., Polyoxometalate Nanostructures, Superclusters, and Colloids: From FunctionalClusters to Chemical Aesthetics, Angew. Chem. Int. Ed.,2005,44,844-846.
[117] Alam M., Kim Y.S., Ogawa S., Tsuda A., Ishii N., Aida T., Directed1D Assembly of a Ring-ShapedInorganic Nanocluster Templated by an Organic Rigid-Rod Molecule: An Inorganic/OrganicPolypseudorotaxane, Angew. Chem. Int. Ed.,2008,11,2070-2073.
[118] Haasnoot J.G., Syntheses and solid-state structural chemistry of polytelluride anions, Coord. Chem. Rev.,2000,200,131-185.
[119] Klingele M.H., Brooker S., Group4ketimide complexes: Synthesis, reactivity and catalytic applications,Coord. Chem. Rev.,2003,241,119-132.
[120] Beckman U., Brooker S., Cobalt(II) complexes of pyridazine or triazole containing ligands: spin-statecontrol, Coord. Chem. Rev.,2003,245,17-29.
[121] Ouellette W., Prosvirin A.V., Chieffo V., Dunbar K.R, Hudson B., Zubieta J., Solid-State CoordinationChemistry of the Cu/Triazolate/X System (X=F-, Cl-, Br-, I-, OH-, and SO42-), Inorg. Chem.,2006,45,9346-9366.
[122] Wu X.Y., Kuang X.F., Zhao Z.G., Chen S.C., Xie Y.M., Yu R.M., Lu C.Z., Synthesis, characterization,and structural studies of mercury(II) complexes of new bidentate phosphorus ylide, Inorg. Chim.Acta.,2010,363,1236-1242.
[123] Zhai Q.G., Lu C.Z., Zhang Q.Z., Wu X.Y., Xu X.J., Chen S.M., Chen L.J., Influence of substituents onthe structures of hybrid complexes constructed from tetranuclear copper(I)1,2,4-triazolate clusters andoctamolybdates, Inorg. Chim. Acta.,2006,359,3875-3887.
[124] Zhai Q.G., Wu X.Y., Chen S.M., Zhao Z.G., Lu C.Z., Construction ofAg/1,2,4-Triazole/Polyoxometalates Hybrid Family Varying from Diverse Supramolecular Assemblies to3-D Rod-Packing Framework, Inorg. Chem.,2007,46,5046-5058.
[125] Wang X.L, Qin C., Wang E.B., Su Z.M., Li Y.G., Xu L., Self-Assembly of Nanometer-Scale
[Cu4+24I10L12]1Cages and Ball-Shaped Keggin Clusters into a (4,12)-Connected3D Framework withPhotoluminescent and Electrochemical Properties, Angew. Chem. Int. Ed.,2006,45,7411-7414.
[126] Wang X.L., Bi Y.F., Chen B.K., Lin H.Y., Liu G.C., Self-Assembly of Organic–Inorganic HybridMaterials Constructed from Eight-Connected Coordination Polymer Hosts with Nanotube Channels andPolyoxometalate Guests As Templates, Inorg. Chem.,2008,47,2442-2448.
[127] Wang X.L., Lin H.Y., Bi Y.F., Chen B.K., Liu G.C., An unprecedented extended architectureconstructed from a2D interpenetrating cationic coordination framework templated by SiW12O4–40anion, J.Solid State Chem.,2008,181,556-561.
[128] Wang X.L., Chen B.K., Liu G.C., Zhao H.Y., Lin H.Y., Hu H.L., Hydrothermal syntheses and structuralcharacterization of two new supramolecular compounds:(H2bbi)2[Mo8O26] and (H2bbi)2[SiW12O40]·2H2O
[bbi=1,1′-(1,4-butanediyl)bis(imidazole)], J. Solid State Sci.,2009,11,61-67.
[129] Wang X.L., Chen B.K., Liu G.C., Lin H.Y., Hu H.L., Three new3-D inorganic–organic coordinationpolymers constructed from polyoxovanadate-based heterometallic network and flexible bis(imidazole)ligand: Syntheses, structures and properties, J. Organomet. Chem.,2010,695,827-832.
[130] Wang X.L., Hu H.L., Liu G.C., Lin H.Y., Tian A.X., Self-assembly of nanometre-scale metallacalixarene building blocks and Keggin units to a novel (3,4)-connected3D self-penetrating framework, Chem.Commun.,2010,46,6485-6487.
[131] Brown I.D., Altermatt D.,1,6-Bis(1-methyl-1H-tetrazol-5-ylsulfanyl)hexane, Acta Crystallogr. B.,1985,41,244-247.
