Visible Light‐Regulated Heterogeneous Catalytic PET‐RAFT by High Crystallinity Covalent Organic Framework

Covalent organic frameworks (COFs) are a class of promising photocatalysts for conversing light energy into chemical energy. Based on the tunable building blocks, COFs can be well-designed as photocatalyst for mediating reversible addition-fragmentation chain-transfer (RAFT) polymerization. Herein, 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) and 2,2″-bipyridine-5,5″-diamine (Bpy) are chosen to construct imine-based TFPPy-Bpy-COFs for catalyzing RAFT polymerization of methacrylates under white light irradiation. The well-defined polymers with precise molecular weight and narrow molecular weight distribution are obtained. The switch on/off light experiments suggest excellent temporal control toward RAFT polymerization system and the chain-extension reaction indicates high chain-end fidelity of macro-initiators. Mechanism study clarifies that the electron transfer between excited state of TFPPy-Bpy-COFs and RAFT agent can form living radicals to mediate polymerization. This methodology provides a novel platform for reversible-deactivation radical polymerization using COFs as heterogeneous catalysts.