Lead Halide Perovskite Nanocrystals as Photocatalysts for PET-RAFT Polymerization under Visible and Near-Infrared Irradiation.

A key challenge of harvesting solar energy for chemical transformations is the scarcity of photocatalysts with broad activation wavelength and easily tunable band structures. Here, we introduce lead halide perovskite (CsPbBr 3 ) nanocrystals as band-edge-tunable photocatalysts for efficient photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. PET-RAFT polymerization of various functional monomers is successfully conducted using a broad range of irradiation sources ranging from blue to red light (460 to 635 nm), resulting in polymer products with narrow dispersity ( Đ = 1.02-1.13) and high degree of chain-end fidelity. Furthermore, the giant two-photon absorption cross-section of CsPbBr 3 enables activation with a light source in the near-infrared region (laser pulses centered at 800 nm) for the PET-RAFT process.