Host–GuestApproach to Enhancing Photocatalysisvia Photoinduced Energy and Electron Transfer from a Photoactive Triphenylamine-BasedMetal–Organic Cage to Bound Guests

The host–guest strategy presents an ideal way to construct versatile supramolecular systems that mimic the structure and functionality of natural enzymes and, therefore, achieve efficient chemical conversions. An emissive triphenylamine-based cage-like host donor was constructed as an energy or electron donor to achieve efficient photoinduced energy or electron transfer (PEnT or PET) by encapsulating the energy or electron acceptor into the cavity of the cage. The host–guest complexes, which served as enzyme-mimicking supramolecular systems, were successfully used as photocatalysts for the selective aerobic oxidation of sulfides and the efficient photocatalytic reduction of aryl halides with high reduction potentials. This work details a promising approach for creating a host–guest system via a host–guest encapsulation strategy to enhance the efficiency of the PEnT or PET process. The resulting designed artificial supramolecular systems achieve efficient chemical conversions by mimicking the structure and functionality of natural enzymes.