【作者】 王文举；

【导师】 许林；

【作者基本信息】 东北师范大学 ， 无机化学， 2005， 硕士

【摘要】 有机-无机杂化材料以其丰富的结构和在催化、材料、生物、磁学、非线性光学以及医学领域的广泛应用近年来引起人们的广泛关注。因此人们致力于合成包含特殊功能的新型有机-无机杂化材料。金属有机配合物与多钼酸盐虽然在各自领域都有了较深入的研究但是二者的杂化材料的研究报道仍然需要更进一步的探索。本文利用水热合成技术,通过调节反应条件和反应原料配比合成过渡金属配合物修饰的多钼酸盐:[Co（bipy）₃]2[Mo₆O₁₉] [β-(H₂Mo₈O₂₆)]·4H₂O 1,Ni（phen）₃][Mo₆O₁₉] 2,（CuO₃ bipy）₂（SeO₃）₂(Mo₄O₁₃)（Mo₂O₅）]₃。链状铜配位聚合物[Cu（bipy）₂Cl]₂Cl₂·nH₂O₄。利用单晶X-ray衍射确定了这三种化合物的结构,并对这三种化合物的合成及晶体结构进行了详细讨论,另外对它们的IR, XPS , TGA等性质进行了研究。化合物1和2分别是由[ Co （bipy）₃]²⁺和[ Ni （phen）₃]²⁺作为阳离子与[Mo₆O₁₉] [β-(H₂Mo₈O₂₆)]和[Mo₆O₁₉]组合成的多钼酸盐。在这两个化合物中,孤立的多钼酸盐之间通过bipy 或phen基团间的π—π相互作用进一步形成有趣的三维超分子结构。化合物3是一个由三角锥体SeO₃及Cu配合物修饰的链式的多钼酸盐。化合物4是一种新颖的由π-π堆积作用形成的链状二价铜配合物,并且讨论了其红外光谱、磁性、结构。更多还原

【Abstract】 The organic–inorganic hybrid compounds, which are expected to be endowed with enhanced or combined functionalization of both organic and inorganic substructures has been focused on the richness of their structures and special properties in the fields of catalysis and materials science as well as in biology, magnetism, nonlinear optics and medicine. Although the polymolybdate and metal complex has recieved considerable attention, it still remains a challenge to synthesize new compounds and investigate the potential properties further. In this paper,three novel polyoxometalate-based organic–inorganic hybrid compound, [Co（bipy）₃]₂[Mo₆O₁₉] [β-(H₂Mo₈O₂₆)] ·4H₂O 1, [Ni（phen）₃][Mo₆O₁₉] 2 and [（CuO₃ bipy）₂（SeO₃）₂(Mo₄O₁₃)（Mo₂O₅）]₃ have been hydrothermally synthesized through modifying synthetic conditions and starting material. Structures of the three complexes have been determined by single crystal X-ray diffraction and the influencing factors on polyoxometalate-based organic-inorganic hybrid compound Mo-O framework have been discussed. Other characterizations for these three complexes by elemental analysis, IR, XPS and thermal analysis have also been described. Both compound 1 and 2 are bimetallic cluster complexes. Compound 1 represents the first example that racemic complexes coexisting with two kinds of polyoxomolybdate anions in the same crystal architecture, which should be of rare chance that four kinds of complexes crystallizes into a compound. Compound 2 contains centrosymmetric [Mo₆O₁₉]^2- hexamolybdate anions, which are built up from distorted MoO₆ units by edge-sharing. The nickel atom in the [Ni（phen）₃]²⁺ cation adopts distorted octahedral coordination with three N, N ′ -bidentate 1,10-phenanthroline （phen） ligands. The crystal packing is stabilized by some weak π–π stacking interactions between neighboring phen ligands and C—H … O interactions. The Ni atom occupies a special position with twofold symmetry. 3-D heteropolymolybdate compound 3 with capping selenite through π-π stacking hydrogen bond.更多还原