[132] Sha J.Q., Peng J., Liu H.S, Chen J., Dong B.X., Tian A.X., Su Z.M., Keggin POMs Modified byBonding to Multitrack Cu(bipy) Chains through Linearly Arrayed Terminal and Bridging Oxygen Atomsof the M3O13Triad, Eur. J. Inorg. Chem.,2007,9,1268-1274.
[133] Meng J.X., Lu Y., Li Y.G., Fu H., Wang E.B., Base-Directed Self-Assembly of Octamolybdate-BasedFrameworks Decorated by Flexible N-Containing Ligands, Cryst. Growth. Des.,2009,9,4116-4126.
[134] L.J. Bellamy, The Infrared Spectra of Complex Molecules, Wiley, New York,1958.
[135] K. Nakamoto, Infrared Spectra and Raman Spectra of Inorganic and Coordination Compound, JohnWiley&Sons: New York,1986.
[136] Dong B.X., Xu Q., Cryst. Growth. Des., Structural Investigation of Flexible1,4-Bis(1,2,4-triazol-1-ylmethyl)benzene Ligand in Keggin-Based Polyoxometalate Frameworks,2009,9,2776-2782.
[137] Dong S., Xi X., Tian M., Study of the electrocatalytic reduction of nitrite with silicotungsticheteropolyanion, J. Electroanal. Chem.,1995,385,227-233.
[138] Sadakane M., Steckhan E., Electrochemical Properties of Polyoxometalates as Electrocatalysts, Chem.Rev.,1998,98,219-238.
[139] Li S.L., Lan Y.Q., Ma J.F., Yang J., Liu J., Fu Y.M., Su Z.M., Inorganic–organic hybrid materials withdifferent dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanionclusters, Dalton Trans.,2008,15,2015-2025.
[140] Chen J., Sha J.Q., Peng J., Shi Z.Y., Dong B.X., Tian A. X., Self-assembly of two novel bisupportingKeggin-polyoxometalate derivatives: Hydrothermal synthesis and structure characterization, J. Mol.Struct.,2007,846,128-133.
[141] She J.B., Zhang G.F., Dou Y.L., Fan X.Z., Li J.Z., Acta. Cryst. E.62(2006) o402-o404.
[142] Wang X.L., Kang Z.H., Wang E.B., Hu C.W., Preparation, electrochemical property and application inchemically bulk-modified electrode of a hybrid inorganic–organic silicomolybdate nanoparticles, Mater.Lett.,2002,56,393-396.
[143] Sheldrick, G.M, Acta Crystallogr. Sect. A: Found. Crystallogr.2008,64,112-122.
[144] Long D.L, Tsunashima R. and Cronin L., Polyoxometalates: Building Blocks for Functional NanoscaleSystems, Angew. Chem. Int. Ed.,2010,49,1736–1758.
[145] Kortz U., Müller A., Slageren J. V., Schnacke J., Dalalf N. S. and Dressel M., Polyoxometalates:Fascinating structures, unique magnetic properties, Coord. Chem. Rev.,2009,253,2315-2327.
[146] Rhule J. T., Neiwert W. A., Hardcastle K. I. B., Do T. and Hill C. L., Ag5PV2Mo10O40, a HeterogeneousCatalyst for Air-Based Selective Oxidation at Ambient Temperature, J. Am. Chem. Soc.,2001,123,12101-12102.
[147] Fu H., Li Y.G., Lu Y., Chen W.L., Wu Q., Meng J.X., Wang X.L., Zhang Z.M., Wang E.B.,Polyoxometalate-Based Metal Organic Frameworks Assembled under the Ionothermal Conditions, Cryst.Growth Des.,2011,11,458-465.
[148] Wang X.L., Li J., Tian A.X., Liu G.C., Gao Q., Lin H.Y., Zhao D., A3D organopolymolybdate polymerwith unusual topology functionalized by1,4-bis(1,2,4-triazol-1-yl)butane through Mo–N bond,CrystEngComm.,2011,13,2194-2196.
[149] Zhai Q.G., Wu X.Y., Chen S.M., Zhao Z.G., Lu C.Z., Construction ofAg/1,2,4-Triazole/Polyoxometalates Hybrid Family Varying from Diverse Supramolecular Assemblies to3-D Rod-Packing Framework, Inorg. Chem.,2007,46,5046-5058.
