| In this thesis, we chose B-type Anderson polyoxoanions as building blocks, employed LnIII, lanthanide and transition-metal coordination complexes, which are decorated or bridged to Anderson polyoxoanions, eight new Anderson polyoxometalates were synthesized. These compounds are characterized by elemental analyses, IR, TG, XRD, and X-ray diffraction analysis, the luminescence, magnetic, and electronic properties were also studied.1. Two lanthanide derivatives of the B-type Anderson Polyoxometalates compounds. [Eu(H2O)7][Al(OH)6Mo6O18]·4H2O (1) {(C2H5NO2)2[Eu(H2O)5]}[Al(OH)6Mo6O18]·10H2O (2)。Compound 1 shows a 1D chain structure, 2 displays a 3D supramolecular network structure containing 1D sandglass-like channels, which were occupied by repetitive array of (H2O)8 clusters. Luminescence measurements reveal that 1 and 2 exhibit the different fluorescent emission which assigned to the different site symmetries of Eu3+ centers.2. Six transition-metal derivatives of the B-type Anderson Polyoxometalates compounds. {[Cu(2,2′-bpy)(H2O)3]2[Cr(OH)6Mo6O18]}{[Cu(2,2′-bpy)(H2O)Cl][Cu(2,2′-bpy)(H2O)(N{[Cu(2,2′-bpy)(H2O)3]2[Cr(OH)6Mo6O18]}{[Cu(2,2′-bpy)(H2O)Cl][Cu(2,2′-bpy)(H2O)(NO3)][Cr(OH)6Mo6O18]}·18H2O (3) [Cu(2,2′-bpy)(H2O)2Cl]{[Cu(2,2′-bpy)(H2O)2][Cr(OH)6Mo6O18]}·4H2O (4) (H3O){[Cu(2,2′-bpy)(H2O)2]2[Cu(2,2′-bpy)(H2O)]2}[Cr(OH)6Mo6O18]3·36H2O (5) (H3O){[Cu(2,2′-bpy)(H2O)2]2[Cu(2,2′-bpy)(H2O)]2}[Al(OH)6Mo6O18]3·33H2O (6) [Cu2(bpy)2(μ-ox)][Al(OH)7Mo6O17] (7) [Cu2(bpy)2(μ-ox)][Cr(OH)7Mo6O17] (8)Compounds 3–6 were all built up of B-type Anderson polyoxoanions and copper coordination complexes, 3 displays a discrete supramolecular structure, 4 shows a 1D chainlike structure, 5 and 6 are isomorphic which exhibit unique 3D open frameworks with lattice water molecules residing in the channels. From the three kinds of crystal structures obtained, it is clear that the intrinsic character of the acidic anions have a decisive influence on the structures of the final compounds. The compounds 5 and 6 represent the first example of 3D open framework in the TMs/2,2′-bpy/POMs system. Compounds 7 and 8 are isomorphic and exhibit a 1D chain structure, it represent the first example of mixed ligands hybrids based on Anderson polyoxoanions. Magnetic susceptibility studies reveal the strong antiferromagnetic coupling in the dinuclear copper complexes. |
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