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.

Automated summary

Covalent organic frameworks (COFs) show promise as photocatalysts in converting light energy into chemical energy for mediating specific types of polymerization reactions. Research results indicate that TFPPy-Bpy-COFs constructed under white light irradiation can achieve excellent temporal control over the RAFT polymerization system and maintain high chain-end fidelity.