基于氮杂环卡宾配体的有机金属框架材料的制备与性能研究

Heterocyclic carbenes have been employed successfully as spectator ligands in organometallic chemistry. The option of fine tuning the electronic properties makes heterocyclic carbenes interesting ligands for the development of novel and efficient functional complexes. This project will design and build a class of multi-nuclear N-heterocyclic carbene ligands, utilize coordinative unsaturated metal centers as "metal corners" to synthesize and characterize a series of multi-nuclear organometallic complexes. We can effectively build the multi-nuclear organometallic complexes containing functional sites by rational design of N-Heterocyclic carbene ligands. The electronic and spectroscopic properties of carbene ligands can be varied over a wide range by modification of the heteroatoms and the substituents at the heteroatoms. By adjusting the size of carbene ligands, reaction conditions, interactions, directions between metal center and organic ligands to control the size and shape of the designed complexes, and utilize the N-Heterocyclic carbene multi-nuclear organometallic complexes to study the mechanism and performance of the catalytic reactions, such above ways can help us to effectively explore the valuable applications of functional carbene-based materials. It can be foreseen that such kind of materials will be widely used for catalysis of small molecules, gas storage, host-guest chemistry and other research fields. This project will greatly expand the application prospects of functional N-Heterocyclic carbene multi-nuclear organometallic materials. Based on this research, we will development our own intellectual property rights of new multi-functional organometallic materials.

卡宾及其金属配合物的制备与性能研究是当代金属有机化学的重要研究领域之一。本项目拟从金属卡宾配位化合物的空间结构出发，利用双齿或多齿氮杂环卡宾配体，综合考虑配位方向、空间位阻、形状调控等因素，利用自组装、溶剂或客体分子诱导等手段构筑基于金属卡宾的分子功能聚集体，深入研究金属卡宾框架配合物的构筑策略，发展具有特色的高效制备路线，探讨各种功能基元对结构的影响，总结其组装规律。在可控制备、物理化学性能、构效关系等方面进行深层次研究，寻求多功能多核金属卡宾材料的制备方法；探索该类材料在有机小分子催化、气体吸附、主客体化学以及光电材料等方面的应用。通过本项目研究，力争在有机金属卡宾框架材料的制备及其相关技术方面取得一些有自主知识产权的研究成果。

卡宾及其金属配合物的制备与性能研究是当代金属有机化学的重要研究领域之一。该项目从金属卡宾配位化合物的空间结构出发，利用双齿或多齿氮杂环卡宾配体，综合考虑配位方向、空间位阻、形状调控等因素，构筑出一系列基于金属卡宾的分子功能聚集体，发展了金属卡宾框架配合物的构筑策略，探讨了功能基元对结构的影响，总结了其组装规律。首次发现了氢气活化诱导制备三维框架化合物，为小分子在框架化合物结构转变中的应用提供了思路。利用光化学反应实现了框架化合物的后修饰，为制备新型功能材料提供了新途径。作为项目研究成果，共发表标注本项目资助论文11篇，其中10篇论文发表在IF大于3.0的国际权威期刊上。