【作者】 唐晓亮；

【导师】 刘伟生；

【作者基本信息】 兰州大学 ， 无机化学， 2009， 博士

【摘要】 超分子化学的一个主要目标是深入地理解和研究有机分子及无机分子间的自组装化学，并能够总结出结构规律，开发出有用的电学、磁学、电化学、光学或催化功能的新型材料。一般来说，配合物的自组装受各种因素的共同影响，如金属离子特殊的配位构型、有机配体的特性、抗衡离子的干扰、溶剂体系和反应条件等。其中，配体是调控超分子配合物结构的关键因素，因此对配体的设计和研究备受关注。使用刚性桥联配体已经构筑了众多具有功能性的配位骨架，近年来，人们开始关注柔性链配体的应用研究，希望通过在配体中引入柔性成分来实现新颖超分子结构的构筑和功能化。本论文选择了几种富含N、O杂原子的不同柔性链配体：以1，3，4-oxadiazole含N、O原子的五元杂环作为骨架部分的柔性链配体；以含O杂原子的线性烷基链来连接两个苯并三氮唑的柔性链配体；以含N、O和羧基的还原型氨基酸席夫碱为骨架的柔性链手性配体。并对所形成配合物的结构和性质进行了细致的研究。全文共分为六部分：一、简单介绍了超分子配合物研究背景和应用，总结了超分子化学的本质和配体分类，重点介绍了柔性链配体对配合物结构调控、螺旋体构筑、聚合物形成、传感器设计和稀土发光材料应用等方面的研究：二、设计并合成一组2，5-diaryl-1，3，4-oxadiazole为骨架的酰胺型柔链配体，考察该类配体骨架的共轭结构能否有效敏化稀土配合物荧光，通过对不同酰胺端基稀土配合物的比较，探讨不同末端基配体对稀土配合物荧光的影响；三、基于1，3，4．oxadiazole连接骨架，设计合成了四个相关联的更为柔性的水杨酰胺型柔链配体，尝试在相同条件下制备稀土硝酸盐配合物晶体，并对所形成的配合物进行了详细的表征和荧光研究，从而探索末端基对稀土配合物结构和发光的微扰作用；四、设计并合成了一个基于1，3，4-oxadiazole和8-羟基喹啉的简单柔性链配体2，5-bis[（quinolin-8-yloxy）methyl]-1，3，4-oxadiazole，通过构建有着潜在合适空腔大小的开放型有机分子，实现了对Cd²⁺离子的荧光选择性识别。配位后产生的荧光增强效应和作用机理被探讨和研究；五、选择苯并三氮唑作为配位端基，使用不同长度含氧杂原子的柔性链来代替一般常见的碳链骨架，得到了一系列相关配体，并且通过改变柔性链配体的间隔基长度和金属盐的种类，实现新颖配合物的制备和结构的有效调控。六、在已有研究工作基础上，合成了对映的手性还原型氨基酸席夫碱，进一步研究了稀土簇合物在自组装过程中的配位化学及特殊螺旋结构，修正并重新确定了包覆小分子的组成，考察了该稀土配位簇合物对CO₂的捕获作用，同时，在溶液中利用手性信号实现了对CO₃^2-的选择性检测。更多还原

【Abstract】 One of the major goals of supramolecular chemistry is to understand theself-assembly of organic and inorganic molecules, which could help us summarize therules of coordination chemistry and extend the range of new materials having potentialapplications in various field, such as electrics, magnetism, electrochemistry, optics andcatalysis. Generally speaking, the generation of self-assembling coordinationarchitectures depends on the combination of several factors—the coordinationgeometry of the metal ions, the performance of the ligands, the coordinated and/ornon-coordinated counter ions, the solvent systems, the reaction conditions, and so on.Among them, the ligand is no doubt the key factor of manipulating the structure of thesupramolecular complexes. Therefore, the application of well-designed ligands tocontrol the assembly of molecular architectures has become a popular and rapidlygrowing discipline.Many coordination architectures have been constructed with rigid bridgingheterocyclic ligands and the various properties of the materials were reviewed. Morerecently, increasing attention has been paid to employ flexible ligands in order todevelop novel supramolecular frameworks and research useful functions. We havedesign and prepared some different flexible ligands with N or O heteroatoms: based on1,3,4-oxadiazole consisting of five-membered heterocyclic as link; based on alkyl linearchain with oxygen atoms in the backbone linking benzotriazoles; based on chiralreduced Schiff Bases of amino acids. The crystal structures and properties of theircomplexes have also been investigated. The thesis is included six parts.1. A brief review of the background and application on supramolecularcoordination compounds was concisely given. The nature of supramolecular chemistryand the class of ligands were summarized. The regulation of basal supramolecularframeworks, the building of helical structure, the forming of coordination polymers, thedesign of sensors and the application of luminescent materials based on lanthanide wereintroduced emphatically.2. A series of amide-based 2,5-diaryl-1,3,4-oxadiazole derivative ligands weredesigned and synthesized. The relationship between the conjugated structure of theseligands and the fluorescence of their lanthanide complexes was studied. The terminalgroup effect of ligands on the fluorescence was explored by comparing the complexesprepared by different amide-based ligands.3. Four salicylamide ligands with different terminal group based on1,3,4-oxadiazole derivative were designed and synthesized. Their lanthanide complexeswere tried to prepare under the same condition. The crystal structure and luminescent properties of the complexes have been investigated. The results suggested that the fineregulation of the terminal group influence the structure and the fluorescence of thecomplexes.4. A new flexible ligand 2,5-bis[（quinolin-8-yloxy）methyl]-1,3,4-oxadiazole basedon 1,3,4-oxadiazole and 8-hydroxyquinoline was designed and synthesized. The organiccompound possess specific space which could selectively accommodate Cd²⁺ accordingto ionic radius and a prominent fluorescence enhancement only for Cd²⁺ was found inaqueous methanol solution. The properties and mechanism of the sensor were studiedand explored.5. A series of structurally related flexible ligands by using benzotriazole as terminalgroup and alkyl linear chain as link were synthesized. On the backbone chain, somebackbone carbon atoms are replaced by oxygen atoms. The disturbance of increasingthe length of the backbone chain and the influence of changing the species of metal ionson the effective regulation of supramolecular complex structures were investigated.6. On the base of the previous research on lanthanide-based clusters, a pair ofenantiomorphous chiral reduced Schiff bases of amino acids was synthesized. Theself-assembly coordination chemistry and unique triple-helical structures oflanthanide-based supramolecular clusters were investigated further, and thecomprehension of small molecule encapsulated into the cluster was rectified. Theexperiment exhibited that CO₂ molecules from the atmosphere were efficiently capturedand fixed into these clusters through chemical conversion. Chiral signal analysis of theligands could be successfully applied to anion-selective recognition for CO₃^2- insolution.更多还原