Achieving Near‐Infrared Phosphorescence Supramolecular Hydrogel Based on Amphiphilic Bromonaphthalimide Pyridinium Hierarchical Assembly

Abstract Phosphorescent supramolecular hydrogels are currently a prevalent topic for their great promise in various photonic applications. Herein, an efficient near‐infrared (NIR) phosphorescence supramolecular hydrogel is reported via the hierarchical assembly strategy in aqueous solution, which is fabricated from amphiphilic bromonaphthalimide pyridinium derivative (G), exfoliated Laponite (LP) nanosheets, and polymeric polyacrylamide (PAAm). Initially, G spontaneously self‐aggregates into spherical nanoparticles covered with positively charged pyridinium units and emits single fluorescence at 410 nm. Driven by electrostatic interactions with negatively charged nanosheets, the nanoparticles subsequently function as the cross‐linked binders and coassemble with LP into supramolecular hydrogels with an engendered red room‐temperature phosphorescence (RTP) up to 620 nm. Benefiting from hydrogen‐bonding interactions‐mediated physical cross‐linkage, the further introduction of PAAm not only significantly elevates the mechanical strength of the hydrogels showing fast self‐healing capability, but also increases phosphorescence lifetime from 2.49 to 4.20 ms, especially generating phosphorescence at even higher temperature ( τ 363 K = 2.46 ms). Additionally, efficient RTP energy transfer occurs after doping a small amount of organic dye heptamethine cyanine (IR780) as an acceptor into hydrogels, resulting in a long‐lived NIR emission at 823 nm with a high donor/acceptor ratio, which is successfully applied for cell labeling in the NIR window.