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.