LAUSR

Due to the limitations of common photoredox catalysts, unlocking their applications in photoreduction reactions remains an ongoing challenge. We herein present a supramolecular radical anion, PDI(CB[7])2, that formed by the assembly of perylene diimide derivative (PDI) and cucurbit[7]uril (CB[7]) via a host-guest interaction for an effective photoreduction reaction. Studies revealed that it could effectively accomplish a consecutive excitation process by two-photon excitation, enabling a potent photoreductant PDI(CB[7])2• - * that can even reduce the inert feedstocks, such as sulfoxides to sulfides. Mechanistic investigations indicate that, besides exceptional photophysical properties, supramolecular PDI(CB[7])2 also significantly enhances the lifetime and robustness of the in situ generated higher energy photoreductant PDI(CB[7])2• - * upon second quantum photon excitation, leading to the observed highly active photoreducing behavior.