Seo JS, Whang D, Lee H, Jun SI, Oh J, Jeon YJ, Kim K
National Creative Research Initiative Center for Smart Supramolecules and Department of Chemistry, Pohang University of Science and Technology, Republic of Korea.
Nature. 2000 Apr 27;404(6781):982-6. doi: 10.1038/35010088.
Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.
无机沸石被用于许多实际应用中，这些应用利用了其晶体结构固有的微孔性。由通过非共价相互作用连接的模块化有机结构单元组装而成的有机类似物，对于类似的应用也很有吸引力。这些应用范围从催化、分离和传感器技术到光电子学，其中对映选择性分离和催化对化学和制药行业尤为重要。这些类似物的模块化结构允许灵活且合理的设计，因为原则上微孔的结构和化学功能都可以被精确控制。已经制备出具有大空隙和高骨架稳定性的多孔有机固体，并已开始对可及的孔功能范围进行研究。例如，已知具有催化活性的有机沸石类似物，以及手性金属有机开放框架材料。然而，后者仅以外消旋混合物形式存在，或者缺乏实际应用所需的骨架稳定性或空隙空间程度。在此，我们报告了一种纯手性金属有机多孔材料的合成，该材料能够在其孔中对映选择性地包合金属配合物，并以对映选择性方式催化酯交换反应。我们的合成策略使用对映纯的金属有机簇作为二级结构单元，应该很容易应用于化学修饰的簇组分，从而提供获得适用于对映选择性分离和催化的多种多孔有机材料的途径。
