吡唑羧酸金属有机配合物的合成、结构及其性能表征

发布时间：2018-03-11 01:31

本文选题：杂环羧酸　切入点：吡唑羧酸　出处：《南昌航空大学》2016年硕士论文　论文类型：学位论文

【摘要】：近几年来,金属有机配合物由于其迷人多变的结构及其优异的光、电、磁、分子识别、催化、生物活性、化学传感等性质而受到了广泛关注。它跨越了诸如配位化学、材料工程学和拓扑学以及晶体工程学等学科在内的无机化学的各个领域,不得不说,所包括的研究方向和内容非常广泛。本论文主要针对吡唑羧酸类金属有机配合物展开研究。吡唑羧酸类配体同时含有五元氮杂环的吡唑基团和羧酸基团,具有多个配位点,容易与金属选择性配位,其灵活多变的配位方式可用于设计、构筑、组装各种新颖配合物。比较简单的吡唑羧酸类配体的吡唑基团与羧酸基团直接相连,例如1H-吡唑-3-甲酸和3,5-吡唑二甲酸,其分子体积较小且呈现共轭性,可以选择性脱去吡唑基团质子和羧酸质子而呈现不同价态,以多种配位方式与金属配位形成各种过渡/稀土配合物。同时,辅助配体的引入对配合物的合成和结构起着十分重要的作用。本论文以1H-吡唑-3-甲酸和3,5-吡唑二甲酸为主要配体,对苯二甲酸、丁二酸为辅助配体成功合成了一系列新颖的过渡/稀土金属配合物,并对所得配合物的晶体结构和性能(光致发光、磁性和热稳定性等)进行了探讨。本论文一共分为五章。第一章介绍了本论文的相关研究背景,概述了配合物的分类、合成方法及应用,系统地介绍了近年来吡唑羧酸类配合物在相关领域的研究进展及主要成果,最后阐述了本论文的选题依据、目的和意义。第二章实验部分。介绍了本论文中所用到的药品和仪器,相关化合物的名称缩写及材料的表征方法。第三章吡唑羧酸类过渡金属配合物的合成、晶体结构和性能研究。采用常规溶液法或水热法分别合成了基于1H-吡唑-3-甲酸的四核钴配合物Co4(pca)2(Hpca)2(py)6(TPA)(H2O)2(1)、一维铜配合物[Cu2(pca)2(Hpa)3]n(2)、二维镉配合物[Cd(Hpca)(Cl)(H2O)]n(3)和一维异核镍钠配合物NiNa(pca)(Hpca)(H2O)4?2H2O(4)和基于3,5-吡唑二甲酸的过渡金属配合物非心三维锌配合物[Zn4(pdc)2(TPA)(H2O)2?3H2O]n(5)和三维镉配合物[Cd(Hpdc)(H2O)2]n(6)。第四章3,5-吡唑二羧酸稀土配合物的合成、晶体结构和性能研究。采用水热法合成了系列同构双核稀土配合物第五章本论文工作的总结。
[Abstract]:In recent years, organometallic complexes have attracted wide attention due to their attractive and changeable structures and their excellent properties such as light, electricity, magnetism, molecular recognition, catalysis, biological activity, chemical sensing and so on. In the fields of inorganic chemistry, such as material engineering and topology and crystal engineering, we have to say, The research directions and contents are very extensive. In this thesis, we mainly focus on the organometallic complexes of pyrazole carboxylic acids. The pyrazole carboxylic acid ligands contain pyrazole groups and carboxylic acid groups with quaternary nitrogen heterocycles, and have many coordination sites. It can be used to design, construct and assemble various novel complexes. The pyrazole group of the simple pyrazole carboxylic acid ligand is directly linked to the carboxylic acid group. For example, 1H-pyrazole-3-formic acid and 3H-5-pyrazole dicarboxylic acid have small molecular volume and conjugate properties, which can selectively remove protons of pyrazole group and carboxylic acid and present different valence states. Various transition / rare earth complexes are formed by coordination with metals in many ways. At the same time, The introduction of auxiliary ligands plays an important role in the synthesis and structure of the complexes. In this thesis, 1H-pyrazole-3-formic acid and 3H-5-pyrazole dicarboxylic acid are the main ligands, terephthalic acid, terephthalic acid, and terephthalic acid. A series of novel transition / rare earth metal complexes were successfully synthesized with succinic acid as auxiliary ligands. The crystal structure and properties (photoluminescence) of the complexes were investigated. This paper is divided into five chapters. The first chapter introduces the research background of this thesis, and summarizes the classification, synthesis methods and applications of the complexes. The research progress and main achievements of pyrazole carboxylic acid complexes in related fields in recent years are introduced systematically. Aim and significance. Chapter 2 experiment. The drugs and instruments used in this thesis, the abbreviations of related compounds and the characterization methods of materials are introduced. Chapter 3: synthesis of transition metal complexes of pyrazole carboxylic acids, Studies on Crystal structure and Properties. Tetranuclear Cobalt complex Co _ 4H _ 4H _ 4P _ (cao) _ 2H _ (4) H _ (1) H _ (2) O _ (2) H _ (2) H _ (2) H _ (2) H _ (1) H _ (2) O _ (1), one dimensional copper complex [Cu2(pca)2(Hpa)3] nn ~ (2), two _ dimensional cadmium complex [CD ~ (2 +) H _ (pcacaC) H _ (2) O _ (H _ 2O)] n ~ (3) and one dimensional heteronuclear nickel sodium complex Ni (Na) (H ~ (2 +)) (H _ (1) O _ (2) H _ (2)) H _ (1) H _ (2) O _ (4)? 2H _ 2O _ 4) and the transition metal complexes based on 3H _ 5- pyrazoledioic acid [Zn _ 4H _ 4H _ 3H _ 2H _ 2H _ 2O _ 2H _ 2O _ 2H _ 2O _ 2H _ 2O _ 2H _ 2H _ 2H _ 2O _ 2? The synthesis, crystal structure and properties of rare earth complexes of 3H _ 2O] n _ (5) and [Cd(Hpdc)(H2O)2] n ~ (6) (4th) have been studied. A series of isomorphic Dinuclear rare earth complexes (5th) have been synthesized by hydrothermal method.
【学位授予单位】：南昌航空大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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