[150] Yang H.X., Guo S.P., Tao J., Lin J.X., Cao R., Hydrothermal Syntheses, Crystal Structures, AndMagnetic Properties of a Series of Complexes Constructed from Multinuclear Copper Clusters andPolyoxometalates, Cryst. Growth Des.,2009,9,4735-4744.
[151] Zhao J.W., Shi D.Y., Chen L.J., Ma P.T., Wang J. P., Niu J.Y., Assembly of Three NiII–Bis(triazole)Complexes by Exerting the Linkage and Template Roles of Keggin Anions, CrystEngComm.,2011,13,3456-3462.
[152] Cui F.Y., Ma X.Y., Li C., Dong T., Gao Y.Z., Han Z.G., Chi Y. N., Hu C.W., Two neworganic–inorganic hybrid compounds based on metal–pyrazine coordination polymers and Kegginpolyoxometalates: effect of metal ions on thestructure, J. Solid State Chem.,2010,183,2925-2931.
[153] Ma F.J, Liu S.X., Sun C.Y., Liang D.D., Ren G.J., Wei F., Chen Y.G., Su Z.M., A Sodalite-Type PorousMetal Organic Framework with Polyoxometalate Templates: Adsorption and Decomposition of DimethylMethylphosphonate, J. Am. Chem. Soc.,2011,133,4178-4181.
[154] Yuan L., Qin C., Wang X.L., Wang E.B., Chang S., Two Extended Organic-Inorganic Assemblies Basedon Polyoxometalates and Copper Coordination Polymers with Mixed4,4′-Bipyridine and2,2′-BipyridineLigands, Eur. J. Inorg. Chem.,2008,31,4936-4942.
[155] Wang X.L., Qin C., Wang E.B., Su Z.M., Li Y.G., Xu L., Self-Assembly of Nanometer-Scale
[Cu24I410L12]1+Cages and Ball-Shaped Keggin Clusters into a (4,12)-Connected3D Framework withPhotoluminescent and Electrochemical Properties, Angew. Chem. Int. Ed.,2006,45,7411–7414.
[156] Bi Y.F., Du S.C., Liao W.P., p-tert-Butylthiacalix[4]arene-supported high-nuclearity {Co24M8}(M=Moor W) nanospheres and the hybrids with Keggin polyoxometalates, Chem. Commun.,2011,47,4724-4726.
[157] Wang X.L., Bi Y.F., Chen B.K., Lin H.Y., Liu G.C., Application of Tetrazole-Functionalized Thioetherswith Different Spacer Lengths in the Self-Assembly of Polyoxometalate-Based Hybrid Compounds, Inorg.Chem.,2008,47,2442-2448.
[158] An H.Y., Li Y.G., Wang E.B., Xiao D.R., Sun C.Y., Xu L., Self-Assembly of a Series of ExtendedArchitectures Based on Polyoxometalate Clusters and Silver Coordination Complexes, Inorg. Chem.,2005,44,6062-6067.
[159] Tian A.X., Han Z.G., Peng J., Ying J., Sha J.Q., Dong B.X., Zhai J.L., Liu H.S., The interplay ofhydrogen bonds and halogen bonds in the structure of NH-pyrazoles bearing C-aryl and C-halogensubstituents, Inorg. Chim. Acta,2008,361,1332-1342.
[160] Zhang P.P., Peng J., Pang H.J., Sha J.Q., Zhu M., Wang D.D., Liu M.G., The factors affecting on theassembly of Ag–H2biim system: size, charge or shape of polyanions?, CrystEngComm.,2011,13,3832-3841.
[161] Sun C.Y., Liu S. X., Liang D.D., Shao K.Z., Ren Y.H., Su Z.M., Highly Stable Crystalline CatalystsBased on a Microporous Metal Organic Framework and Polyoxometalates, J. Am. Chem. Soc.,2009,131,1883-1888.
[162] Wang X.L., Guo Y.Q., Li Y.G., Wang E.B., Hu C.W., Hu N.H., Novel Polyoxometalate-Templated,3-DSupramolecular Networks Based on Lanthanide Dimers: Synthesis, Structure, and Fluorescent Propertiesof [Ln2(DNBA)4(DMF)8][Mo6O19](DNBA=3,5-Dinitrobenzoate), Inorg. Chem.,2003,42,4135-4140.
[163] Knaust J.M., Inman C., Keller S. W., A host–guest complex between a metal–organic cyclotriveratryleneanalog and a polyoxometalate:[Cu6(4,7-phenanthroline)8(MeCN)4]2PM12O40(M=Mo or W), Chem.Commun.,2004,5,492-493.
