Multiple hydrogen bonding enables large-area doped phosphorescent glasses with robust stability and high-temperature afterglow

Molecular room-temperature phosphorescence (RTP) materials with compact and ordered structures organized by intermolecular interactions have proven to be a newly-emerged strategy for high-performance luminescence. However, typical crystalline materials exhibit intrinsic brittleness and compromised optical transparency due to their highly ordered packing, thereby restricting their applicability in diverse functional systems. Herein, a universal non-conjugated molecule (1,2,3,4-butane tetracarboxylic acid) with abundant hydrogen-bonding positions is introduced as a host matrix for supramolecular glasses (SGs) through a convenient evaporation-induced self-assembly procedure. A series of SGs doped with aromatic anhydride derivatives is fabricated, exhibiting highly efficient ultralong phosphorescence with afterglow up to 40 s and quantum yields of 56.8%. Experimental and computational studies show that the multiple hydrogen bonds synergistically facilitate glass formation by stabilizing disordered structures while establishing a rigid molecular matrix, which effectively suppressed non-radiative decay of triplet excitons. The doped SGs demonstrate largely enhanced phosphorescent performance, including high temperature afterglow up to 200 oC and robust tolerance in various extreme environments compared with crystal counterparts. Particularly, a large-scale fabrication (25 cm × 25 cm) and shaping capability that is unattainable by traditional crystals. This work thus offers significant potential of these SGs for advanced displays and anti-counterfeiting applications. Materials with room temperature phosphorescence have a range of potential applications, but when crystalline can be brittle and optically non-transparent. Here, the authors report the development of supramolecular glasses by evaporation-induced assembly, with high-temperature afterglow properties.