Designed Synthesis of a 2D Porphyrin-Based sp2 Carbon-Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis

Angew Chem Int Ed Engl. 2019 May 6;58(19):6430-6434. doi: 10.1002/anie.201902543. Epub 2019 Apr 4.

Abstract

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.

Keywords: conjugated polymers; covalent organic frameworks; high stability; metal-free photocatalyst; porphyrin chemistry.