[164] Lozan V., Solntsev P.Y., Leibeling G., Domasevitch K.V., Kersting B., Tetranuclear Nickel ComplexesComposed of Pairs of Dinuclear LNi2Fragments Linked by4,4′-Bipyrazolyl,1,4-Bis(4′-pyrazolyl)benzene,and4,4′-Bipyridazine: Synthesis, Structures, and Magnetic Properties, Eur. J. Inorg. Chem.,2007,20,3217-3226.
[165] Zhang J.P., Horike S., Kitagawa S., A Flexible Porous Coordination Polymer Functionalized byUnsaturated Metal Clusters, Angew. Chem. Int. Ed,.2007,46,889-892.
[166] Wang X.L., Qin C., Wu S.X., Shao K.Z., Lan Y.Q., Wang S., Zhu D.X., Su Z.M., Wang E.B., Bottom-UpSynthesis of Porous Coordination Frameworks: Apical Substitution of a Pentanuclear Tetrahedral Precursor,Angew. Chem. Int. Ed.,2009,48,5291-5295.
[167] Yang E.C., Zhao H. Ding K., B., Wang X. G., Zhao X. J., Four Novel Three-Dimensional Triazole-BasedZinc(II) Metal Organic Frameworks Controlled by the Spacers of Dicarboxylate Ligands: HydrothermalSynthesis, Crystal Structure, and Luminescence Properties, Cryst. Growth. Des.,2007,7,2009–2015.
[168] Lu J., Zhao K., Fang Q.R., Xu J.Q., Yu J.H., Zhang X., Bie H.Y., Wang T.G., Synthesis andCharacterization of Four Novel Supramolecular Compounds Based on Metal Zinc and Cadmium, Cryst.Growth. Des.,2005,53,1091–1098.
[169] Wu T., Li M., Li D., Huang X.C., Anionic CunIn Cluster-Based Architectures Induced by In SituGenerated N-Alkylated Cationic Triazolium Salts, Cryst. Growth. Des.,2008,8,568.568–574.
[170] Tangoulis V., Raptopoulou C.P., Terzis A., Polynuclear Nickel(II) Complexes: Preparation,Characterization, Magnetic Properties, and Quantum-Chemical Study of [Ni5(OH)(Rbta)5(acac)4(H2O)4](RbtaH=Benzotriazole and5,6-Dimethylbenzotriazole), Inorg. Chem.,1998,37,3142–3153.
[171] Jones L.F., Raftery J., Teat S.J., Collison D., Brechin E. K., Manganese (III) fluoride as a new synthonin Mn cluster chemistry, Polyhedron,2005,24,2443-2449.
[172] S. Biswas, M. Tonigold, M. Speldrich, P. K gerler and D. Volkmer, Nonanuclear CoordinationCompounds Featuring {M69L12}+Cores (M=NiII, CoII, or ZnII; L=1,2,3-Benzotriazolate), Eur. J. Inorg.Chem.,2009,21,3094–3101.
[173] Buschbaum K.M., Mokaddem Y., Eur. J. Rare Earth Benzotriazolates: Coordination PolymersIncorporating Decomposition Products from Ammonia to1,2-Diaminobenzene in∞1[Ln(Btz)3(BtzH)](Ln=Ce, Pr),∞1[Ln(Btz)3{Ph(NH2)2}](Ln=Nd, Tb, Yb), and∞1[Ho2(Btz)6(BtzH)(NH3)], Inorg. Chem.,2006,10,2000–2010.
[174] Han Z.B., Luan G.Y., Wang E. B., Synthesis, properties and crystal structure of a novelorganic–inorganic hybrid constructed from tungstophosphoric acid and benzotriazole, Transition Met.Chem.,2003,28,63-68.
[175] Han Z.B., Wang X.L., Wang L., Wang E.B., Luan G.Y., Hu N.H., Jia H.Q., Synthesis, ElectrocatalyticProperties and Crystal Structure of a New Organic-inorganic Hybrid Constructed fromDodecamolybdophosphoric Acid and Benzotriazole, Chem. Res. Chinese U.,2003,19,127.
[176] Wang X.L., Hu H.L., Liu G.C., Lin H.Y., Tian A.X., Self-assembly of nanometre-scalemetallacalix[4]arene building blocks and Keggin units to a novel (3,4)-connected3D self-penetratingframework, Chem. Commun.,2010,46,6485-6487.
[177] Wang X.L., Hu H.L., Tian A.X., Lin H.Y., Li J., Application of Tetrazole-Functionalized Thioetherswith Different Spacer Lengths in the Self-Assembly of Polyoxometalate-Based Hybrid Compounds, Inorg.Chem.,2010,22,10299–10306.
