自由基MOF晶态材料的构筑及其辅助结构解析与性能研究

自由基物质是含不成对电子的原子、分子或离子，具有很强的化学反应活性，它们的寿命非常短，如何分离稳定自由基己成为自由基化学领域中的研究热点。本项目提出了利用金属有机配位聚合物（MOFs）特殊的空间限域和电子分布效应对自由基物质进行分离稳定的构想。通过选取合适的含有活性自由基结构单元的配体和客体，运用晶体生长或后修饰法合成含有自由基组分的MOF。结合晶体海绵技术和量子化学计算, 自由基MOF能够不需要结晶过程实现对不稳定自由基组分的结构解析，有利于对自由基成键本质和反应机理进行结构可视化研究。同时，MOF结构有序多样性和自由基特殊的开壳层电子结构，将会在荧光、磁性、导电和催化等方面呈现新颖有趣的性质, 对其深入挖掘最终将发展出一种全新的自由基MOF晶态功能材料。

As organic radicals is a kind of atoms, molecules or ions containing unpaired electrons, their life is very short with high chemical reactivity. Therefore, the stabilization of transient radicals has become one of the frontier topics in the field of free radical chemistry. In this project, we propose the concept of separating and stabilizing unstable radicals by the special spatial confinement and electron distribution of metal organic frameworks (MOFs). By selecting suitable ligands or guests with active radical structural units, radical MOF can be synthesized by crystal growth or post-synthesis modification. According to crystal sponge technique and quantum chemistry calculation, radical MOF can be able to realize the structural analysis of unstable radicals without the crystallization process, which is conducive to visualize the bond and reaction mechanism of radicals. Considering that the ordered structure diversity of MOF and open shell electronic structure of radical species endows the materials with novel and intriguing electronic, magnetic, optical, and redox properties, the intensive study of property and function will eventually open new perspective for developing radical MOF crystalline materials.