Photoexcitation-Induced Assembly: A Bottom-Up Physical Strategy for Driving Molecular Motion and Phase Evolution

CONSPECTUS: In the field of molecular assembly, photodriven self-assembly is a smart and crucial strategy to regulate the molecular orderliness, multiscale structure, and optoelectronic properties. Traditionally, photodriven self-assembly is based on photochemical processes, through molecular structural change induced by photoreactions. Despite great progress in the photochemical self-assembly, there still exists disadvantages (e.g., the photoconversion rate never reaches 100% with the possible side reactions). Therefore, the photoinduced nanostructure and morphology are often difficult to predict due to insufficient phase transition or defects. In contrast, the physical processes based on photoexcitation are straightforward and can fully utilize photons to avoid the drawbacks of photochemistry. The photoexcitation strategy excludes the change of molecular structure, only utilizing the molecular conformational change from the ground state to excited state. Then, the excited state conformation is employed to drive molecular movement and aggregation, further promoting the synergistic assembly or phase transition of the entire material system. The regulation and exploration of molecular assembly upon photoexcitation can open up a new paradigm to deal with the "bottom-up" behavior and develop unprecedented optoelectronic functional materials. This Account starts with a brief introduction to the problems faced by photocontrolled self-assembly and presents the photoexcitation-induced assembly (PEIA) strategy. Then, we focus on exploring PEIA strategy based on persulfurated arenes as the prototype. The molecular conformational transition of persulfurated arenes from the ground state to the excited state is conducive to the formation of intermolecular interactions, successively driving molecular motion, aggregation, and assembly. Next, we describe our progress in exploring PEIA of persulfurated arenes at the molecular level and then demonstrate that the PEIA of persulfurated arenes can synergistically drive molecular motion and phase transition in various block copolymer systems. Moreover, we provide the potential applications of PEIA in dynamic visual imaging, information encryption, and surface property regulation. Finally, an outlook on further development of PEIA is prospected.