| Five new compounds based on lacunary heteropolymolybdate building blocks have been synthesized. we studied the process of reaction condition, which includes pH value, temperature, counterion and ratio of mixture and so on. We analyzed the structures of these compounds through single X-ray diffraction, and characterized them via elemental analysis, IR and UV. The electrochemical properties and magnetic properties have also been studied.1. The reaction of GeO2, (NH4)6Mo7O24·4H2O and transition-metal in aqueous solution produce two new germanomolybdate: (Him)8Na7H7[Cu(im)4(CuGeMo9O33)2] [(CuGeMo9O33)2]﹒41H2O (im = imidazole) (1) (Him)5Na2H5[Mn2(GeMo9O33)2]﹒20.5H2O (2)Compound 1 exhibits a one-dimensional chain-like framework [Cu(im)4(CuGeMo9O33)2]10- with isolated [(CuGeMo9O33)2]12– units residing among the chains. In the compound 2, the polyanion [(CuGeMo9O33)2]12– is composed of two unusual [GeMo9O33]8– moieties linked with a {Cu2O10} group.2. By using a"one-pot"synthetic route, two new polymolybdates were obtained and structurally characterized: (C3H5N2)14Na2(NH4)10[Mn(AsMo10O35)2][(AsMo10O35)2]·19H2O (3) (C3H5N2)16(NH4)2H4[Na1.6Cu0.4(C3H4N2)0.5(AsMo10O35)2]2·23H2O (4)In the compound 3, the [Mn(H2O)2]2+ connects to two [AsШMo10O35]7- clusters through the four terminal oxo groups of two MoO6 octahedron. The other two [AsШMo10O35]7- clusters are resided beside the central [Mn(H2O)2(AsШMo10O35)2]12- frament, which are connected to the [Mn(H2O)2(AsШMo10O35)2]12- frament by the sodium through two bridge oxygen atoms, respectively. The polyanion of 4 consists of two{[Na1.6Cu0.4(C3H4N2)(AsMo10O35)2]2} fragments, which are connected by one [Cu(H2O)2]2+. To our knowledge, the {AsШMo10O35} fragment is in compound 3 and 4 is first reported.3. Choosing NaAsO2, (NH4)6Mo7O24·4H2O and rare earth as the starting materials, one novel heteropolymolybdate were obtained and structurally characterized: (Him)8[Na(im)2]2H6[Ce(H2O)8]2[Ce(H2O)6(AsMo10O35)2]2﹒23H2O (im = imidazole) (5)It is expected that strong hydrogen bonds between the ammonium ion, trans aqua ligand and the terminal Mo=O oxygen atoms stabilize this configuration. |
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