金属配位导向合成有机笼状化合物及主客体识别研究

The strategy of metal coordination templated synthesis has played a significant important role for the construction of catenanes, rotaxanes, molecular knots and other complex supramolecular structures. This proposal is aimed at overcoming the synthesis inefficiency of organic cage compounds and investigating their host-guest recognition behavior. The rational construction of organic cage compound with special polyhedron structure will be achieved through employing molecular clips to close the vertexs of coordination cage by using metal coordination templated synthesis strategy. Through extension the examples and modification the structures of organic cage, we try to summarize the assembly conditions and factors which affect the metal coordination oriented synthesis of organic cage. Systemic investigation about the host-guest recognition of neutral, cationic and anionic guest molecular will be implemented. The structural features of the organic cages influence on the weak interactions and molecular recognition sites inside the cage cavity will also be analyzed. The relationship between the structure of organic cages and their host-guest behavior, and host-guest recognition mechanism will be revealed. The study of chemical reactions inside the cage cavity will be carried out to further expand the applications of organic cage with nanoscale cavity in the field of molecular containers and catalysis. This proposal can not only provide theoretical and experimental basis for the rational and efficient construction of organic cage compounds, but also promote the development of coordination chemistry and supramolecular science.

金属配位模板合成法在构筑索烃、轮烷和分子结等复杂结构超分子过程中发挥着极其重要的作用。本项目针对有机笼状化合物合成低效和主客体识别等问题，采用金属配位导向的合成组装方法，通过分子夹对金属配位笼顶点进行封装，实现特定多面体结构的有机笼状化合物的定向合成；通过对有机笼结构的拓展和修饰，总结归纳金属配位导向合成有机笼的组装条件和影响因素。系统研究有机笼状化合物对中性、阳离子和阴离子客体的识别性能，考察有机笼基元结构对弱相互作用和笼内分子识别位点构建的影响；揭示有机笼状化合物主客体识别性能和结构之间的关系规律及识别机制；探索有机笼空腔内的分子受限反应，进一步拓展这类具有纳米级空腔的有机笼状化合物在分子容器和催化领域的应用。项目研究不仅可为定向高效构筑有机笼状化合物提供理论和实验依据，同时推动配位化学和超分子科学相关领域的发展。

项目针对笼状化合物合成效率低、结构难以修饰和主客体识别位点调控等问题，采用金属配位导向合成法实现了一系列具有丰富多面体结构和纳米空腔的笼状化合物的定向构筑及功能应用。（1）设计合成了二芳基乙烯类光致变色有机笼状化合物、同手性四面体金属有机笼状化合物、咪唑亚铁类金属有机笼状化合物等多种类、结构多样、空腔可调的笼状化合物，系统研究了金属配位在笼状化合物形成中的预组织结构导向作用，阐明了多组分自组装过程中金属配位的影响因素及模板机制。（2）详细研究了笼状化合物对中性、阳离子和阴离子客体的识别性能，追踪了笼状化合物选择性识别富勒烯、碘分子、有机染料、卤素离子、Aβ蛋白以及原位包载贵金属纳米粒子的过程，考察了笼状化合物空腔识别位点与客体分子相互作用的模式，揭示了笼状化合物主客体识别性能和结构之间的规律及识别机制。（3）进一步将金属配位导向合成法应用于金属有机框架和共价有机框架的合成，证实了其在功能材料结构构筑中的通用性，研究了材料的自旋转换性能以及在超级电容、传感、催化等领域的应用。项目研究推动了我国笼状化合物超分子的发展，为晶态多孔功能分子材料的构筑提供了新的思路。