| Inorganic-organic molecular materials have received more and more attentions because of their diversity of structures and collective properties such as nonlinear optical, superconductivity, ferromagnetism properties, ect. Polyoxometalate anions present several characteristics that have made them suitable and attractive as active counterions for new radical cation salts.This paper mainly focuses on charge transfer salts based on ferrocene and its derivatives with polyoxometalates. We synthesized several new charge transfer salts: [NBu4]6[Fe(C5H5)2][AsMo12O40]2(1), [NBu4]2[Fe(C5H5)2]2[SiMo12O40]·CH3CN(2) , and the charge transfer salts of AsMo12O403-, or SiMo12O404-, or PMnW11O403- with Fe(C5H5)2, and those of AsMo12O403-, or PMo12O403-, or AsMo12O403-, PMo12O403-, with Fe(C5H5)2CHO, and that of PMo12O403-, SiMo12O404- with Fe(C5H5)2COCH3. Some of them were partly charactered by IR, UV-vis, ESR and CV. The crystal structures of compounds 1 and 2 were determined by X-ray diffraction analysis.In the charge transfer salt [NBu4]6[Fe(C5H5)2][AsMo12O40]2, the layers of the organic donors FeCp2+ and inorganic acceptor [AsMo12O40]3- are alternatively arranged in (100) planes. Each FeCp2+ ion is surrounded by four anion [AsMo12O40]3-, and each anion is surrounded by two ferrocene. There are distinct ESR signals of FeCp2+ and Mo5+ in the 110K.In the crystal structure of [NBu4]2[Fe(C5H5)2]2[SiMo12O40]·(CH3CN), each anion is surrounded by four [Fe(C5H5)2]+, The layers of the organic donors and inorganic acceptors are alternatively arranged and the molecules of acetonitrile and NBu4+ are filled to thier interspaces. It is showed that the charges transfer took place between ferrocene and anion [SiMo12O40]4- by the bond valance calculation, IR, UV-Vis spectra and CV. It is very interesting that there are different composition ratios of Keggin anion and ferrocene in 1 and 2, which shows diversity of thier compositions and structures.On the other hand, we synthesized two new polyoxometalates, Na4[NiAs6Mo6O30]·8H2O and [NH(CH3)3]4Mo2O4(NCS)6·H2O. Under hydrothermal conditions, we got a schiff base complex Co(C5H5NCOO)2·4H2O by chance. The structures of all of the three new compounds were determined by x-ray diffraction analysis. The polyanion Na4[NiAs6Mo6O30]·8H2O is the first one with the same structure as [CoAs6Mo6O30]4- found in 1991. The compound [NH(CH3)3]4Mo2O4(NCS)6·H2O is a new kind of polyoxometalates with NCS- anion coordinating to the Mo atom.
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