含混合配体的MOFs基不对称催化剂的设计、合成及修饰

Chiral MOFs-based catalysts have broad application prospects in the asymmetric catalytic reaction region. Now, the introduction of sole chiral ligand is the most common strategy for the building of chiral MOFs materials. While those based on mixed ligands have been rarely reported. Oriented by outstanding asymmetric catalytic functions, the chiral and achiral ligands as mixed building units will be designed and synthetized to construct the chiral MOFs-based catalysts. Using crystal engineering strategy,their structures will be studied by changing the proportion of metal/ligand, the reaction system pH value, reaction temperature, reaction time and other factors. According to the structure characteristics, their catalytic performance to the special asymmetric catalytic reaction will be investigated, and the best MOFs-based catalyst will be filtrated. The reaction assembly rules and the catalytic ability-structure relationships will be analysed and summarized. By rational design, modification and optimization of the structure, the excellent chiral MOFs-based catalysts will be synthetized controllably, and their asymmetric catalytic ability will be enhanced and optimized.

手性MOFs基催化材料有广阔的应用前景，但目前其构筑策略主要集中于使用单一的手性配体，而基于混合配体构筑手性MOFs材料的研究鲜见报道。本项目拟以优良的不对称催化性能为导向，设计、合成手性和非手性多齿配体作为混合构筑单元，构建具有不对称催化功能的手性MOFs材料。结合晶体工程策略，通过改变金属/配体比例、反应体系的pH值、反应温度、反应时间等因素，研究这些因素对手性MOFs结构的影响。结合结构特点，研究其对特定反应的不对称催化性能，筛选出对特定不对称反应具有优良催化功能的MOFs基催化剂。分析总结组装规律及催化性能-结构的关系，通过对手性MOFs结构的合理设计、修饰裁剪及优化，实现优良手性MOFs基催化剂的可控合成、结构调控、不对称催化功能的增强与优化。

手性MOFs基催化材料有广阔的应用前景，但其构筑策略主要集中于使用单一的手性配体，而基于混合配体构筑手性MOFs材料的研究鲜见报道。本项目自启动以来，在项目基金支持下，以优良的不对称催化性能为导向，设计、筛选了多类手性、非手性多齿配体，如三联吡啶多羧酸类配体、1,2-二(吡啶-4-亚甲基)肼、邻羧基苯乙酸、甲基丙二酸等为构筑单元，构建了系列具有不对称催化功能的MOFs材料，研究了其对特定反应（如以二氧化碳和环氧化合物为原料催化合成各种环状碳酸盐等）的不对称催化性能，筛选出了对特定不对称反应具有优良催化功能的MOFs基催化剂。此外，在本项目基金的支持下，还从事了一些相关工作，采用单一或混合配体策略，构建了多类MOFs材料，并详细研究了其磁、光等性能。此部分工作对目标催化材料的合成具有重要的借鉴意义。