[178] Sheldrick, G. M, Acta Crystallogr. Sect. A: Found. Crystallogr. A short history of SHELX2008,64,112.
[179] Dong S., Xi X., Tian M., Electroanal J.. Chem.,1995,395,227.
[180] Brown I. D., Altermatt D., Bond-valence parameters obtained from a systematic analysis of the InorganicCrystal Structure Database, Acta Crystallogr. B,1985,41,244.
[181] Wang X.L., Qin C., Wang E.B., Su Z.M., An unusual polyoxometalate-encapsulating3D polyrotaxaneframework formed by molecular squares threading on a twofold interpenetrated diamondoid skeleton,Chem. Commun.,2007,41,4245-4247.
[182] Liu C.M., Zhang D.Q., Zhu D.B., One-and Two-Dimensional Coordination Polymers Constructed fromBicapped Keggin Mixed Molybdenum Vanadium Heteropolyoxoanions and Polynuclear Copper(I)Clusters Bridged by Asymmetrical Bipyridine (2,4‘-bipy and2,3‘-bipy) Ligands, Cryst. Growth Des.,2006,6,524–529.
[183] Li S.L., Lan Y.Q., Ma J.F., Yang J., Liu J., Fu Y.M., Su Z.M., Inorganic–organic hybrid materials withdifferent dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanionclusters, Dalton Trans.,2008,15,2015.2015-2025.
[184] Buschbaum K. M. and Mokaddem Y., Rare Earth Benzotriazolates: Coordination PolymersIncorporating Decomposition Products from Ammonia to1,2-Diaminobenzene in∞1[Ln(Btz)3(BtzH)](Ln=Ce, Pr),∞1[Ln(Btz)3{Ph(NH2)2}](Ln=Nd, Tb, Yb), and∞1[Ho2(Btz)6(BtzH)(NH3)], Eur. J. Inorg.Chem.,2006,10,2000–2010.
[185] Tian A.X., Ying J., Peng J., Sha J.Q., Pang H.J., Zhang P.P., Chen Y., Zhu M., Su Z.M., Assemblies ofCopper Bis(triazole) Coordination Polymers Using the Same Keggin Polyoxometalate Template, Inorg.Chem.,2009,48,100.100–110.
[186] Dong B.X., Xu Q., Structural Investigation of Flexible1,4-Bis(1,2,4-triazol-1-ylmethyl)benzene Ligandin Keggin-Based Polyoxometalate Frameworks Cryst. Growth. Des.,2009,9,2776–2782.
[187] Tian A.X., Ying J., Peng J., Sha J.Q., Han Z.G., Ma J.F., Su Z.M., Hu N.H., Jia H.Q., Assembly of theHighest Connectivity Wells-Dawson Polyoxometalate Coordination Polymer: the Use of Organic LigandFlexibility, Inorg. Chem.,2008,47,3274–3283.
[188] Sha J.Q., Peng J., Tian A.X., Liu H.S., Chen J., Zhang P.P., Su Z.M., Assembly of Multitrack Cu NCoordination Polymeric Chain-Modified Polyoxometalates Influenced by Polyoxoanion Cluster andLigand, Cryst. Growth. Des.,2007,7,2535–2541.
[189] Zhang C.J., Pang H.J., Tang Q., Wang H.Y., Chen Y.G., Three3D octamolybdate-based hybrids with1D–3D CuI/CuII-bis(triazole) motifs: influence of the amount of Et3N, New J. Chem.,2011,35,190-196.
[190] Gao G.G., Xu L., Qu X.S., Liu H., Yang Y.Y., New Approach to the Synthesis of anOrganopolymolybdate Polymer in Aqueous Media by Linkage of Multicarboxylic Ligands, Inorg. Chem.,2008,47,3402–3407
[191] Hou G.F., Bi L.H., Li B., Wang B., Wu L.X., Polyoxometalate charge directed coordination assemblies:Macrocycles and polymer chains, CrystEngComm,2011,13,3526-3535.
[192] Yang E.C., Zhao H.K., Ding B., Wang X.G., Zhao X.J., Four Novel Three-Dimensional Triazole-BasedZinc(II) Metal Organic Frameworks Controlled by the Spacers of Dicarboxylate Ligands: HydrothermalSynthesis, Crystal Structure, and Luminescence Properties, Cryst. Growth. Des.,2007,7,2009–2015.
