| The aim of this thesis was the synthesis of the organic-inorganic materials with novel structures and the characterazation and properties of them. Using Na7HNb6O19 15H2O, Cu(O2CCH3)2 H2O and en as materials, we first synthesized an heteropolyanion [Cu(H2O)2(Nb7O22)]321- with a discrete triangol cluster structure, resulting from alterating three [Nb7O22]9- units and three [Cu(H2O)2]2+ units through Nb-Ot-Cu-Ot-Nb lineage. A novel yttrium(III) coordination compound supported by plenary Dawson cluster, [Y(NMP)5(H2O)2][Y(NMP)4(H2O)2(P2Mo,8O62)] NMP 5.5 H2O, (NMP = N-methyl-2- pyrrolidone) has been synthesized by reaction of a-H6P2Mo18O62 nH2O, Y2O3 and NMP in water. The results of the single crystal X-ray diffraction analyses show the title compound forms a neutral and discrete cluster through [P2Mo18O62]6-being coordinated to [Y(NMP)4(H2O)2]3+ through its terminal oxygen atom. We also synthesized two organic-inorganic complexes, [{Nd (NMP)2(H2O)6Cl} {Nd (NMP)2(H2O)7}H(P2Mo18O62)] and [Ce (NMP)3(H2O)6]2 [P2Mo,8O62] 0.5 NMP H2O. In addtion, using plenary Keggin structure polyanion [PM012O40]3" as based building block and using NMP and DMSO as organic coordination, we have synthesized a serial of organic-inorganic composite compounds, [{Ln(NMP)6}(PMo12O40)]n(Ln = La, Ce, Pr,Nd, Gd), [{La(DMSO)6(H2O)}(PMo12O40) H2O ]n and[{Pr(DMSO)6(H2O)}(PMo12O40) CH3CN]n. The results of the single crystal X-ray diffraction analyses show these 1:1 composite compounds present three types zigzag chains with alternating cations and anions through Mo-Ot-Ln-Ot-Mo links in the crystal.The compounds are characterized by IR, UV, and ESR spectrosbpy, single crystal X-ray structural analysis, and studied by TG/DTA, CV, the variable-temperature magnetic susceptibilities. Besides heteropolyanion [Cu(H2O)2(Nb7O22)]321- , IR results of other compounds indicate that the polyanions in the compounds still retain the basic Keggin or Dawson structure, but are distorted due to the effects of coordination, and the NMP or DMSO ligands are coordinated to the rare-earth ions by means of their oxygen atoms; ESR spectra of powder of the compounds after exposure to sunshine are typical of Mo5+or Gd3+; the results of cyclic voltammetry (CV) show that [PM012O40]3" or [P2Mo18O40]6-anions are active centres for electrochemical redox reactions in solution, while corresponding cations have a small effect on the electrochemical properties. The studies of magnetic properties of [{Ln(NMP)6}(PMo12O40)]n[Ln = La(1), Ce(2), Pr(3)] show that compound 1 exhibits diamagnetism, while that 2and 3 exhibit antiferromagnetic Pr-Pr or Ce-Ce exchange interactions. The crystal data of all compounds were shown as follow:1. [Cu(en)2]2Na4H13[Cu(H2O)2(Nb7O22)]3 en 9.5H2O: It belongs to triclinic space group Pi, with unit cell dimensions a = 16.182(3), b = 23.808(5), c = 24.472(5) A, a = 119.07°(3), B= 93.99°(3),r = 91.80°(3), V= 8198(3) A3, Z= 2, Dc = 1.626 Mg /cm, GOF =0.933, F(000) = 3831.2. [Y(NMP)5(H2O)2][Y(NMP)4(H2O)2 (P2Mo18O62)] NMP 5.5 H2O: It belongs to monoclinic space group P2 (l)/c, with unit cell dimensions a = 30.683(6) A, b = 14.130(3) A, c = 28.931(6) A,B = 117.97(3)°, V= 11079 (4) A3, Dc = 2.471Mg/m3, Z = 4, GOF =1.023, F(000) = 7980.3 . [{Nd (NMP)2(H2O)6Cl}{Nd (NMP)2(H2O)7}H(P2Mo18O62)]: It belongs to monoclinic space group Cc, with unit cell dimensions a = 24.528(5) A,b= 19.495(4) A,c = 24.405(5) A, B = 109.94(3)°, Z = 4, V= 10970(4) A 3, Dc = 2.262 Mg/m3, GOF =0.978, F(000) = 7064.4. [Ce (NMP)3(H2O)6]2 [P2Mo18O62] 0.5 NMP H2O: It belongs to monoclinic space group Cc, with unit cell dimensions a = 24.511(5) A, b = 19.587(4) A, c = 24.320(5) A, P= 110.22(3)°,V= 10957(4) A 3, Dc = 2.371Mg/m3, Z = 4, GOF =1.012, F(000) = 7432.5. [{La(NMP)6}(PMo12O40)]n It belongs to monoclinic space group Pn, with unit cell dimensions a = 12.954(3) A, b = 13.417(3) A, c = 18.810(4) A, B = 99.67(3)°, V = 3222.6(11) A3, Dc = 2.634Mg/m3, Z = 2, GOF =1.036, F(000) = 2440.6. [{Ce(NMP)6}(PMo12O... |
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