Oligomerization‐Induced Supramolecular Glass with Superior Processability and Optical Functions

The fabrication of glasses, including silicate glasses, polymers, and amorphous metals, typically relies on the melting‐quenching technique. However, this approach faces significant challenges when applied to recently emerging molecular glasses due to the inherent thermal instability of small molecules. Herein, the discovery of a new supramolecular glass (BGG) is presented, formed by a unique melting‐quenching method that leverages unusual chemistry pathways. By manipulating the heating of a small molecule (benzoguanamine, BG), catalyst‐free self‐condensation reactions occur and produce multiple oligomers in a liquid state. The resulting high compositional and conformational entropy suppresses crystallization, allowing solidification into a rigid supramolecular glass under robust conditions. Despite being composed of low‐weight molecules, the extensive intermolecular interactions endow BGG with distinct aggregation‐induced emission (AIE, quantum yield up to 60%), polymer‐like Young's modulus (7.95 GPa), and superior glass transition temperature (100.1 °C). BGG's excellent processability is exemplified by the fabrication of thin films and fibers, showcasing potential applications in photovoltaics and photonic waveguides. BGG also serves as a platform for synthesizing diverse donor‐acceptor hybrids with > 95% energy transfer efficiency, enabling the creation of advanced materials with customizable functionalities.