D-A Type Perylene Micelles With Synergistic Charge/Energy Transfer for Dual-Path ROS Generation and Enhanced Photocatalysis.

Efficient generation of reactive oxygen species (ROS) through synergistic regulation of charge transfer (CT) and energy transfer (ET) pathways is key to enhancing photocatalytic reaction rates. Nevertheless, simultaneously optimizing both singlet (S1) and triplet (T1) exciton utilization to maximize ROS generation and its subsequent effective exploitation remains challenging. Herein, a series of amphiphilic perylene-based nanomicelles is designed via donor engineering, in which spatial coupling between dual-path ROS generation and pollutant oxidation is achieved. Experiments and theoretical calculations certify that the micelle with triphenylamine as the donor can boost the CT efficiency of S1 to engender superoxide radical (•O2 -) production, while concurrently improving the intersystem crossing (ISC) efficacy from S1 to T1 to prolong the T1 lifetime and activate the ET process for singlet oxygen (1O2) yielding. Additionally, the pre-enrichment of pollutants by micelles shortens the migration distance of ROS and extends their lifetime, thereby maximizing the directed utilization efficiency of ROS. The strategy that combines photophysical properties with structural optimization, successfully surmounts the confinements of organic photocatalytic materials in solar-driven chemical reactions.