Phosphine-Manipulated p-π and π-π Synergy Enables Efficient Ultralong Organic Room-Temperature Phosphorescence

Organic room temperature phosphorescence (RTP) attracts extensive attentions, but still faces the challenge of achieving both high RTP efficiencies (η_RTP ) and long lifetimes (τ_RTP ), due to the intrinsic contradiction between triplet radiation and stabilization. In this work, we developed three carbazole-triphenylphosphine hybrids named xCzTPP, in which phosphine groups provide nonbonding electrons and steric hindrance to modulate intermolecular p-π and π-π interactions. With the rational orientations and spatial positions of functional groups, para-substituted pCzTPP achieves high η_RTP over 10 % and more than twofold increased τ_RTP (>600 ms), compared to ortho- and meta- isomers. Theoretical simulation and photophysical investigation indicate that the strongest intermolecular p-π and π-π electronic interplays of pCzTPP harmonize high transition probability of ³ pπ state and triplet stability of ³ ππ state, reflecting the p-π and π-π synergy in RTP process.