Construction of Ultrastable Nonsubstituted Quinoline‐Bridged Covalent Organic Frameworks via Rhodium‐Catalyzed Dehydrogenative Annulation

Exploring new routes to lock the dynamic C=N bonds in imine-linked covalent organic frameworks (COFs) is highly desired for enhancing their stability and functionality. Herein, a novel C=N bridge locking strategy via rhodium-catalyzed [4+2] annulation is developed to construct nonsubstituted quinoline-linked COFs (NQ-COFs). The notable feature of this strategy includes high C=N conversion efficiency, oxidant-free, and generality for synthesis of a variety of NQ-COFs with high chemical stability. Particularly, after post-synthetic modification, the crystallinity, topology, and porosity of pristine imine-linked COFs are well retained. When used as photocatalysts, NQ-COFs display better visible light absorption and carriers' separation efficiency due to enhanced in-plane π conjugation ability, as well as more facile generation of superoxide anion radicals than their counterparts, thus leading to efficient synthesis of 2,4,6-tris(aryl)pyridines, benzimidazole, and sulfoxide derivatives.