Elucidating the Crystallization‐Caused Phosphorescence Quenching Mechanism to Achieve Efficient Photoactivated Persistent Luminescence for High‐Quality Light Printing

Abstract The development of polymer‐based luminescent materials with efficient photoactivated ultralong organic phosphorescence (UOP) is of great importance but very challenging. Herein, a new class of organic phosphorescent luminogens is constructed by attaching phenyl rings and/or ethyl benzoates to the nitrogen atoms of a planar aromatic heterocycle pyrrolodiindole (PDI). The compounds show a significant elevation in phosphorescence emission capability after incorporating the ester group(s). However, they cannot produce room‐temperature phosphorescence in the crystalline state. These observations are identified to be associated with the formation of dimers and excimers and the motions of substituents within the molecules. In this context, the PDI derivatives are doped into epoxy polymers with compact and permanent 3D covalent networks. The resulting polymer films show reversible photoactivated UOP under ambient conditions, with quantum yields and lifetimes of up to 24.4% and 2.03 s, respectively, thereby enabling high‐quality and erasable light printing and multi‐level anti‐counterfeiting applications. In addition, they also exhibit excellent water and chemical resistance. This work is conducive to understanding the generation and decay mechanisms of the triplet excitons of organic luminophores with planar aromatic heterocycles in the crystalline state and provides a direction for the development of high‐performance photoactivated UOP materials.