Sequential Oxidation/Cyclization of Readily Available Imine Linkages to Access Benzoxazole-Linked Covalent Organic Frameworks

Angew Chem Int Ed Engl. 2024 Mar 11;63(11):e202319909. doi: 10.1002/anie.202319909. Epub 2024 Feb 2.

Abstract

Benzoxazole-linked covalent organic frameworks (BO-COFs), despite their exceptional chemical stability, are still in their infancy. This is primarily because the current prevalent methods require the use of special ortho-hydroxyl-substituted aromatic amines as monomers. Herein, we report an innovative strategy to access BO-COFs directly from imine-linked COFs (Im-COFs) without pre-embedded OH groups, using a two-step sequential oxidation/cyclization process. The two-step process included the oxidation of Im-COFs into amide-linked COFs, followed by a copper-catalyzed oxidative cyclization. Five representative BO-COFs were synthesized with retained crystallinity and high oxidization efficiency, offering the potential to convert a significant portion of Im-COFs into BO-COFs. The structural advantages of the newly designed BO-COFs were demonstrated through their application to photocatalytic organic transformations.

Keywords: Covalent organic frameworks; benzoxazole links; generality; post-synthetic modifications.