Heteroatom‐Doped Carbon Dots (CDs) as a Class of Metal‐Free Photocatalysts for PET‐RAFT Polymerization under Visible Light and Sunlight

A key challenge of photoregulated living radical polymerization is developing efficient and robust photocatalysts. Now carbon dots (CDs) have been exploited for the first time as metal-free photocatalysts for visible-light-regulated reversible addition-fragmentation chain-transfer (RAFT) polymerization. Screening of diverse heteroatom-doped CDs suggested that the P- and S-doped CDs were effective photocatalysts for RAFT polymerization under mild visible light following a photoinduced electron transfer (PET) involved oxidative quenching mechanism. PET-RAFT polymerization of various monomers with temporal control, narrow dispersity (Đ≈1.04), and chain-end fidelity was achieved. Besides, it was demonstrated that the CD-catalyzed PET-RAFT polymerization was effectively performed under natural solar irradiation.