Cocrystallization‐Induced Red Ultralong Organic Phosphorescence

Organic cocrystals formed through multicomponent self-assembly have attracted significant interest owing to their clear structure and tunable optical properties. However, most cocrystal systems suffer from inefficient long-wavelength emission and low phosphorescence efficiency due to strong non-radiative processes governed by the energy gap law. Herein, an efficient long-lived red afterglow is achieved using a pyrene (Py) cocrystal system incorporating a second component (NPYC4) with thermally activated delayed fluorescence (TADF) and ultralong organic phosphorescence (UOP) properties. The cocrystal (NPYC4-Py) not only inherits the excellent luminescence of its monomeric counterparts, but also exhibits unique dual-mode characteristics, including persistent TADF and UOP emission with a high quantum yield of 58 % and a lifetime of 362 ms. The precise cocrystal stacking distinctly reveals that intermolecular interactions lock the cocrystal formation and weaken the intermolecular π-π interactions between NPYC4 and Py, thereby stabilizing the excited triplet excitons. Furthermore, the favorable energy level of NPYC4 acts as a bridge, reducing the energy gap between the S₁ and T₁ states for Py, therefore activating its red phosphorescence from Py. This research provides direct insights into achieving efficient red UOP through co-crystallization.