导　　师： 胡升

学科专业： 0852

授予学位： 硕士

作　　者： ;

机构地区： 广东工业大学

摘　　要： 簇配位聚合物材料因为其多种多样的拓扑结构和在光、电、磁、催化、气体吸收和离子交换等方面的潜在应用价值而引起人们越来越浓厚的兴趣。在合成这类型材料的主要策略是利用晶体工程的方法,它提供了一种简便可行的方式,就是通过有机桥连配体代替各种天然矿物结构内的分子键,模仿天然矿物的结构,从而控制各种框架结构的组装。多元羧酸配体在配合物方面连接方式是十分灵活的,因此被广泛用来合成配位聚合物。在一般情况下,结构较长的配体将形成较大的空隙,也可能会形成多重穿插结构。本论文将介绍一些多元羧酸配体在不同的反应条件下与金属离子作用,并选择适当的第二配位体与多元羧酸配体组成混合配体体系,例如选用经典联吡啶支柱4,4’-联吡啶/(bpy/),1,2-二/(4-吡啶基/)乙烯/(bpe/)和1,3-二/(4-吡啶基/)丙烷/(bpp/)。全文总共五章： 第一章是前言,主要内容是无机-有机配位聚合物的研究课题背景、合成方法和性质作用,还介绍了晶体工程与分子拓扑学在课题研究中的指导作用,以及本论文的选题意义。 第二章中,我们介绍三个配位聚合物,分别是具有pcu拓扑致密三维结构的/[Co2/(ceta/)/(bpy/)1,5/(H2O/)3/]·4H2O/(1/),具有一维圆形通道三维微孔结构的/[Ni2/(ceta/)/(bpe/)2/(H2O/)3/]·11H2O/(2/)和具有二维含孔结构的/[Ni2/(ceta/)/(bpp/)2/(H2O/)2/]·2H2O/(3/)。对几个化合物的实验对比及晶体结构描述不难发现含有骑烯基六元环架构的四羧酸配体ceta /(bicyclo/[2.2.2/]oct-7-ene-2,3,5,6-tetracarboxylate/)与不同尺寸及柔韧性的毗啶类辅助桥连配体在构造环形单元以及微孔型金属-有机骨架时的协同效应。我们选用的bpe配体得到一例微孔配位聚合物,bpe在配合物的整体结构中长度非常合适。长度与主配体ceta的配位跨度匹配,在环与环的连接时,既加强了结构的稳定性,又不遮挡一维通道,整体结构非常独特与奇妙。从结果来看,我们使用比bpe长的bpp配体和比bpe短的bpy配体,都没有得到含六元环和一维通道的配合物,证明bpe配体在微孔型配合物的形成过程中,起到了决定性的作用。我们已将该研究结果撰文发表在Polyhedron上。 第三章中,我们介绍了两例基于五核Cd簇和十核Cd环的三维荧光配位聚合物Cd5/(OH/)2/(psa/)4/(bpe/)/(H2O/)2/(4/)和Cd5/(psa/)5/(bpp/)-2H2O /(5/),/(H2psa=phenylsuccinic acid/)。对含苯环侧基的psa配体的配位功能和两个化合物的化学性能进行修饰和对比,体现了psa侧基和吡啶类辅助桥连配体长链对生成最终产物的配位导向作用。成功将发光功能五核Cd链单元和十核Cd环形簇单元引入三维结构框架。我们已将该研究结果撰文发表在Journal of Molecular Structure上 第四章中,我们选择1,4-Phenylenediacetic acid /(pda,对苯二乙酸/),4,4'-propane-1,3-diyldipyridine /(bpp=1,3-二吡啶基丙烷/)及吡腈/(pyrazine/)作为连接体组装形成金属有机聚合物。对苯二乙酸配体因为较长的结构特征表现出多样的配位模式和构象结构,因此对苯二乙酸对合成出更多有趣的框架结构很有潜力。 第五章中,我们采用水热方法合成了配合物/[Zn/(bba/)/(bpt/)/]·0.5H2O。二苯甲酮2,4’-二甲酸是一个多齿羧酸,它的L型构造在组装过程中必定发挥出立体化学调节作用而与众不同。我们还选用了3,5-二/(4-吡啶/)-1,2,4-三氮唑作为辅助桥连配体,在构筑孔型框架及提高化合物的维度和稳定性方面发挥了作用。 最后对研究的课题进行了总结与展望。 Metal-Organic Frameworks /(MOFs/) have attracted intense interest for their various intriguing topologies and the potential applications such as magnetism, luminescence, catalysis, gas storage and ion exchange, etc. The main strategy used in this area is crystal engineering approach, which provides a facile way to imitate the structure of natural minerals by replacement of the bonds with organic bridges so as to control the assembly of various frameworks. Aliphatic polycarboxylic acids, being very flexible when they involve long carbon chains, have been widely used for the synthesis of coordination polymers. In general, long ligands will lead to larger voids that may result in multi-fold interpenetrating structures. However, we present some different cases where the secondary ligands chosen are classical bipyridine pillars4,4'-bipyridine /(bpy/),1,2-bis/(4-pyridyl/) ethylene /(bpe/) and1,3-bis/(4-pyridyl/)propane /(bpp/). There are five chapters in all papers. In Chapter1, the main content is the background task organometallic polymers, synthetic methods and properties of the role, but also introduces a guiding role in crystal engineering and molecular