8-羟基喹啉类金属-有机配位分子笼的设计组装及其催化性能研究

Owing to the confined cavity, tunable structures and properties, metal-organic coordination cages have shown great application prospect in many technological areas such as host-guest chemistry, catalysis and received much attention in the past decades. Herein, a variety of organic ligands based on 8-hydroxyquinoline skeletons with different structures and functions will be designed and synthesized (Some ligands are organic chiral molecules containing post-modification groups). Based on the principle of coordination and supramolecular chemistry, various novel coordination cages with catalytic activity will be prepared. After being characterized by a variety of spectra techniques, the as-synthesized cages will be explored for catalysis (e.g. photodimerization reaction, knoevenagel condensation and henry reaction and so on) on the basis of their structural features and microenvironment. A special emphasis will be given to study the tuning of catalytic properties through introducing functional groups, changing the shape and size of cavity, the coorperative effect of active metal centers. We will further study the influence of synthetic methods, structures of building units on structures and catalytic properties, and the relationship between structures and properties. All these efforts will help us to effectively control the structures and functions of coordination cages at the molecular level. However, above study will facilitate further synthesis of novel metal-organic coordination cages with potential applications.

金属-有机分子笼具有限域性空腔、结构和性能可调等优点，在主客体化学和催化等领域具有重要的研究价值和应用前景。本项目拟以8-羟基喹啉骨架为平台，设计合成结构和功能多样的有机桥联配体（其中包含具有后修饰功能基团的手性配体），利用配位化学和超分子化学原理，与不同金属离子组装制备各种具有新颖结构并兼具催化活性的配位分子笼，通过多种谱学手段表征其结构和物理性能；根据配位分子笼的结构特征和微环境，选择合适的催化反应(如光二聚、Knoevenagel缩合、Henry反应等)评估其催化性能，探索笼状分子功能基团、内部空腔尺寸和形貌、多个活性金属中心间协同作用等对其催化性能的影响，总结配位分子笼催化剂的组装方法、构建单元结构、材料结构和催化性能之间的规律性关系，实现分子水平上对其结构和催化性能的有效控制，为进一步指导合成新型具有良好应用前景的金属-有机配位分子笼催化剂奠定基础。

本项目基于8-羟基喹啉骨架，合成了结构和功能多样的有机柔性配体，利用配位化学和超分子化学原理，与不同金属组装制备出各种结构和功能不同的柱形和哑铃形配位分子笼，还合成了多种金属-有机环状结构、簇合物和多面体。通过X-射线单晶衍射等多种谱学手段表征了其结构；研究了以上金属-有机分子配合物在结晶分离、发光和催化方面的性能，通过配体修饰、合成方法改变和辅助配体的引入达到调控功能配合物的结构和功能的目的。探索了配位分子笼的组装方法、构建单元结构、材料结构和性能之间的关系。本项目取得的研究成果为进一步指导合成新型具有良好应用前景的金属-有机配位分子笼奠定基础。