【作者】 王晶；

【导师】 段春迎；

【作者基本信息】 大连理工大学 ， 无机化学， 2011， 硕士

【摘要】 超分子化学是由两个或更多的化学实体通过分子间弱相互作用而构建的高度有序的体系。通过主客体之间的相互作用引起主体结构的变化,是分子识别、均相以及非均相催化的理论基础。多核金属有机配合物的空腔不仅有利于对特定底物分子的选择性识别；同时还可以通过非共价弱相互作用将不同的底物分子限定在特定的区域中,进而选择性的催化某些特定反应的进行。1.四面体笼状化合物的组装及其在不对称催化中的应用：设计了具有C3对称性三双齿席夫碱配体L1,与一系列的过渡金属离子自组装得到四面体笼状化合物。晶体结构表明该笼状化合物具有理想的四面体对称性。园二色谱测试,确定其具有空间手性结构,并通过荧光分析的方法研究了其主客体化学行为。含有正电荷的四面体笼状化合物可通过静电作用、π-π堆积作用将具有大共轭基团的蒽的衍生物客体包合在其空腔内部特定的区域,进一步诱导其进行不对称Diels-Alder催化反应。2.双核金属配合物的组装及其在非均相催化中的应用：合成并表征新型的双核过渡金属席夫碱配合物L2-Zn以及L2-Cd的晶体结构。研究了两种双核配合物在水溶液中非均相催化磷酸二酯BNPP的水解反应。通过分析反应体系在400nm处紫外可见吸收光谱,表明此两种双核金属配合物可以有效地在非均相体系中催化BNPP水解反应,其反应速率常数分别为7.7*10-7S-1和8.84*10-7S-1。更多还原

【Abstract】 The supramolecular chemistry is highly ordered system constructed by two or more moleculars through interaction between different molecules. The interaction between host and guest could lead to the structure changing of host and is the base of molecule recognition, homogeneous catalysis and heterogeneous catalysis. The cavity of the polynuclear metal-organic complex can encapsulate and stabilize guest substrates through interaction with selective signal response and some special chemical reactions can be catalyzed.1. Self-assembly of tetrahedral metal-organic cage-like compound and it application in asymmetric catalysis:It is based on using a C3-symmetric Schiff base ligand L1 which comprises three bidentate coordinating sites, forces various metal ions to form metal-organic tetrahedral cage-like compounds. Crystal structure shows that the cationic cage has an ideal tetrahedral symmetry. By CD tests, we find the tetrahedral compound with chiral structure. Host-guest complexation behaviour between the tetrahedron compound and anthracene derivatives was investigated using the method of fluorescence titration. The cation tetrahedron host could encapsulate the anthracene derivative vis static andπ-πinteraction. Asymmetric Diels-Alder reaction catalyzed by the tetrahedral complex.2. The hydrolysis of BNPP catalyzed by dinuclear metal complexes:The crystal structures of two new Schiff base dinuclear transitional metal complexes L2-Zn and L2-Cd were synthesized and characterized. Two dinuclear complexes were used in heterogeneous catalysis phosphodiester cleavage in an aqueous solution. The process of BNPP hydrolysis has been proposed based on analyses at 400nm UV-visible absorbance spectra. The result shows these dinuclear metal complexes are highly active heterogeneous catalysis BNPP cleavage, with a rate constant of 7.7*10-7S-1 and 8.84*10-7S-1, respectively.更多还原