负载L-脯氨酸席夫碱的镧系金属-有机骨架材料的设计合成及催化不对称羟醛缩合反应的研究

In recent years, proline and proline derivative have been widely studied by the chemists and making them in MOFs to synthesize support catalysts which have the high catalytic activity are attracting more and more interest. In our project, we make use of the specific lanthanide ions (Sm3+，Eu3+，Gd3+，Tb3+，Dy3+，Ho3+，Er3+)and the di-carboxylic acids with amino functional groups and alkynes bond connectivity to synthesize a new type of lanthanide metal-organic frameworks (Ln-MOFs) by hydrothermal / solvothermal methods, using postsynthetic covalent modification and the condensation reaction of aldehyde and the amino group to put L-prolinal into the pore of supported Ln-MOFs, study Ln-MOFs which supported L-proline Schiff in asymmetric aldol reaction of aromatic aldehydes and acetone to explore on change law of property between modified MOFs and unmodified MOFs, comprehensive summarize the relation in the synthesis, structure, asymmetric catalytic property of supported MOFs to provide experimental support and theoretical guidance for the controllable synthesis and directed assembly of the specific function and structure of MOFs。

近年来，脯氨酸及其衍生物催化的不对称羟醛缩合反应受到了广泛关注，将其负载于 MOFs 上制备高催化活性的负载型催化剂也引起了人们的极大兴趣。本项目利用带氨基官能团、炔键连接的二元羧酸为构筑模块，采用水热 / 溶剂热方法，与特定镧系金属离子（Sm3+，Eu3+，Gd3+，Tb3+，Dy3+，Ho3+，Er3+）组装，构筑新型镧系金属-有机骨架材料（Ln-MOFs）；采用共价键修饰的方法，通过未配位氨基与L-脯氨醛的缩合反应，将L-脯氨醛负载于Ln-MOFs孔道中，研究负载L-脯氨酸席夫碱的 Ln-MOFs材料在芳香醛与丙酮的不对称羟醛缩合反应中的作用，探讨修饰前后性质变化规律，全面总结负载型 MOFs的合成－结构－不对称催化性能关系，从而为特定功能和结构的 MOFs 可控合成与定向组装提供实验支持和理论指导。

采用经典的有机合成方法对 MOFs 进行共价键修饰是目前配位化学重要研究领域之一。本项目采用水热、溶剂热、扩散法，利用多元羧酸配体与特定金属离子组装，构筑新型金属－有机骨架材料；研究了其固体荧光、磁性、催化等性能，探讨了性质变化规律，总结了负载型 MOFs 的合成－结构－性能关系，为特定结构和功能 MOFs 的可控合成与定向组装奠定了基础。