Recognition of “Oxygen-/Water-Fueled” PET-RAFT Protocol Matched to Covalent Organic Frameworks

The reactive oxygen species (ROS)-mediated photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) process is an attractive tool to enhance the oxygen tolerance of radical polymerization systems. In this paper, we investigate the relationship between the covalent organic framework (COF) structure and polymerization performance based on the O2 •–/H2O system by modulating the COF at atomic and molecular levels. We combine density functional theory (DFT) calculations and experiments to clarify the “oxygen-/water-fueled” PET-RAFT polymerization mechanism and identify the key steps of the protocol. Based on the modulation of the TD-1 COF template structure, the relatively efficient charge–hole separation efficiency allows the matching of TD-2 COF and TD-3 COF with the O2 •–/H2O system to achieve high-quality RAFT polymerization, providing insights into the rational design and development of catalytic systems with better performance.