新型手性构件导向的手性微孔配位聚合物的设计合成及不对称催化性能研究

The designed syntheses, structures and properties of chiral porous coordination polymers have been the focus of chemical and material subjects. In this project, we will introduce rigid N-[(carboxyphenyl)-sulfonyl] or N-[(carboxybiphenyl)-sulfonyl] group into amino groups of flexible amino acids to produce two kinds of new chiral organic components of amino acid derivatives containing both carboxylic and amino groups. And then they will be used to react with transition metal ions to construct new chiral porous coordination polymers. The synthetic conditions, crystal structures and porous structures of this kind of material will be studied systematically. Their applications in the catalytic asymmetric reactions, including asymmetric Michael addition, asymmetric Cyanosilylation, asymmetric Biginelli and asymmetric Aldol reaction will be investigated. The crucial aim of this project is to explore the influence of chiral organic components on the structures and catalytic effect of chiral porous coordination polymers and summarize their intrinsic relationship. From these studies, we hope to disclose the advantages and limitations of the functional characteristics/mechanism in porous coordination polymers, reveal the intrinstic factors of influencing catalytic application in the targeted coordination polymers. This will provide a way for constructing new catalytic materials and collect some experimental and theoretic facts for furhter developments and applications of catalytic materials.

手性微孔配位聚合物的设计合成、结构与性能研究一直是化学、材料等学科关注的前沿研究领域。本项目以天然氨基酸为手性源，将刚性苯甲酸磺酰基或联苯甲酸磺酰基引入到柔性氨基酸氨基基团中，设计合成兼有羧基和氨基酸基团的两大类手性氨基酸衍生物配体，以其为导向构筑手性微孔配位聚合物。系统研究该类材料的合成条件、晶体结构和孔道结构,进而以不对称Michael addition、不对称Cyanosilylation、不对称Biginelli以及不对称Aldol等反应为探针评估材料的不对称催化性能,重点探索手性氨基酸衍生物结构基元对手性微孔配位聚合物的结构和不对称催化性能的影响规律，总结其中的内在关联。深刻认识手性氨基酸衍生物微孔配位聚合物不对称催化特性/机理及其优势和局限性，揭示此类配位聚合物中影响其催化性质的内在因素,为定向构筑新型催化材料提供新的思路与方法，为催化材料的开发与应用在理论与实验上奠定基础。

本项目通过选择不同有机配体与特定的金属离子反应设计合成了一系列微孔配位聚合物，测试并解析了它们的晶体结构，并利用元素分析、红外、热重、X-射线粉末衍射等对其进行了表征。进而以Knoevenagel反应、芳香酚的酰化反应以及环氧开环反应等反应为探针评估此类材料的催化性能, 重点探索微孔配位聚合物不同结构基元对催化性能的影响规律，总结其中的内在关联。同时对所合成的其它配位聚合物进行了磁学、荧光及光催化性能研究，揭示此类配位聚合物中影响其功能的内在因素,为定向构筑新型功能材料提供新的思路与方法。项目研究期间，在J.Mater.Chem.A, J. Mater. Chem. C, Green Chem., Dalton Trans, Cryst. Growth. Des., CrystEngComm., RSC Adv., New J. Chem.等国内外期刊发表SCI收录论文26篇，其中影响因子3.0以上论文18篇，授权国家发明专利7项，培养硕士研究生11名，6人已通过硕士论文答辩。