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