【作者】 张秀清；

【导师】 梁宏；

【作者基本信息】 南开大学 ， 无机化学， 2009， 博士

【摘要】 含有氮杂环的羧酸配体,羧基可以多种方式与金属离子键合,同时氮杂环的多个氮原子可能与金属离子配位,所以可用于合成结构和性能多样的配合物。利用溶液法,本文合成了二十二个配合物。通过红外光谱、元素分析、X-射线单晶衍射等手段,较系统地研究了其中二十一个晶体的结构,并应用紫外光谱、荧光光谱、CD光谱、黏度分析方法和琼脂糖凝胶电泳等手段研究了部分配合物的化学核酸酶活性,测定了部分配合物的固体荧光性质和磁性质。本论文分为以下三部分:第一章:通过溶液法合成了四氮唑-5-甲酸的13个配合物并解析了12个配合物的晶体结构。测定了配合物(1)～(4)和(7)～(9)的磁性质。配合物(1)～(4)均为反铁磁性物质;对于配合物(7)～(9),由于稀土离子的强旋轨耦合作用,其磁性质比较复杂。利用光谱学方法和粘度法研究了配合物(1)、(4)、(5)、(10)、(11)与DNA的相互作用,发现五个配合物均以中等强度的插入方式与DNA作用。利用凝胶电泳法研究了配合物(1)、(4)、(5)、(10)、(11)对质粒pBR 322的切割作用,结果发现五个配合物都具有核酸酶活性,均可在一定程度上切割DNA。在室温下测了配合物(13)的固体荧光,在338 nm的激发波长条件下,在519 nm处有荧光发射。第二章:通过溶液法合成了四氮唑-5-乙酸的6个配合物并解析了它们的晶体结构。测定了配合物(15)～(19)的磁性质。配合物(15)是一个反铁磁性物质。配合物(16)～(19)的中心金属离子分别是Pr(Ⅲ)、Nd(Ⅲ)、Sm(Ⅲ)、Gd(Ⅲ)。对于配合物(16)和(17)的磁性质我们用配体场近似进行了计算,计算表明这两个配合物也是反铁磁性的。配合物(18)是Sm(Ⅲ)的一维链状聚合物,Sm(Ⅲ)离子间存在着反铁磁相互作用。配合物(19)则是一个双核钆的反铁磁性物质。第三章:通过溶液法合成了四氮唑-5-甲酸乙酯的3个配合物并解析了其晶体结构。在室温下测定了配合物(20)和(21)的固体荧光质。配合物(20)在352 nm的激发波长条件下,在378 nm处有荧光发射。配合物(21)在336 nm的激发波长条件下,在396 nm处有荧光发射。测定了配合物(22)的磁性质并利用光谱学方法、粘度法及凝胶电泳法研究了配合物(22)与DNA的相互作用,发现该配合物以插入方式与DNA作用,具有核酸酶活性,可在一定程度上切割DNA。更多还原

【Abstract】 The ligand, which has carboxyl groups and nitrogen heterocyclic rings, can coordinate to the metal ions by all kinds of mode. In this dissertation, twenty two new coordination complexes have been synthesized by the solution method. Twenty one of them were studied by IR, Elemental Analysis and single crystal X-ray diffraction methods. The interactions between part of complexes and DNA were studied by UV, CD, fluorescence spectra, viscosity measurement and gel electrophoresis. The solid fluorescence and magnetic properties of part of complexes were measured.There are three chapters in this dissertation:Chapter one: Thirteen new complexes of 1H-tetrazole-5-formic acid were synthesized, and twelve crystal structures of them were determined by X-ray diffraction methods. Variable-temperature magnetic susceptibility of complexes （1） to （4） and （7） to （9） are measured. The complexes （1） to （4） are antiferromagnetic. The magnetic properties of complexes （7） to （9） were complicated because of strong spin-orbit coupling. The interactions between complexes （1）, （4）, （5）, （10）, （11） and DNA were studied by UV, CD, fluorescence spectra, viscosity measurement and gel electrophoresis. The results showed that all of the five complexes can interact with DNA. At room temperature, the fluorescence of complex （13） was measured in the solid state. Complex （13） shows the fluorescence emission withλ_em = 519 nm (λ_ex = 338 nm).Chapter two: Six new complexes of 1H-tetrazole-5-acetic acid were synthesized and the crystal structures were determined by X-ray diffraction methods. Variable-temperature magnetic susceptibility of complexes （15） to （19） were performed by using powder samples. The antiferromagnetic interaction among the metal ions was evident from the susceptibility data in complex （15）. The metal ions of complexes （16） to （19） were Pr（III）, Nd（III）, Sm（III） and Gd（III）, respectively. The antiferromagnetic interactions are showed in complex （16） and （17） analyzed by the theory of ligand fields approximation. The magnetic property of complex （18） was antiferromagnetic interactions. For complex （19）, the antiferromagnetic interactions was showed between two Gd（III） ions.Chapter three: Three new complexes of ethyl tetrazole-5-carboxylate were synthesized and the crystal structures were determined by X-ray diffraction methods. At room temperature, the fluorescence of complexes （20） and （21） are measured in the solid state on the same condition. Complexes （20） and （21） showed the fluorescence emission withλ_em = 378 runλ_ex = 352 nm),λ_em = 396 ran (λ_<sub>ex = 336 run), respectively. The emission observed in complexes （20） and （21） are tentatively assigned to the ligands fluorescence. Variable-temperature magnetic susceptibility of complexes （22） was performed by using powder samples. The interaction between complex （22） and DNA was studied by UV, CD, fluorescence spectra, viscosity measurement and gel electrophoresis. The results showed that the complex can interact with DNA by intercalating mode and can cleavage pBR322 DNA to some extent.更多还原