Developing pure organic materials with ultralong lifetimes is attractive but challenging. Here we report a concise chemical approach to regulate the electronic configuration for phosphorescence enhancement. After the introduction of d-pπ bonds into a phenothiazine model system, a phosphorescence lifetime enhancement of up to 19 times was observed for DOPPMO, compared to the reference PPMO. A record phosphorescence lifetime of up to 876 ms was obtained in phosphorescent phenothiazine. Theoretical calculations and single-crystal analysis reveal that the d-pπ bond not only reduces the (n, π*) proportion of the T1 state, but also endows the rigid molecular environment with multiple intermolecular interactions, thus enabling long-lived phosphorescence. This finding makes a valuable contribution to the prolongation of phosphorescence lifetimes and the extension of the scope of phosphorescent materials.
Keywords: crystal engineering; d-pπ bonds; excited states; organic phosphorescence; phenothiazines.
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