多孔配位笼电荷调控及特异性反应开发

多孔配位笼（又称“分子笼”）具有结构和性质可调控的空腔，在主客体化学、分子容器和催化反应等方面展现出独特的应用。虽然目前已报导的多孔配位笼具有多种拓扑结构和电荷属性，然而没有一种多孔配位笼能够在单一拓扑结构下，只调整电荷性质，从而研究其对催化反应的影响。在本项目中，申请人设计了多种具备电荷基团的有机配体，结合稳定型金属簇，通过自组装合成一系列稳定的电荷可调控型多孔配位笼。申请人拟计划使用氮唑类有机配体与过渡金属簇形成稳定的配位结构，计划得到同一种拓扑结构下具备正电荷、负电荷和中性的不同电荷性质。并将该材料用于包裹催化剂和反应底物，通过分析多孔配位笼空腔负载的客体分子类型，分析得出多孔配位笼电荷性质对于催化反应的影响，希望建立一种研究多孔材料催化性能的普适性策略。本项目将提供一种新型制备特定拓扑结构多孔配位材料的设计合成策略和电荷调控方法，为探索多孔材料的催化反应和特异性反应打下坚实基础。

Porous coordination cages, also known as “molecular cages”, are sort of supramolecular assembly which has tunable cavity. The unique property allows it to be used in host-guest chemistry, molecular flask and catalysis. Although there’s a lot of porous coordination cages with a variety of topology and electronic property, there’s no report of a porous coordination cage with tunable electronic property under a single topology/structure. Thus, it is difficult to discuss how the cage dictate catalytic reactions. In this proposal, the applicant proposed to prepare multiple organic ligand with electronic modification property. By engineering the coordination bond with metal cluster, stable and charge tunable porous coordination cages are expected to be obtained. The applicant will use azolate-based organic ligands and transition metal clusters to prepare a series of porous coordination cages and tune their charge to be positive, negative and neutral under a single topology. Then, the cages will be used to encapsulate catalysts and substrates in different solvent systems, in order to clarify the relationship between the electronic property of the cage and the species of the guest molecules (catalysts or substrates). The information will guide applicant to set up a universal methodology to investigate the catalytic property of porous materials. This project will not only provide a novel synthetic strategy for preparing charge tunable porous coordination cages, but also readily install a foundation of exploring catalytic and specific reactions by using porous coordination cages.