| In this paper, using series of 1:11 and 1:12 Keggin-Heteropolytungstates anions as building units, we get successfully nine new kinds of unreported polyoxometalate-based organic-inorganic complexes under hydrothermal condition. These complexes are characterized by X-ray single crystal diffractions, elemental analyses, IR, XRD, TG and CV. Some of them are preliminary studied on electrocatalytic oxidation of H2O to O2.1. Using series of 1:11 Keggin anions as building units, three kinds of organic-inorganic complexes were synthesized. [Hpy]2{[Co(4,4'–Hbpy)2(H2O)2][SiCoW11O39] (1) [Hpy]2{[Co(4,4'–Hbpy)2(H2O)2][GeCoW11O39] (2) [H2bpy]3[SiMnW11O39]·2H2O (3) Complexes 1 and 2 are isomorphic. They exhibit a 2D layered structure constructed from polymeric [XCoW11O39]6- [X=Si(1); X=Ge(2)] chains and [Co(4,4'–Hbpy)2(H2O)2]4+ subunits.The 4,4'–bpy molecules of neighboring layers are inserted and overlapped each other, generating a 3D supramolecular structure. In complex 3, the Keggin anions are connected through a common oxygen atom to give a one-dimensional chain. 1-CPEs are active for the electrocatalytic oxidation of H2O to O2 in 0.5 M sodium acetate buffer (pH 4.5) containing 1 mM [Ru(bpy)3]2+ solution.2. Using Keggin [SiW12O40]4- anions as building units, two new complexes of 2D network structure were synthesized. [{Mn(2,2'–bipy)2}2{SiW12O40}] (4) [{Co(2,2'–bipy)2}2{SiW12O40}] (5) Complexes 1 and 2 are isomorphic. They are constructed into a diamond-shaped grid network through bridgeding polyoxometalate cluster {SiW12O40} and {M(2,2'–bipy)2} fragments.3. Using Keggin [SiW12O40]4- anions as building units, four Cu(II) and Ag(I) complexes were synthesized. {Cu(4,4'–bipy)3/2·H2O}2{SiW12O40}·4H2O (6) [{Ag4(4,4'–bipy)3(2,2'–bipy)2}{SiW12O40}] (7) [{Ag(py)2}4{SiW12O40}] (8) [{Ag(4,4'–bipy)}2(Hpy)2{SiW12O40}] (9) Complexes 6 and 7consist of [SiW12O40]4- anions and Cu(Ag)–bipy complex units, forming a one-dimensional chain structure. Complexes 8 and 9 exhibit a 2D structure constructed from [SiW12O40]4- and [{Ag(py)2}4]4+ subunits for 8, [{Ag(4,4'–bipy)}2(Hpy)2]4+ subunits for 9. |
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