Biomimetic Thermoresponsive Nanoassemblies With Three-Step Energy Funneling for Switchable ROS Generation and Photocatalysis.

Mimicking the adaptive light-energy management of natural photosynthetic systems remains challenging, particularly in aqueous media where efficient multistep energy transfer and environmental responsiveness are rarely integrated within a single nanoscale architecture. Herein, we report thermoresponsive biomimetic supramolecular nanoassemblies featuring three-step cascade Förster resonance energy transfer, constructed by coassembly of a minimalist amphiphilic aggregation-induced emission luminogen (TPEG) with eosin Y (ESY), Nile Red (NiR), and chlorin e6 (Ce6). The resulting hierarchical nanoassemblies enable efficient directional energy funneling and enhanced generation of reactive oxygen species (ROS), including 1O2 and O2 •-. Consequently, the harvested excitation energy is effectively converted into photochemical activity, promoting aerobic oxidative amidation and benzimidazole synthesis in water with yields up to 91% and 92%, respectively. Moreover, the lower critical solution temperature transition of the oligo(ethylene glycol) corona of TPEG provides a reversible mechanism for regulating supramolecular organization, energy flow, ROS generation, and photocatalytic activity, enabling thermally switchable photochemical outputs. This work establishes a biomimetic strategy for thermally adaptive light-energy management and controllable light-energy conversion, providing new opportunities for responsive artificial light-harvesting systems and functional supramolecular nanomaterials.