research in topology, and significance of the topic of this paper. In Chapter2, In this research, three coordination polymers,/[Co2/(ceta/)/(bpy/)1.5/(H2O/)3/]·4H2O /(1/) with pcu topology,/[Ni2/(ceta/)/(bpe/)2/(H2O/)3/]·11H2O /(2/) with1D circular channels and /[Ni2/(ceta/)/(bpp/)2/(H2O/)2/]·2H2O /(3/) with2D structure,were obtained as their single crystals. Through the experimental comparison and crystal structure of several compounds are described, it is easy to find ceta /(bicyclo/[2.2.2/]oct-7-ene-2,3,5,6-tetracarboxylate/) contains four carboxylic groups and an interesting riding alkenyl group, as well as the different lengths and conformations of the bipyridine ligands play cooperativel roles in modulating the structures of the coordination polymers. we successfully synthesized coordination polymers constructed from a tetracarboxylate ligand with the assistance of selective bipyridine ligands of increased length. The length of bpe match the coordination span of the primary ligand, when connecting the rings, both to strengthen the stability of the structure, without blocking the one-dimensional channel, the overall structure is very unique and wonderful. From the results, neither the longer ligand bpp nor the shorter ligand bpy could synthesis coordination polymers with6-membered metallocycle and1D circular channels, and these proved that the bpe ligands play crucial roles in modulating the structures of the coordination polymers. We have published the results of the study in the Polyhedron. In Chapter3, two coordination polymers Cd5/(OH/)2/(psa/)4/(bpe/)/(H2O/)2/(4/) and /[Cd5/(psa/)5/(bpp/)/]-2H2O /(5/) with different cluster-based building blocks were obtained as their single crystals. The details of structures show the side group effects of the psa ligands on the conformations of frameworks. We have published the results of the study in the Journal of Molecular Structure. In Chapter4, in this work we chose1,4-benzenediacetic acid and3.5-di/(1H-imidazol-1-yl/)benzoic acid as linkers to construct metal-organic frameworks.1.4-benzenediacetic acid ligand may show a variety of coordinationmodes and conformations because of the increased flexibility of two carboxylate groups. thus make it easier to form polynuclear cluster. In Chapter5, a novel coordination polymers /[Zn/(bba/)/(bpt/)/]·0.5H2O have been synthesized under hydrothermal conditions. Benzophenone-2,4'-dicarboxylic acid is a polycarboxylate ligand, it is L-shaped structure process must play a regulatory role of stereochemistry and distinctive in the assembly. We also choose3,5-bis/(4-pyridyl/)-1,2,4-triazole as the auxiliary bridging ligand, it plays a vital role in improving the stability of the compounds and the terms of demensions. Finally, brief conclusions on these work and an outlook are provided.

关 键 词： 金属有机聚合物 晶体结构 拓扑 羧酸配体 稳定性

分 类 号： [O627]

领　　域： [理学] [理学]