Amino-Yne Click Polymerized β-Ketoenamine-Based Covalent Organic Frameworks for Enhanced Photocatalytic Performance

Constructing β-ketoenamine-linked covalent organic frameworks (COFs) for photocatalysis is highly attractive but remains challenging due to limited reaction types and monomer availability. Herein, we highlight the critical role of amino-yne click polymerization in overcoming these challenges and enabling the successful synthesis of a novel β-ketoenamine-linked COF, named En-COF-P. This new approach not only simplifies the synthesis process but also significantly expands the types of chemical linkages available for COF construction. The resulting En-COF-P exhibits an enhanced visible light absorption range, facilitating improved charge generation and separation. These properties translate into remarkable photocatalytic performance, particularly in the blue-light-driven selective oxidation of organic sulfides, where En-COF-P achieves up to 99% conversion and 99% selectivity. Remarkably, En-COF-P’s photocatalytic efficiency is eight times higher than that of traditional imine-linked COFs. This work underscores the potential of click polymerization in COF synthesis and advances a new strategy for the design of highly efficient photocatalysts.