手性锆-有机框架的设计组装及不对称催化性能

Owing to the excellent water thermal stability and chemical stability, zirconium-based Metal-Organic Frameworks (MOFs) constructed from multi nuclear zirconium clusters have shown great application prospect in technological areas such as adsorption, separation, heterogeneous catalysis and received much attention over the past decades. The proposal is aimed at rational design and controlled synthesis of chiral porous MOFs catalysts with high stability using enantiopure TADDOL derivatives as bridging ligands, based on the principle of coordination chemistry and supramolecular chemistry. After being characterized by a variety of techniques, the as-synthesized compounds will be explored for asymmetric catalysis (e.g. Diels-Alder reaction and Aldol reaction) on the basis of their structural features and chiral microenvironment. We will extensively study the influence of synthetic methods, steric and electronic features of building units on structures and properties including stability and catalytic activities and the relationship between structures and properties. All these efforts will help us to obtain heterogeneous catalysts with high reactivity and enantioselectivity through modular design of functional molecules and efficient control of the structure and function at the molecular level, and help us to further understand and facilitate the development of chiral science.

含多核金属锆簇的金属-有机框架(MOFs)材料，由于其优异的水热稳定性和化学稳定性，在吸附和多相催化等领域具有重要的研究价值和应用前景。本项目以手性TADDOL骨架为平台，合成结构和功能多样的手性有机桥联配体，利用配位化学原理和超分子化学的方法，与金属锆簇组装制备具有不对称催化性能的、高稳定性的手性多孔锆基MOFs，对其结构和物理性能进行表征；根据材料的结构特征和手性微环境，选择合适的不对称催化反应(如Diels-Alder、Aldol反应等)评估其催化性能，探索组装方法、构建单元的空间和电子结构与材料结构、稳定性和催化性能之间的关系；实现分子水平上对结构和功能的有效控制，通过模块化功能分子设计实现功能手性材料的一体化的制备和强化，获得具有高反应活性和高选择性多相催化剂。

以手性TADDOL、联苯和希夫碱骨架为平台，制备了系列具有不同结构类型的手性锆基和其它金属基MOFs等手性多孔框架；研究了这些多孔材料的不对称催化、手性分离和传感方面的应用，探索和总结了手性多孔结构形成过程各基本结构单元的电子和空间结构、制备方法与结构之间的关系，以及结构和性能之间的关系。利用手性联苯配体与具有不同配位能力的金属组装得到了包含锆基MOF在内共16种同构的手性多孔MOFs材料，具有良好的热稳定性及耐水、耐酸碱性，且可作为优异的Lewis酸催化剂催化不对称烯硼酯加成、双烯硼酯加成、Friedel-Crafts烷基化和硫醚氧化等重要的不对称催化反应，选择性高达99%。羧酸官能化的希夫碱配体和金属锌分级组装得到一个具有介孔尺寸的手性MOF，可通过酸碱相互作用吸附固载手性有机胺催化剂催化不对称Aldol反应。在分级组装过程中，螺旋体的对称性和手性得以保持、传递和放大。. 在国际重要学术期刊发表SCI论文19篇，包括J. Am. Chem. Soc 6篇，Angew. Chem. Int. Ed 1篇，Nat. Commun 1篇，Coord. Chem. Rev 1篇，ACS Catal 1篇和Chem. Commun 3篇；论文发表后被Synfacts选作研究亮点进行专题报道。