Precise Supramolecular Nanoarchitectonics for Simultaneous Enhanced Photoluminescence and Photocatalysis in a Co‐Assembly by a Biomimetic Isolation‐Conduction Strategy

Abstract Limited by the two mutually exclusive physicochemical processes of separation and recombination of photogenerated carriers, achieving photoluminescence and photocatalysis simultaneously is extremely challenging but essential for ever‐growing complex issues and specialized scenarios. Here we proposed a biomimetic isolation‐conduction strategy induced by an arene‐perfluoroarene (A−P) interaction for enabling photoluminescence and photocatalytic hydrogen evolution reaction (HER) activity in the co‐assembly of aromatic monomers and octafluoronapthalene ( OFN ). Inspired by the isolation‐conduction effect of periodic isolation of myelin sheaths on the axons of vertebrate nerve fibers by node of Ranvier, we use OFN as a molecular isolator embedded in the aromatic monomers array to block the singlet‐to‐triplet pathway, while the enlarged intermolecular dipoles resulting from the A−P interactions facilitate the conduction of photogenerated carriers in the isolated regions. The resultant co‐assembly exhibits an enhanced monomeric green emission compared to the corresponding monocomponent self‐assembly with weak red emission. Meanwhile, it also has an enhanced photocatalytic HER performance with a rate of 2.45 mmol g −1 h −1 , which is 15.2 times more than the self‐assembled one. On this basis, a sequential fluoric wastewater reuse system that includes real‐time fluorescence detection/removal of perfluorooctanoic acids and photocatalytic HER device is constructed.