手性多孔联苯型金属-有机骨架材料的不对称合成与性能研究

Chiral porous metal-organic frameworks have attracted extensive attention recently due to their potential applications in adsorption and seperation, asymmetric catalysis, and nonlinear optics, etc. This proposal is to build chiral porous metal-organic frameworks by designing nonsymmetric and potential axial chiral biphenyl ligands with the use of coordinate self-assembly strategy. By changing the type and size of the ortho substituents of connection axes of the ligands, it is also proposed to control the rotation of the biphenyl group and explore symmetric breaking mechanism. As a result, this provides the basis for rational design and construction of chiral porous metal-organic frameworks. Efficient asymmetric synthesis route are to be proposed with further contribution to the theory of asymmetric synthesis. Moreover, by studying the adsorption and separation properties and catalytic properties in asymmetric catalytic reactions of porous materials, this proposed research is to provide a theoretical basis for constructing a novel porous functional materials with selective adsorption and separation and highly efficient catalytic performance. The rare earth industry is a strategic emerging industry with great significance in Fujian Province and Longyan City during "12th Five-Year Plan" period. This project is to play a significant role in the development and utilization of rare earth resources of Longyan City. This project is to select the rare earth ion as the second metal and introduce it into the transitional metal-organic frameworks. By using the synergistic effect, a new structure of heteronuclear metal-organic frameworks materials are to be built with the study of its adsorption and catalytic performance.

手性多孔金属有机骨架材料由于在选择性吸附与分离、不对称催化、非线性光学等领域有着潜在的应用而受到广泛关注。本项目通过设计分子结构非对称的、具有潜在轴手性的联苯类配体，利用配位自组装技术，构筑手性多孔金属-有机骨架材料; 通过改变配体连接轴邻位取代基类型及尺寸，调控联苯基团旋转受阻，探索对称性破缺机制，为手性多孔金属-有机骨架材料的定向设计与构筑提供依据，提出有效的不对称合成路线，丰富不对称合成理论; 研究多孔材料的吸附分离性能及其在不对称催化反应中的催化性能，为构筑具有选择性吸附分离与高效催化性能的新型多孔功能材料提供理论基础。稀土产业是福建省和龙岩市"十二五"期间重点培育的战略性新兴产业，本项目选择稀土离子作为第二金属，引入到过渡金属-有机骨架中，利用协同效应，构筑结构新颖的异核金属-有机骨架材料，研究吸附与催化性能，对开发利用龙岩市稀土资源具有重要意义。

金属-有机骨架材料是由金属离子和有机配体自组装而成的一类新型多孔材料，手性配位聚合物在吸附、不对称催化、手性分离、非线性光学等领域具有较好的应用前景。本项目重点开展的工作：一、设计合成分子结构非对称的、具有潜在轴手性的配体。（1）以联苯基团为结构基元，设计端基为水杨酸取代基的结构非对称的有机桥联配体，并期望通过改变配体连接轴邻位的不同取代基类型及尺寸，调节诱导联苯基团旋转受阻，实现配体的轴手性。（2）新设计刚性联萘基多羧酸配体，区别于C-C单键联萘基多羧酸配体，利用wittig反应设计C=C双键的平面型联萘基多羧酸配体，并期望通过平面型刚性配体合成孔洞配合物。二、采用配位自组装技术，构筑多孔金属-有机骨架材料，以期获得手性配合物。项目利用结构不对称的联苯多羧酸配体、水杨酸及其它多羧酸衍生物配体合成金属-有机配位化合物，进行结构表征，探讨了配合物合成影响因素及合成机理；三、对合成配合物的性质表征，研究潜在应用。主要研究进展：项目设计的潜在轴手性联苯类配体合成和平面型联萘类羧酸配体合成未达预期目的；选用结构非对称的刚性/半刚性联苯类羧酸配体，利用水热合成法，得到16个配合物，进行结构分析和部分性质表征；利用水杨酸及其它多羧酸衍生物配体合成配合物，研究其应用领域，发表 1篇SCI收录论文，授权 1项发明专利。对结构非对称的联苯类羧酸配合物合成研究，分析配体骨架的不同取代基类型及尺寸等对主体结构对称性的选择规律，有助于揭示非对称结构反应物实现手性的反应机制。