A Porphyrinic Donor-Acceptor Conjugated Porous Polymer as Highly Efficient Photocatalyst for PET-RAFT Polymerization.

Heterogeneous catalysts offer a highly desirable platform for exploring environmental-benign transformation systems, yet, they typically suffer from significant loss of catalytic efficiency compared with their homogeneous counterparts. Here, the facile synthesis of a porphyrinic conjugated porous polymer incorporated with imidazolium bromide moieties by taking advantage of the Debus-Radziszewski reaction is reported. Owing to the unique donor-acceptor structure, this heterogeneous and metal-free photocatalyst exhibits much improved catalytic activity compared with its small molecular analogs in photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, producing polymers with narrow distribution (Đ = 1.06-1.18) and high degree of chain-end fidelity. Moreover, the heterogeneous catalyst can be easily separated at the end of polymerization by centrifugation and recycled for five independent PET-RAFT polymerizations without obvious decreases in catalytic efficiency.