Designed Synthesis of a 2D Porphyrin‐Based sp²Carbon‐Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis

The construction of stable covalent organic frameworks (COFs) for various applications is highly desirable. Herein, we report the synthesis of a novel two-dimensional (2D) porphyrin-based sp² carbon-conjugated COF (Por-sp² c-COF), which adopts an eclipsed AA stacking structure with a Brunauer-Emmett-Teller surface area of 689 m² g⁻¹ . Owing to the C=C linkages, Por-sp² c-COF shows a high chemical stability under various conditions, even under harsh conditions such as 9 m HCl and 9 m NaOH solutions. Interestingly, Por-sp² c-COF can be used as a metal-free heterogeneous photocatalyst for the visible-light-induced aerobic oxidation of amines to imines. More importantly, in comparison to imine-linked Por-COF, the inherent structure of Por-sp² c-COF equips it with several advantages as a photocatalyst, including reusability and high photocatalytic performance. This clearly demonstrates that sp² carbon-linked 2D COFs can provide an interesting platform for heterogeneous photocatalysis.