| In this paper, we adopted the Keggin polyoxometalates as the basic building blocks and synthesized six new organic-inorganic hybrid compounds by introducing organic N-donor ligands in the hydrothermal conditions. All these compounds have been structurally characterized by IR, XPS, TG, elemental analyses and X-ray single crystal diffractions. The studies on the synthetic conditions, the reaction rules, the electrochemical properties and the partial fluorescence of these compounds under hydrothermal conditions and the factors influencing the structures of these compounds have also been carried out.1.Three new organic-inorganic Keggin polyoxometalates have been prepared by introducing organic chelating ligands 2,2'-bipy and phen in the hydrothermal conditions: in the experiment, we synthesized two isostructural bisupporting compounds 1 and 2 by using pre-synthesized Keggin polyoxometalates: [Cu(2,2'-bpy) 2]2[HPMoVI10MoV2O40]·2H2O (1), [Cu(2,2'-bpy)2]2[H2SiMoVI10MoV2O40]·2H2O(2) (2,2'-bpy = 2,2'-bpyridine) . Compound 3, [Ag(phen)2]7 [{Ag(phen)}2Ag(HVW12O40)2] (phen=1,10-phenaanthroline), was obtained via the synthesis in situ and showed a new dimeric structure.2.Three new organic-inorganic Keggin polyoxometalates have been prepared by introducing mixed ligands in the hydrothermal conditions: Compound 4, [Cu(phen)(4,4'-bpy)]2[H2SiMo12O40](4,4'-bipy = 4,4'-bipyridine , phen = 1,10-phenaanthroline), shows a isolated polyoxometalate cluster. Compounds 5 and 6, [Ag3(4,4'-bipy)2(2,2'-bipy)2][Ag(2,2'-bipy)2] [{Ag(2,2'-bipy)}HSiW11VO40] (5) and [Ag3(4,4'-bipy)2(2,2'-bipy)2][Ag(2,2'-bipy)2] [{Ag(2,2'-bipy)}PW11VO40] (6), were two isostructural monosupporting compounds. The two compounds show 3-D supramolecular network via face-to-faceπ…πstacking and weak Ag…O interactions.
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