Syntheses, Structures And Properties Of Single Ion Magnets And Magnetic Molecules Based On Cyanide And Nitrogen-Containing Polyatomic Ring Ligand

In this work, we chose the polycyanometallate and nitrogen-containing polyatomic ring ligands as building blocks, and synthesized twenty seven complexes. All the complexes were characterized by X-ray single crystal diffraction, elemental analysis, spectroscopy analysis and magnetic susceptibility studies. The specific contents are shown as follows:1. Nine1-D4d-4f complexes and three1-D5d-4f complexes have been synthesized by using [(n-Bu)3NH]3[Mov(CN)8]-2H2O and [(n-Bu)3NH]3[Wv(CN)8]·2H2O as building blocks. The4d-4f complexes have two different structures, complexes [PrⅢ(DMF)6Mov(CN)8]∞(1) and [Nd(DMF)6Mov(CN)8]∞(2) are in the P21chiral space group while other [LnⅢ(DMF)6Mov(CN)8]∞complexes are in the P21/c achiral space group. Magnetic studies reveal that there are ferromagnetic interactions between LnⅢ and Mov ions in complexes [SmⅢ(DMF)6Mov(CN)8]∞(3) and [EuⅢ(DMF)6Mov(CN)8]∞(4), and antiferromagnetic interactions between LnⅢ and MoⅤ/WⅤions in other complexes. We used Seiden’s classical-quantum model to analyze the magnetic interactions in complex [GdⅢ(DMF)6Mov(CN)8]∞(5) and the result is reasonable.2. Two mononuclear DyⅢ-complexes and three3d-metal complexes have been synthesized by using3,4,7,8-tetramethly-1,10-phenanthroline as main ligand. Magnetic properties indicate that complexes [DyⅢ(hfac)3(tmphen)](13) and [DyⅢ(acac)3(tmphen)]·2H2O (14) exhibit SIM behaviors and the effective energy barriers are35.09K and130.42K, respectively. Complex13is the first D2d-Dy(Ⅲ) based SIM with derivative of phenanthroline.3. Three3d-4f ion-pair complexes and two binuclear MnⅢcomplexes have been synthesized by using MnⅢ-Schiff base fragment as building blocks. We used an approximate model to analyze the magnetic interactions in complexes18and19. Magnetic studies indicate that there are antiferromagnetic interactions among the paramagnetic ions in complexes [MnⅢ(MeOSalen)DyⅢ(hfac)2(CF3COO)(H2O)] [DyⅢ(hfac)3(CF3COO)(H2O)]-2CHC13(18),[MnⅢ(MeOSalen)(H2O)][TbⅢI(hfac)4]·CHCl3(19) and [MnⅢ2(MeOSalen)2(N3)(H2O)]C1O4-CH3CN(21).4. Three hexanuclear LnⅢ-complexes, one trinuclear CuⅡ-complex and one1-D CuⅡ-complex have been synthesized by using4-amido-3,5-dimethyl-1,2,4-triazole as ligand. Magnetic studies show that there are antiferromagnetic interactions among the paramagnetic ions in complexes [Gd6Cl2(O)(OH)8(L)4(H2O)14]Cl6·9H2O (24),[Cu3(N3)6(L)4](26) and{[Cu3(NO3)5(OH)(L)3]·0.5H2O}n(27).