富含酰胺基手性多孔金属有机骨架材料的有效组装及催化性能研究

Functional design and synthesis of porous metal-organic frameworks has an important application prospect in the field of materials, gas storage, catalysis is the current frontier of international research. In this project, we will introduce rigid trimesoyl acyl group or biphenyl dimethyl acyl into amino groups of chiral amino acid to produce two kinds of new chiral organic ligands containing both carboxyl and amide groups. Then they will be used to construct chiral porous metal-organic framework complexes with different metal ions, which crystal structures, thermal stability, surface area will be studied. On the other hand, the effect of structure on the properties of bulk products will be also investigated include the location of the coordination atoms, the impact of metal ion and the size of the porous. Their applications in the catalytic reactions, including asymmetric Cyanosilylation, asymmetric Aldol and Knoevengel reaction will be investigated. The crucial aim of this project is to explore the influence of chiral organic ligands on the structures and catalytic effect of chiral porous metal-organic frameworks and summarize their relationship of structure-function. From these studies, we hope to disclose the advantages and disadvantages of the functional characteristics in porous metal-organic frameworks, and reveal the intrinsic factors of influencing catalytic application in the targeted complexes. This will provide a way for constructing new catalytic MOFs materials and collect some experimental and scientific evidence for further developments and applications of catalytic materials.

设计合成在材料、气体存储、催化等领域具有重要应用前景的功能多孔金属有机骨架是当前国际新材料研究的前沿领域。本项目拟利用刚性均苯三甲酰卤基、联苯二甲酰卤基与手性氨基酸构筑兼有羧基和酰胺基团的手性氨基酸类配体, 以其与金属离子有效组装手性多孔金属有机骨架化合物。通过晶体结构、热稳定性、比表面的测定，深入研究配体中配位原子的位置、金属离子的配位需求与体积大小对产物的结构与性能的影响，获得对不对称Cyanosilylation、不对称Aldol及Knoevengel反应具有良好催化性能的骨架结构，重点探求手性配体构筑单元对手性多孔骨架结构和催化性能的影响规律，总结其构效关系。进一步认识手性功能化氨基酸类多孔配合物的催化特性，揭示此类金属有机骨架化合物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实验思路与方法，并为开发新一类催化功能MOFs材料提供科学依据。

本课题采用常规化学合成方法和水（溶剂）热合成方法成功合成多种维数不同的配位超分子和配位聚合物，探索多孔配位聚合物的分子设计方法，包括各种组装条件和溶液组装机理、对聚合物超分子和微孔材料的空间结构的影响和调控；系统研究了单晶—单晶转换过程、酰胺基超分子催化反应与、不同拓扑结构化合物构筑方法，为进一步实现具有微孔结构和磁性结构的配位聚合物的合理组装提供基础；进而系统了研究了系列配位聚合物的空间结构与功能关系，部分无机—有机杂化材料的吸附与分离、电磁、发光、催化等物理化学性质以的应用。其中在稳定微孔配位聚合物的酰胺基对气体小分子吸附，通过单晶衍射，固体核磁和理论计算进行详细表征，取得有特色的重要进展。总共发表研究论文11篇，含影响因子3以上论文共3篇（Chem. Mater.，RSC. Adv. 和.Ceramics International）。另外，发表会议论文3篇，申请发明专利2项，并都已经授权。