| Polyoxometalate anions exhibit the superiority of coordinative diversity and nano-scale size in building new coordination polymers with nano-pore structure. In this paper, using Keggin-Molybdophosphate anions, transition metal ions and rigid bipyridine ligand as building blocks, 13 kinds of unreported polyoxometalate-based organic-inorganic hybrid compounds were designed and synthesized. They are characterized by elemental analysis, XPRD, IR, TG, XPS and single crystal X-ray diffraction analysis and some of them were preliminary studied on fluorescent properties and electrochemical properties. The major results are as follows:1. Using Keggin-Molybdophosphate anions as a template, five kinds of organic-inorganic hybrid framework compounds of metal-oxides were synthesized. [Mo2Mn2IV(OH)O8(bpy)10][PMo12O40] (1) [Mo4VO8(bpy)6][PMo11VO40]·4H2O (2) [MnIVMnIIMo(bpy)5O5][PMo11VO40][bpy]·2H3O (3) Ca[Mo5O14(bpy)5][PMo11VO40][0.5bpy]·4.5H2O (4) [Mo9VO28(bpy)9][PMo12O40] (5)They are all based on Keggin anions as a template compound. The host frames are as follows: Compounds 2 and 4 consist of the pure Mo-oxide. Compounds 1 and 3 consist of the heterometal-oxide of the Mo and Mn. Compounds 1, 2 and 3 consist of finite metal-atoms to form organic-inorganic hybrid 0D chain-shaped structure. Compound 4 exhibits an infinite 1D Z-shaped chain. Compound 5 is formed by heterometal-oxide of the Mo and V and exhibit a 2D honeycomb-like structure with 1D pore, where Keggin anions are located in.2. With Keggin-Molybdophosphate anions as building blocks, two kinds of coordination polymers with the Ag-Ag interactions were synthesized. [{Ag3(bpy)4}{PMo12O40}]·2H2O (6) [{Ag(bpy)}2{Ag4(bpy)6}{PMo11VO40}][{Ag(bpy)}2{PMo11VO40}] (7)Compounds 6 and 7 are coordination polymers with a 1D chain structure, in which two compounds contain (Ag3)3+ and (Ag4)4+ high-nuclear clusters, respectively. Through theoretical calculations it proved that they exist in Ag-Ag interactions. Fluorescence spectroscopy shows that they have photoluminescence properties.3. With Keggin-Molybdophosphate anions as building blocks, two kinds of coordination polymers of 2D network structure of the Cd (II) and Zn (II) were synthesized. [{Cd(2, 2′-bpy)2}2{PMo11VO40}] (8) [{Zn(2, 2′-bpy)2}2{PMo11VO40}] (9)Compounds 8 and 9 exhibit a 2D layered structure. They are isomorphic, and are constructed into a diamond-shaped grid network through bridgeding polyoxometalate cluster {PMo11VO40} and {M(2, 2′-bpy)2} fragments. Polyanions are located in the node of the diamond lattice. The fluorescence spectra of two compounds show that they have luminescence properties.4. Utilizing isopolyoxometalate anions {Mo6O22} and heteropolyoxometalate anions {PMo12O40} as building blocks, the 1D organic-inorganic hybrid compound is constructed through bridging of the {CuII(2, 2′-bpy)} fragments . [{CuII(2, 2′-bpy)}6(MoVMo5VIO22)][PMo12VIO40]·H2O (10)In compound 10, {Mo6O22} is a relatively new structure. It is coordinated by six {Cu(2, 2′-bpy)} complex fragments to form a stable structure because each molybdenum has three the terminal oxygen atoms.5. With Keggin-Molybdophosphate anions as building blocks, three kinds of Cu(II)/Cu(I) coordination compounds were synthesized. {[Cu(2, 2′-bpy)(4, 4′-bpy)(H2O)]2(H2PMo11VO40)2}(4, 4′-bpy)·H2O (11) [Cu3(4, 4′-bpy)3{PMo12O40}](en)·3H2O (12) [Cu2(OH)2(H2O)2(4, 4′-bpy)3{HPMo12O40}]·4H2O (13)Compound 11 is based on {PMo11VO40} as the building blocks, through the [Cu(2, 2′-bpy)(4, 4′-bpy)(H2O)]2+ fragments, forming 1D chain organic-inorganic hybrid compounds. While the compounds 12 and 13 are organic-inorganic hybrid 2D layered compounds with a molecular ladder structure. They were formed by using {PMo12O40} as the building block brigded the Cu (II) and organic ligands 4, 4′-bpy.
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