Perylene Diimide-Based Multicomponent Metallacages as Photosensitizers for Visible Light-Driven Photocatalytic Oxidation Reaction

Self-assembled supramolecular structures with efficient singlet oxygen (¹O₂)-generation ability are expected to enable photocatalytic oxidation reactions. Herein, we use two photosensitizers, perylene diimide and benzothiadiazole derivative, as the boards to prepare two barrel-shaped metallacages via metal-coordination-driven self-assembly. The integration of two photosensitizers takes advantage of Pt(II)-based coordination bonds to promote the intersystem crossing, offering the metallacages with high ¹O₂ generation efficiency (quantum yield up to 56%). The metallacages are further used to oxidize a series of alkenes. The yields of the photooxidation reaction exceed 90% when even 1 mol % metallacage is used. This study uses a type of metallacages for visible light-driven photocatalytic oxidation reactions, which will guide the future design and applications of metallacages toward photocatalysis.