Efficiently photocatalytic conversion of amine to imidine via perylene diimides supramolecules with oxygen vacancy

The utilization of photocatalytic oxidation technology for sustainable production of value-added chemicals has garnered significant attention. In the photocatalytic process, the transfer rate of photogenerated holes is considerably slower (2-3 orders of magnitude) than that of electrons. Consequently, the migration of photogenerated holes emerges as a critical bottleneck in achieving the efficient conversion of solar energy into valueadded chemicals. To address these challenges, we synthesized a perylene diimides supramolecule with abundant oxygen vacancies (R-Ov-PDI) to enhance holes transfer processes. Photogenerated holes were selectively captured by negatively charged defect sites, triggering an attack on the C-N bond. Noticeably, the catalyst exhibited a remarkable benzylamine oxidation efficiency (31.3 mmol.g(- 1).h(-1)) under visible light, with a selectivity for imine surpassing 99%. Furthermore, it demonstrated excellent substrate generality, outperforming most reported all -organic photocatalysts by 1-2 orders of magnitude. This study prove a novel perspective for the systematic design of efficient organic photocatalysts.