[193] Yu K., Chen W.L., Zhou B.B., Li Y.G., Yu Y., Su Z.H., Gao S., Chen Y., New extendedpoly(oxomolybdophosphates) based on strontium(II) linkers, CrystEngComm,2011,13,3417-3424.
[194] Liu H.Y., Wu H., Yang J., Liu Y.Y., Ma J.F., Bai H.Y., Solvothermal Assembly of a Series ofOrganic–Inorganic Hybrid Materials Constructed from Keggin Polyoxometalate Clusters andCopper(I)–Organic Frameworks, Cryst. Growth Des.,2011,11,1786–1797.
[195] Wu X.Y., Dong P., Yu R., Zhang Q.K., Kuang X.F., Chen S.C., Lin Q.P., Lu C.Z., A2Dpolyoxometalate-based complex: spin-canting and metamagnetism, CrystEngComm,2011,13,3686-3688.
[196] Reinoso S., Vitoria P., Gutie′rrez-Zorrilla J. M., Lezama L., Madariaga J. M., Felices L. S. and IturrospeA., Coexistence of Five Different Copper(II) Phenanthroline Species in the Crystal Packing ofInorganic Metalorganic Hybrids Based on Keggin Polyoxometalates andCopper(II) Phenanthroline Oxalate Complexes, Inorg. Chem.,2007,46,4010–4021.
[197] Zhao L.L., Luo X.Z., Xu L., Jiang N., Li F.Y., Li Y.G., One-dimensional inorganic frameworkconsisting of the sandwich-type germanomolybdate and the copper complex linker: Synthesis, crystalstructure, and magnetic property, Inorg. Chem. Commun.,2010,13,554.
[198] Wang C.M., Zheng S.T., Yang G.Y., Novel Copper-Complex-Substituted Tungstogermanates, Inorg.Chem.,2007,46,616–618.
[199] Zhao J.W., Zheng S.T., Li Z.H., Yang G.Y., Combination of lacunary polyoxometalates and high-nucleartransition-metal clusters under hydrothermal conditions: first65·8CdSO4-type3-D framework built byhexa-CuIIsandwiched polyoxotungstates, Dalton Trans.,2009,8.1300-1306.
[200] Lin H.Y., Wang X.L., Hu H.L., Chen B.K., Liu G.C., A novel copper(II) complex constructed with mixedligands of biphenyl-4,40-dicarboxylic acid (H2bpdc) and dipyrido [3,2-d:20,30-f]quinoxaline (Dpq):Synthesis, structure, electrochemistry and electrocatalysis, J. Solid State Chem.,2009,11,643-650.
[201] Hu Y., Luo F., Dong F.F., Design synthesis and photocatalytic activity of a novel lilac-likesilver-vanadate hybrid solid based on dicyclic rings of [V4O12]4with {Ag7}7+cluster, Chem. Commun.,2011,47,761-763.
[202] Wu Q., Chen W.L., Liu D., Liang C., Li Y.G., Lin S. W., Wang E.B., New class of organic–inorganichybrid aggregates based on polyoxometalates and Metal–Schiff-base, Dalton Trans.,2011,40,56-61.
[203] Katsoulis D.E., A Survey of Applications of Polyoxometalates, Chem. Rev.1998,98,359–388.
[204] Pope M.T., Müller A., Polyoxometalate Chemistry: An Old Field with New Dimensions in SeveralDisciplines, Angew. Chem., Int. Ed.1991,30,34–48.
[205] Long D.L., Burkholder E., Cronin L., Polyoxometalate Clusters, Nanostructures and Materials: FromSelf Assembly to Designer Materials and Devices, Chem. Soc. Rev.2007,36,105–121.
[206] Yu R.M., Kuang X.F., Wu X.Y., Lu C.Z., Stabilization and immobilization of polyoxometalates in porouscoordination polymers through host–guest interactions, Coord. Chem. Rev.2009,253,2872–2890.
[207] Rarig Jr R. S., Zubieta J., Octamolybdate subunits as building blocks in the hydrothermal synthesis oforganically templated mixed metal oxides: the synthesis and X-ray characterization of
[Cu2Mo4O13(3,3′-bipy)2]·H2O,[CuMo4O13(Hdipyreth)], and [Cu(dpp)]2[Cu2(α-Mo8O26)(dpp)2]·2H2O(3,3′-bipy=3,3′-bipyridine; DIPYRETH=1,2-bis(2-pyridyl)ethylene; DPP=4,4′-trimethylenedipyridine),Polyhedron.2003,22,177–188.
