Liu Chao, Jin Yucheng, Qi Dongdong, Ding Xu, Ren Huimin, Wang Hailong, Jiang Jianzhuang
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing Beijing 100083 China
Chem Sci. 2022 May 20;13(23):7014-7020. doi: 10.1039/d2sc01876d. eCollection 2022 Jun 15.
Chiral recognition and discrimination is not only of significance in biological processes but also a powerful method to fabricate functional supramolecular materials. Herein, a pair of heterochiral porous organic cages (HPOC-1), out of four possible enantiomeric products, with mirror stereoisomeric crystal structures were cleanly prepared by condensation occurring in the exclusive combination of cyclohexanediamine and binaphthol-based tetraaldehyde enantiomers. Nuclear magnetic resonance and luminescence spectroscopy have been employed to monitor the assembly process of HPOC-1, revealing the clean formation of heterochiral organic cages due to the enantioselective recognition of (,)-binaphthol towards (,)-cyclohexanediamine derivatives and . Interestingly, HPOC-1 exhibits circularly polarized luminescence and enantioselective recognition of chiral substrates according to the circular dichroism spectral change. Theoretical simulations have been carried out, rationalizing both the enantioselective assembly and recognition of HPOC-1.
手性识别与区分不仅在生物过程中具有重要意义，也是制备功能性超分子材料的有力方法。在此，通过环己二胺和联萘酚基四醛对映体的独特组合发生缩合反应，从四种可能的对映体产物中干净利落地制备出一对具有镜像立体异构晶体结构的异手性多孔有机笼（HPOC-1）。利用核磁共振和发光光谱监测HPOC-1的组装过程，揭示了由于（，）-联萘酚对（，）-环己二胺衍生物的对映选择性识别而干净地形成异手性有机笼。有趣的是，HPOC-1根据圆二色光谱变化表现出圆偏振发光和对手性底物的对映选择性识别。已经进行了理论模拟，阐明了HPOC-1的对映选择性组装和识别。
