Chiral 3D Covalent Organic Frameworks for High Performance Liquid Chromatographic Enantioseparation

作者：Xing Han, Jinjing Huang, Yuan Chen, Yan Liu, Yong Cui · 发表于：Journal of the American Chemical Society · 年份：2018 · DOI：10.1021/jacs.7b12110 · 被引用次数：519 · 研究领域：Covalent Organic Framework Applications、Metal-Organic Frameworks: Synthesis and Applications、Luminescence and Fluorescent Materials

In spite of their great promise for enantioselective processes due to the rich host-guest chemistry, it remains a challenge to construct covalent organic frameworks (COFs) with chiral three-dimensional (3D) structures. Here we report bottom-up synthesis of the first example of 3D chiral COFs by imine condensation of an enantiopure 2-fold symmetric TADDOL-derived tetraaldehyde with a tetrahedral tetra(4-anilyl)methane. After postsynthetic oxidation of imine linkages, the framework is transformed into an amide-linked COF with retention of crystallinity and permanent porosity as well as enhanced chemical stability. The resultant isostructural COFs feature a 4-fold interpenetrated diamondoid open framework with tubular channels decorated with chiral dihydroxy auxiliaries. Both COFs can be used as chiral stationary phases for high performance liquid chromatography to enantioseparate racemic alcohols, and the oxidized COF shows superior separation performance compared to the pristine framework.