CsPbBr₃ Perovskite Nanocrystals for Photocatalytic [3+2] Cycloaddition

Visible-light-induced halide-exchange between halide perovskite and organohalide solvents has been studied in which photoinduced electron transfer from CsPbBr₃ nanocrystals (NCs) to dihalomethane solvent molecules produces halide anions via reductive dissociation, followed by a spontaneous anion-exchange. Photogenerated holes in this process are less focused. Here, for CsPbBr₃ in dibromomethane (DBM), we discover that Br radical (Br⋅) is a key intermediate resulting from the hole oxidation. We successfully trapped Br⋅ with reported methods and found that Br⋅ is continuously generated in DBM under visible light irradiation, hence imperative for catalytic reaction design. Continuous Br⋅ formation within this halide-exchange process is active for photocatalytic [3+2] cycloaddition for vinylcyclopentane synthesis, a privileged scaffold in medicinal chemistry, with good yield and rationalized diastereoselectivity. The NC photocatalyst is highly recyclable due to Br-based self-healing, leading to a particularly economic and neat heterogeneous reaction where the solvent DBM also acts as a co-catalyst in perovskite photocatalysis. Halide perovskites, notable for efficient solar energy conversion, are demonstrated as exceptional photocatalysts for Br radical-mediated [3+2] cycloaddition. We envisage such perovskite-induced Br radical strategy may serve as a powerful chemical tool for developing valuable halogen radical-involved reactions.