Guest‐Regulated Generation of Reactive Oxygen Species from Porphyrin‐Based Multicomponent Metallacages for Selective Photocatalysis

Abstract The development of novel materials for highly efficient and selective photocatalysis is crucial for their practical applications. Herein, we employ the host‐guest chemistry of porphyrin‐based metallacages to regulate the generation of reactive oxygen species and further use them for the selective photocatalytic oxidation of benzyl alcohols. Upon irradiation, the sole metallacage ( 6 ) can generate singlet oxygen ( 1 O 2 ) effectively via excited energy transfer, while its complex with C 70 ( 6 ⊃C 70 ) opens a pathway for electron transfer to promote the formation of superoxide anion (O 2 ⋅ − ), producing both 1 O 2 and O 2 ⋅ − . The addition of 4,4′‐bipyridine (BPY) to complex 6 ⊃C 70 forms a more stable complex ( 6 ⊃BPY) via the coordination of the Zn‐porphyrin faces of 6 and BPY, which drives fullerenes out of the cavities and restores the ability of 1 O 2 generation. Therefore, benzyl alcohols are oxidized into benzyl aldehydes upon irradiation in the presence of 6 or 6 ⊃BPY, while they are oxidized into benzoic acids when 6 ⊃C 70 is employed as the photosensitizing agent. This study demonstrates a highly efficient strategy that utilizes the host‐guest chemistry of metallacages to regulate the generation of reactive oxygen species for selective photooxidation reactions, which could promote the utilization of metallacages and their related host‐guest complexes for photocatalytic applications.