Efficient Photoredox Cycles to Control Perylenediimide Self‐Assembly

Photoreduction of perylenediimide (PDI) derivatives has been widely studied for use in photocatalysis, hydrogen evolution, photo‐responsive gels, and organic semiconductors. Upon light irradiation, the radical anion (PDI⋅−) can readily be obtained, whereas further reduction to the dianion (PDI2−) is rare. Here we show that full 2‐electron photoreduction can be achieved using UVC light: 1) in anaerobic conditions by ‘direct photoreduction’ of PDI aggregates, or 2) by ‘indirect photoreduction’ in aerobic conditions due to acetone ketyl radicals. The latter strategy is also efficient for other dyes, such as naphthalenediimide (NDI) and methylviologen (MV2+). Efficient photoreduction on the minute time‐scale using simple LED light in aerobic conditions is attractive for use in dissipative light‐driven systems and materials. Photoreduction can be used to disassemble perylenediimide‐based supramolecular structures by creating repulsive dianions. Typically, photoreductions are done in oxygen‐free conditions. Here we show that ‘indirect photoreduction’ by acetone ketyl radicals is very efficient and can be done in open air. Repeated photoreduction/disassembly followed by oxidation/assembly cycles can in this way be performed by simple UV−C LED light.