Achieving High‐Temperature Phosphorescence by Organic Cocrystal Engineering

Abstract Organic phosphors offer a promising alternative in optoelectronics, but their temperature‐sensitive feature has restricted their applications in high‐temperature scenarios, and the attainment of high‐temperature phosphorescence (HTP) is still challenging. Herein, a series of organic cocrystal phosphors are constructed by supramolecular assembly with an ultralong emission lifetime of up to 2.16 s. Intriguingly, remarkable stabilization of triplet excitons can also be realized at elevated temperature, and green phosphorescence is still exhibited in solid state even up to 150 °C. From special molecular packing within the crystal lattice, it has been observed that the orientation of isolated water cluster and well‐controlled molecular organization via multiple interactions can favor the structural rigidity of cocrystals more effectively to suppress the nonradiative transition, thus resulting in efficient room‐temperature phosphorescence and unprecedented survival of HTP.