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配位聚合物的合成、表征及性能研究

The Studies for the Synthesis, Crystal and Properties of Coordination Polymers

【作者】 刘法谦

【导师】 陆路德; 建方方; 杨绪杰; 汪信;

【作者基本信息】 南京理工大学 , 材料学, 2006, 博士

【摘要】 配位聚合物是金属离子和有机配体形成的具有无限结构的配位化合物。由于它在光、电、磁、催化等领域具有诱人的应用前景,被认为是当前最有潜在能力的功能材料,已成为无机化学和材料化学领域的研究热点之一。本文围绕当前关于配位聚合物研究的若干热点,采用溶剂热合成、水热合成等方法,设计、合成并解析了18个配合物的单晶结构,其中12个为配位聚合物,并对其电化学及热性能等进行了研究。 第一章:阐述了本课题的选题背景和意义,介绍了配位聚合物的基本概念、发展过程、国内外的研究热点并总结了本课题所取得的成果。 第二章:设计并合成了一种Hg(SCN)42-阴离子,分别和Ni(Im)62+,Mn(Im)62+及Cu(N-MeIm)62+反应,得到了三个异双核配位聚合物;以SCN-为基本构建单元,并加入辅助中性配体,设计得到了8个配合物,其中4个为配位聚合物,4个为单核配合物。其中,对Ni的单核配合物采用紫外,电化学等方法详细研究了其与DNA的相互作用。 第三章:分别采用邻苯二甲酸和对苯二甲酸为构建单元,设计并得到了两种一维链状配位聚合物;采用对甲基苯甲酸铜与2,2’联吡啶反应,得到一种新型的铜配合物,采用紫外,电化学等方法详细研究了其与DNA的相互作用。 第四章:采用氰根为基本构建单元,设计并得到了两种配位聚合物,配合物Cu3(en)2(cn)4·H2O具有金刚烷结构,主体为菱形的阴离子三维网[Cu2(CN)4]22-,客体分子为起空间填充和电荷平衡作用的[Cu(en)2·H2O]2+阳离子。 第五章:采用叠氮为基本构建单元,和烟酸共同桥联金属Zn得到一种一维链状配位聚合物;和2—甲基咪唑反应,得到一种银的三维超分子配合物。 第六章:设计、合成并表征了两个系列共19个新型的三氮唑配体,虽然没有得到配合物的单晶,但是我们得到了其中5个化合物的单晶,并初步测试了所有化合物的生物活性。

【Abstract】 Coordination polymer, that is coordination complexes with extended structure self-assembled through metal ions and organic ligands, is regarded the most promising functional materials currently and has been an active area in inorganic and materials chemistry due to its interesting potential application in optics, electronic, magnetic and catalytic ect fields. Herein, using hydrothermal and solvothermal ect. syntheses methods, we report the self-assembly and characterization of twelve novel one-, two- and three-dimensional coordination polymers and seven monomers. Their single crystal structures have been determined using X-ray difraction methods.Chapter Ⅰ: A survey on the hot spot of coordination polymers, is concisely presented, as well as scientific significance and the results in this dissertationChapter Ⅱ: Three heteronulear coordination polymers are designed and synthesized by the reaction of Hg(SCN)42 anion with Ni(Im)62+, Mn(Im)62+ and Cu(N-MeIm)62+ cation; Four mononuclear coordination polymers and four monomers have been synthesized from SCN- and transition metals with the presence of neutral ligands. Their single crystal structures have been determined using X-ray difraction methods. The interaction of the Ni 2+ complex to native fish sperm DNA is investigated through electrochemistry, electric absorption spectroscopy and viscosity experiments.Chapter Ⅲ: Two 1-D coordinatin polymers are synthesized by the using of phthalic acid and terephthalic acid. A novel copper complex is synthesized by the reaction of copper 4-methylbenzoate and 2,2’ -bipyridine and the interaction of the complex to native fish sperm DNA was investigated through electrochemistry, electric absorption spectroscopy and viscosity experiments.Chapter Ⅳ: Two coordinatin polymers are synthesized by the using of cuprous cyanide. The structure of Cu3(en)2(cn)4·H2O consists of a three-dimensional diamond-related anionic framework host, [Cu2(CN)4]2-, and enclathrated [Cu(en)2·H2O]2+ cations.Chapter Ⅴ: A 1-D Zn coordinatin polymers is synthesized by the reaction of sodium azide, nicotinic acid and zinc chloride. A 3-D Ag supramolecular complex is synthesized by the reaction of sodium azide, 2-methylimidazole and silver chloride.Chapter Ⅵ: Nineteen novel ligands containg triazole and benzotriazole are designed and synthesized. Although we did not get the single crystal of complexes, we get five single crystals of compounds and test the biological activity of all the compounds.

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