[208] Ren Y.P., Kong X.J., Hu X.Y., Sun M., Long L.S., Huang R.B., Zheng L.S., Influence of StericHindrance of Organic Ligand on the Structure of Keggin-Based Coordination Polymer, Inorg. Chem.2006,45,4016–4023.
[209] Sha J. Q., Peng J., Liu H. S., Chen J., Dong B. X., Tian A. X., Su Z. M., Keggin POMs Modified byBonding to Multitrack Cu(bipy) Chains through Linearly Arrayed Terminal and Bridging Oxygen Atomsof the M3O13Triad, Eur. J. Inorg. Chem.2007,46,1268–1274.
[210] Tian A.X., Ying J., Peng J., Sha J.Q., Han Z.G., Ma J.F., Su Z.M., Hu N.H., Jia H.Q., Assembly of theHighest Connectivity Wells-Dawson Polyoxometalate Coordination Polymer: the Use of Organic LigandFlexibility, Inorg. Chem.2008,47,3274–3283.
[211] Hagrman D., Zubieta C., Rose D.J., Zubieta J., Haushalter R.C., Composite Solids Constructed FromOne-Dimensional Coordination Polymer Matrices and Molybdenum Oxide Subunits: PolyoxomolybdateClusters within [{Cu(4,4′-bpy)}4Mo8O26] and [{Ni(H2O)2(4,4′-bpy)2}2Mo8O26] and One-DimensionalOxide Chains in [{Cu(4,4′-bpy)}4Mo15O47]·8H2O, Angew. Chem., Int. Ed.1997,36,873–876.
[212] Tian A. X., Ying J., Peng J., Sha J. Q., Pang H. J., Zhang P. P., Chen Y., Zhu M., Su Z. M., Tuning theDimensionality of the Coordination Polymer Based on Polyoxometalate by Changing the Spacer Lengthof Ligands, Cryst. Growth Des.2008,8,3717–3724.
[213] Dang D.B., Bai Y., He C., Wang J., Duan C.Y., Niu J.Y., Structural and Catalytic Performance of aPolyoxometalate-Based Metal Organic Framework Having a Lanthanide Nanocage as a SecondaryBuilding Block, Inorg. Chem.2010,49,1280–1282.
[214] Reinoso S., Vitoria P., Felices L.S., Montero A., Lezama L., Gutiérrez-Zorrilla J.M.,Tetrahydroxy-p-benzoquinone as a Source of Polydentate O-Donor Ligands. Synthesis, Crystal Structure,and Magnetic Properties of the [Cu(bpy)(dhmal)]2Dimer and the Two-Dimensional
[{SiW12O40}{Cu2(bpy)2(H2O)(ox)}2]·16H2O Inorganic Metalorganic Hybrid, Inorg. Chem.2007,46,1237–1249.
[215] Allain C., Favette S., Chamoreau L.M., Vaissermann J., Ruhlmann L., Hasenknopf B., HybridOrganic–Inorganic Porphyrin–Polyoxometalate Complexes, Eur. J. Inorg. Chem.2008,22,3433–3441.
[216] Zhai Q.G., Wu X.Y., Chen S.M., Zhao Z.G., Lu C.Z., Construction ofAg/1,2,4-Triazole/Polyoxometalates Hybrid Family Varying from Diverse Supramolecular Assemblies to3-D Rod-Packing Framework, Inorg. Chem.2007,46,5046–5058.
[217] Long D.L, Tsunashima R. and Cronin L., Polyoxometalates: Building Blocks for Functional NanoscaleSystems, Angew. Chem. Int. Ed.,2010,49,1736–1758.
[218] Kortz U., Müller A., Slageren J. V., Schnacke J., Dalalf N. S., Dressel M., Polyoxometalates:Fascinating structures, unique magnetic properties, Coord. Chem. Rev.,2009,253,2315-2327.
[219] Rhule J. T., Neiwert W. A., Hardcastle K. I. B., Do T. and Hill C. L., Ag5PV2Mo10O40, a HeterogeneousCatalyst for Air-Based Selective Oxidation at Ambient Temperature, J. Am. Chem. Soc.,2001,123,12101-12102.
[220] Fu H., Li Y.G., Lu Y., Chen W.L., Wu Q., Meng J.X., Wang X.L., Zhang Z.M., Wang E.B.,Polyoxometalate-Based Metal Organic Frameworks Assembled under the Ionothermal Conditions, Cryst.Growth Des.,2011,11,458-465.
[221] Xiao L.N., Wang Y., Pan C.L., Xu J.N., Wang T.G., Ding H., Gao Z.M., Zheng D.F., Cui X.B., Xu J.Q.,Three novel supramolecular hybrid compounds based on keggin polytungstates, CrystEngComm.2011,13,4878-4885.
