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) 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 ( = 1.02-1.13) and high degree of chain-end fidelity. Furthermore, the giant two-photon absorption cross-section of CsPbBr enables activation with a light source in the near-infrared region (laser pulses centered at 800 nm) for the PET-RAFT process.