Enhanced Singlet Oxygen Production in Supramolecular Artificial Light‐Harvesting System for Photooxidation of 4‐(Methylthio)toluene

An enhanced singlet oxygen ( 1 O 2 ) production artificial light‐harvesting systems (LHSs) was constructed by supramolecular assembly of water‐soluble pillar[5]arene (WP5) and naphthylhydroxyphenyl derivative (NHD). After WP5 and NHD binding to form WP5‐NHD amphiphiles, WP5‐NHD complex self‐assembled to WP5‐NHD nanoparticles, which exhibited significantly teal aggregation‐induced emission (AIE) fluorescence to serve as donors. By loading eosin Y (ESY) and sulforhodamine 101 (SR101) acceptors, two artificial LHSs of WP5‐NHD‐ESY and WP5‐NHD‐SR101 were constructed by Förster resonance energy transfer (FRET) process, whose energy transfer efficiency and antenna effect were 53.8%, 15.0 and 59.7%, 21.9, respectively. Notably, through the energy transfer in WP5‐NHD‐SR101, UV region solar energy was efficiently absorbed by WP5‐NHD and transferred to SR101 for enhancing 1 O 2 production. In order to mimic natural LHS's photocatalytic utilization, WP5‐NHD‐SR101 LHS was used as a clean‐green oxidant to catalyze the photooxidation of 4‐(methylthio)toluene to 4‐(methylsulfinyl)toluene, whose yield was significantly improved to 62%, showing potential in solar energy transfer and utilization.