New Polyoxometalate Constructed From The Second Transition Metal And Organonitrogen Molecule

Recently, the design and synthesis of inorganic-organic hybrid compounds, which introduced transition metals/alkaline-earth as charge-compensation, polyoxometalates (POMs) as template blocks, are of great interest owing to their intriguing structures and potential applications in catalysis, optics, biological medicine and materials.In this thesis, nine new POMs, based on polyoxoanions and appropriate transition metal cations or organic ligands, have been synthesized under the conventional aqueous and hydrothermal reaction methods. These complexes are determined by single crystal structure X-ray diffraction and characterized by elemental analysis, IR, XPS, thermal properties, fluorescence spectroscopy, cyclic voltammograms and magnetic properties. The main works are as follows:1. Based on Keggin-type POMs as template, transition metal-Cu, Et3N, phen and flexile ligand bpp as bridging cations, 4 new supramolecular compounds were structured, respectively.[HN(C2H5)3]3[N(C2H5)3]2H2[PW10VIW2VO40]·2H2O (1)[Cu(phen)(H2O)3]0.5[Cu(phen)2(H2O)][PMo12O40] (2)[Hbpp]3[PW12O40] (3)[Cu(bpp)]2[Cu2(bpp)3][SiW12O40] (4)All of these supramolecular assemblies are built upon extensive hydrogen bonding interaction. Compound 1 contains a supramolecular inclusion structure through hydrogen bonds directing organic molecular Et3N and anions arranged orderly. Compound 4 with 2D wave-type layer is a bi-supported silico-tungstate modified by copper-bpp.2. Based on pseudo-Dawson type polyoxoanions, organic molecules bpe and bpp as bridging cations, two pseudo-Dawson type inorganic-organic compounds have been gained via hydrothermal method, respectively.(H2bpe)3.5H2[SbW18O60]·5H2O (5)[Cu2(Hbpp)4](H2bpp)0.5H2[SbW18O60]·3H2O (6)3. Based on tri-lacunary Keggin anions [AsW9O34]9- as template, introduced transition metals cobalt and nickel, three TMSPs sandwich-type compounds have been gained. Na10[Co4(AsW9O34)2(H2O)2]·32H2O (7)[H2bpp]5[Ni4(AsW9O34)2(H2O)2]·1/2H2O (8)[H2bpe]5[Ni4(AsW9O34)2(H2O)2]·3H2O (9)Compound 7 has been gained via conventional aqueous method with high-dimensional, sodium ion plays a role of"adhesive"with various cooperate fashions, which connected with terminal oxygen atoms by covalent bonds. Compounds 8 and 9 are similar in structural features, except the different fashions forming multi-point capped hydrogen bonds by organic cations. Compound 8 shows classical paramagnetic.