Hydrothermal Disturbance‐Driven Coordination Assembly of Supramolecular Glasses With Multi‐Excitation‐Tunable Afterglow

The bottom‐up fabrication of transparent bulk glasses remains a significant challenge, particularly due to decomposition of molecular components before melting. Supramolecular glasses (SMGs), built from non‐covalently cross‐linked networks with favorable optical properties, are generally inaccessible via conventional melt‐quenching. Solvent evaporation methods, in turn, tend to produce disordered powders rather than uniform macroscopic glassy solids. Here, we present a hydrothermal disturbance strategy to synthesize a family of structural water‐containing SMGs based on indium‐triazole coordination complexes. These monolithic SMGs display high transparency, mechanical robustness, and excitation‐dependent ultralong room‐temperature phosphorescence, with emission colors tunable from blue to yellow. These characteristics originate from dense metal–ligand coordination frameworks reinforced by hydrogen bonding. Doping with L ‐tyrosine further enhances the phosphorescent performance, yielding a prolonged blue afterglow (204.6 ms), while also introducing chiroptical functionality. This study thus establishes a new coordination‐driven strategy for SMG formation and introduces a class of multifunctional afterglow glasses with promising applications in UV sensing and secure optical encryption.