Remote and Spatiotemporal Modulation of Supramolecular Self‐Assembly of Croconaine Dyes via NIR Laser Irradiation

Abstract Supramolecular polymerization holds great promise for the fabrication of well‐defined nanostructures. However, achieving precise spatiotemporal control over the dynamic assembly of supramolecular polymers using external stimuli remains a significant challenge. Here, we present a near‐infrared (NIR) laser irradiation strategy that exploits the intrinsic photothermal properties of croconaine‐based molecular building blocks to modulate the aggregation–dissociation equilibrium of seeds, thereby enabling the formation of supramolecular polymers and copolymers. Light irradiation provides enhanced tunability through adjustments in laser power, irradiation time, and wavelength. Notably, the spatial precision afforded by laser irradiation allows for localized seed dissociation, offering a new approach for spatially controlled supramolecular polymerization. This method also enables efficient light‐mediated gel formation, spatially selective sol–gel transitions, and healing in supramolecular organogels. These findings demonstrate a light‐responsive strategy for regulating supramolecular polymerization and open new avenues for constructing nanomaterials with programmable structures and functions.