Ultralong organic phosphorescence strongly depends on the formation of aggregation, while it is difficult to obtain in dilute environments on account of excessive internal and external molecular motions. Herein, ultralong single-molecule phosphorescence (USMP) at room temperature was achieved in the monomer state by coassembling biphenyl and naphthalene derivatives at low density with poly(vinyl alcohol) (PVA), where PVA provides a confined environment to stabilize the triplet state. Various factors that affect the USMP were studied, including aggregation, conformation, temperature, and moisture. In these systems, the formation of aggregates through intermolecular stacking and hydrogen bonding interactions in the film or crystal phases completely suppresses the USMP. However, the fluorescence is enhanced when coassembling these compounds at high concentration with PVA and becomes stronger in their powder state, indicating that the intersystem crossing process is blocked by the aggregation. Theoretical calculations suggest that the aggregation depresses spin-orbit coupling between the excited singlet and triplet states and enhances the nonradiative quenching process. Moreover, a relatively twisted conformation is more conducive to the occurrence of intersystem crossing than planar conformation. The USMP shows delicate and reversible sensitivity to the changes of temperature and moisture, rendering them with the applicability as smart organic optoelectronic materials.
Keywords: polymer matrix; reversible sensitivity; self-assembly; single-molecule phosphorescence; ultralong organic phosphorescence.