Phototriggered Aggregation‐Induced Emission and Direct Generation of 4D Soft Patterns

Abstract Microscopic control of macroscopic phenomena is one of the core subjects in materials science. Particularly, the spatio‐temporal control of material behaviors through a non‐contact way is of fundamental importance but is difficult to accomplish. Herein, a strategy to realize remote spatio‐temporal control of luminescence behaviors is reported. A multi‐arm salicylaldehyde benzoylhydrazone‐based aggregation‐induced emission luminogen (AIEgen)/metal‐ion system, of which the fluorescence can be gated by the UV irradiation with time dependency, is developed. By changing the metal‐ion species, the fluorescence emission and the intensity can also be tuned. The mechanism of the UV‐mediated fluorescence change is investigated, and it is revealed that a phototriggered aggregation‐induced emission (PTAIE) process contributes to the behaviors. The AIEgen is further covalently integrated into a polymeric network and the formed gel/metal‐ion system can achieve laser‐mediated mask‐free writing enabled by the PTAIE process. Moreover, by further taking advantage of the time‐dependent self‐healing property of hydrazone‐based dynamic covalent bond, transformable 4D soft patterns are generated. The findings and the strategy increase the ways to manipulate molecules on the supramolecule or aggregate level. They also show opportunities for the development of controllable smart materials and expand the scope of the materials in advanced optoelectronic applications.