Amino-Yne Click Polymerized β‑Ketoenamine-Based\nCovalent Organic Frameworks for Enhanced Photocatalytic Performance

Constructing β-ketoenamine-linked\ncovalent organic frameworks\n(COFs) for photocatalysis is highly attractive but remains challenging\ndue to limited reaction types and monomer availability. Herein, we\nhighlight the critical role of amino-yne click polymerization in overcoming\nthese challenges and enabling the successful synthesis of a novel\nβ-ketoenamine-linked COF, named En-COF-P. This new approach\nnot only simplifies the synthesis process but also significantly expands\nthe types of chemical linkages available for COF construction. The\nresulting En-COF-P exhibits an enhanced visible light absorption range,\nfacilitating improved charge generation and separation. These properties\ntranslate into remarkable photocatalytic performance, particularly\nin the blue-light-driven selective oxidation of organic sulfides,\nwhere En-COF-P achieves up to 99% conversion and 99% selectivity.\nRemarkably, En-COF-P’s photocatalytic efficiency is eight times\nhigher than that of traditional imine-linked COFs. This work underscores\nthe potential of click polymerization in COF synthesis and advances\na new strategy for the design of highly efficient photocatalysts.