[222] Wang Y., Peng Y., Xiao L.N., Hu Y.Y., Wang L.M., Gao Z.M., Wang T.G., Wu F.Q., Cui X.B., Xu J.Q.,New compounds constructed from polyoxometalates and transition metalcoordination complexes withlower positive charge, CrystEngComm.,2012,14,1049-1056.
[223] Pang H.J., Ma H.Y., Peng J.n, Zhang C.J., Zhang P.P., Su Z.M., Study of a hydrothermal reactionsystem of copper, imidazole andpolyoxometalates: selective assembly of a3D porous metal–organicpseudorotaxaneframework and encapsulation of polyoxometalate clusters, CrystEngComm.2011,13,7079-7085.
[224] Wang X.L., Chen B.K., Liu G.C., Lin H.Y., Hu H.L., Chen Y.Q., Synthesis, structure and electrochemicalproperty of a new three-dimensional inorganic–organic vanadate coordination polymer
[Cu2(bbi)2(V4O12)·4H2O](bbi=1,1-(1,4-butanediyl)bis(imidazole), J. Inorg. Organomet. Polym.2008,19，176-180.
[225] Wang X.L., Li J., Tian A., Liu G.C., Gao Q., Lin H.Y., Zhao D., A3D organopolymolybdate polymerwith unusual topology functionalized by1,4-bis(1,2,4-triazol-1-yl)butane through Mo-N bond,CrystEngComm.,2011,13,2194-2196.
[226] Tian A.X., Ying J., Peng J., Sha J.Q., Pang H.J., Zhang P.P., Chen Y., Zhu M., Su Z.M., Tuning theDimensionality of the Coordination Polymer Based on Polyoxometalate by Changing the Spacer Lengthof Ligands, Cryst.Growth&Des.,2008,8,3717-3724.
[227] Wang X.L., Bi Y.F., Chen B.K., Lin H.Y., Liu G.C., Self-Assembly of Organic–Inorganic HybridMaterials Constructed from Eight-Connected Coordination Polymer Hosts with Nanotube Channels andPolyoxometalate Guests As Templates, Inorg. Chem.,2008,47,2442-2448.
[228] I. D. Brown and D. Altermatt. Bond-valence parameters obtained from a systematic analysis of theInorganic Crystal Structure Database Acta Crystallogr. B.1985,41,244-247.
[229] Hu Y., Luo F., Dong F.F., Design synthesis and photocatalytic activity of a novel lilac-likesilver-vanadatehybrid solid based on dicyclic rings of [V4O12]4-with {Ag7}7+cluster, Chem. Commun.,2011,47,761-763.
[230] Wu Q., Chen W.L., Liu D., Liang C., Li Y.G., Lin S.W., Wang E.B., New class of organic–inorganichybrid aggregates based on polyoxometalates and Metal–Schiff-base, Dalton Trans.,2011,40,56-61.
[231] Tian, A. X.; Ying, J.; Peng, J.; Sha, J. Q.; Pang, H. J.; Zhang, P. P.; Chen, Y.; Zhu, M.; Su, Z. M. Tuningthe Dimensionality of the Coordination Polymer Based on Polyoxometalate by Changing the SpacerLength of Ligands, Cryst. Growth. Des.2008,8,3717-3724.
[232] Wang, X. L.; Bi, Y. F.; Chen, B. K.; Lin, H. Y.; Liu, G. C. Self-assembly of Organic-Inorganic HybridMaterials Constructed from Eight-connected Coordination Polymer Hosts with Nano-tubes Channel andPolyoxometalate Guests as Templates, Inorg. Chem.2008,47,2442-2448.
[233] Dong S., Xi X., Tian M., Study of the electrocatalytic reduction of nitrite with silicotungsticheteropolyanion, J. Electroanal. Chem.1995,385,227-233.
[234] Tian A. X., Ying J., J. Peng, Sha J. Q., Pang H. J., Zhang P. P., Chen Y., Zhu M., Su Z. M., Assembliesof Copper Bis(triazole) Coordination Polymers Using the Same Keggin Polyoxometalate Template, Inorg.Chem.2009,48,100-110.
[235] Li S. L., Lan Y.Q., Ma J.F., Yang J., Liu J., Fu Y.M. and Su Z.M., Inorganic–organic hybrid materialswith different dimensions constructed from copper–fluconazole metal–organic units and Kegginpolyanion clusters, Dalton Trans.,2008,15,2015-2025.