【作者】 王文华；

【导师】 刘伟生；

【作者基本信息】 兰州大学 ， 无机化学， 2006， 博士

【摘要】 金属离子与有机配体之间通过配位作用以及配体之间的弱相互作用（如氢键、π—π堆积作用等）来构筑结构新颖、性能独特的金属—有机超分子配合物，近年来已经成为配位化学、超分子化学、晶体工程交叉领域的热点。其中多核、3d-4f杂多核以及螺旋金属—有机超分子配合物因具有新颖的拓扑结构和光、电、磁学、催化和吸附存储等性质而备受青睐，同时配体及金属配合物的超分子同质异构现象也引起了广大学者的兴趣。 本论文以此为目标，以含氮芳香羧酸为主要构筑单元与过渡或稀土金属离子进行探索性组装，选择性的合成了一系列结构新颖的金属—有机超分子配合物，基于晶体结构分析，讨论了经典和新型分子间氢键、π—π堆积在构筑新颖的金属—有机框架的作用和超分子异构化现象中的角色，并对相关化合物的荧光性能、生物活性和同质多晶现象进行了的研究，对利用不同的物理和化学的方法定向合成出结构新颖的零至三维配合物和对已有结构进行结构调控进行了有益的探索。 全文共分五个部分： 1)简单介绍了配位化学、金属—有机超分子、金属—有机框架、晶体工程和同质多晶等基本概念及其研究方法。综述了水簇、3d-4f和手性螺旋金属—有机超分子配合物的研究意义和现状。 2)利用含N，O芳香配体和Co（Ⅱ）在较低温条件下得到了椅式构象的同质异构体，并实现了对其在溶剂热条件下的异构化，多重C—H…O（NO₃^-）及新颖的C—H…π₄⁶（NO₃^-）氢键在构象同质多晶和超分子异构化现象中扮演着特殊角色，而新颖的C—H…π₄⁶（NO₃^-）氢键的发现拓展了C—H…π_mⁿ氢键在晶体工程中研究领域。 3)首次在同一单晶体中发现了开链四元水簇的异构化现象，由氧原子桥联的开链四元水簇的二聚体组成了新颖的假八元、十元水簇并呈现椅式构象，分析它们在桥联金属—有机配合物单元成超分子框架中的作用。采用“Water+4A MS”的策略，在温和条件下，成功的实现了对上述水簇配合物的结构调整，得到了含多元配体的、完全去水的MOFs。利用成熟的晶体结构模型，设计合成了含四重游离羟胺酸官能团的双核水轮型配合物，探讨此类新型游离羟胺酸金属化合物（Free hydroxamic acid metal complexes：FHAMCs）的细胞毒性。 4)利用配体和金属离子间类似酶的专一反应性能，首次通过原位生成配体策略，在合成单核，多核羧酸配合物和3d-4f配位聚合物中进行了探索，对于3d-4f金属羧酸超分子配合物的合成及单链磁体（SCMs）的构筑提供现实可行的新方法。通更多还原

【Abstract】 In recent years, the most important subjects of intensively current research in coordination chemistry, supramolecular chemistry and crystal engineering have focused on building novel metal-organic supramolecular compounds through metal-ligand coordination and intermolecular interactions （hydrogen bonds, π-π stacking, etc.） between ligands. Design and synthesis of polynuclear, 3d-4f heterometallic and helical metal-organic supramolecular complexes with novel topological structures or special properties are of great interest at present, due to their ability to impart nonlinear optical, electro-chemicals, magnetics, catalysts, molecular devices, highly selective and specific molecular transformations, transport, and storage and polymorphism.However, based on the principles of crystal engineering and supramolecular self-assembly, control of molecular self-assembly to form novel metal-organic frameworks （MOFs） through reacting special ligand with some metal ions and structural adjustment of them by chemical and physical technique have been encountering considerable challenges and opportunities for chemists. With these aims, several carboxylate ligands with N atom are selectively used as building units reacting with 3d or 4f metal ions, and a series of complexes with novel structure have been prepared. Based on crystal diffraction analysis, novel hydrogen bonds （HBs）, π-π stacking interactions and their role in building 0-3 D MOFs and supramolecular isomerism have been studied. The primary investigations on polymorphism, fluorescence properties and cytotoxicity of some complexes have been performed.This thesis covers following five parts:1) In this part the concepts of coordination chemistry, metal organic supramolecular, metal-organic frameworks （MOFs）, polymorphism and crystal engineering were simply introduced. The structural research approaches, single crystal growth technology, along with the significance and application of the study, were also discussed. Systematical review on the research background and significances of water cluster, 3d-4f heterometallic and helical metal-organic supramolecular complexes which are related with this thesis were made.2) Boat conformational isomer cis-1 sustained by novel C-H…π（NO₃^-） （delocalized π-electron system） HBs was first obtained within an I-shape tube at low-temperature and transformation of cis-1 to chair conformational isomer trans-2 assembled via multiple C-H … O（NO₃^-） HBs was realized by solvothermal process. The Ag⁺ can enhance the fluorescence of the Tb（III） complex.3) Novel twin chair-like pseudo-decameric water clusters, namely, the dimer of metal bound acyclic water tetramers conformational isomers linked with two O_carboxylate atoms have been observed in complex for the first time. The metal bound acyclic water更多还原