Amorphization of Metal–Organic Crystals into a Supramolecular Framework Yields Hybrid Glasses with High Adhesive Strength

Untraditional glassy materials, including biomolecular glass, supramolecular glass, and metal–organic-framework (MOF)-derived glass, have attracted increasing attention due to their structural flexibility and promising biomedical and chemical engineering applications. Herein, we report a strategy for synthesizing a Zn-Im@BGG (zinc-imidazole@benzoguanamine glass) hybrid glass by integrating metal–organic coordination units into a supramolecular framework through a grinding-and-heating approach. The coordination crystals are formed in situ during the mechanochemical step, and subsequently amorphized upon heating, coalescing with the BGG supramolecular matrix into a homogeneous glassy state. Crucially, the metal–organic coordinating bond is retained postamorphization, and the BGG molecules become polarized by metal ions and establish hydrogen bonds with the ligands, resulting in an interconnected framework. The hybrid glass combines the structural features of both MOF and supramolecular frameworks, exhibiting exceptional adhesive strength on a variety of substrates (up to 3.41 MPa on glass), which surpasses many molecular adhesives of comparable or even higher molecular weight. This glassy material also demonstrates high optical transparency (>95%) and tunable fluorescence through Förster Resonance Energy Transfer. Its excellent processability is demonstrated through the successful fabrication of thin fibers and films, which have potential applications in optoelectronics and waveguides.