Heterogeneous organophotocatalytic HBr oxidation coupled with oxygen reduction for boosting bromination of arenes

Developing mild photocatalytic bromination strategies using sustainable bromo source has been attracting intense interests, but there is still much room for improvement. Full utilization of redox centers of photocatalysts for efficient generation of Br⁺ species is the key. Herein we report heterogenous organophotocatalytic HBr oxidation coupled with oxygen reduction to furnish Br₂ and H₂O₂ for effective bromination of arenes over Al₂O₃ supported perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). Mechanism studies suggest that O-vacancy in Al₂O₃ can provide Lewis-acid-type anchoring sites for O₂, enabling unexpected dual-electron transfer from anchored photoexcited PTCDA to chemically bound O₂ to produce H₂O₂. The in-situ generated H₂O₂ and Br₂ over redox centers work together to generate HBrO for bromination of arenes. This work provides new insights that heterogenization of organophotocatalysts can not only help to improve their stability and recyclability, but also endow them with the ability to trigger unusual reaction mode via cooperative catalysis with supports. © The Author(s) 2024.