Achieving pure room temperature phosphorescence (RTP) in phenoselenazine-based organic emitters through synergism among heavy atom effect, enhanced n → π* transitions and magnified electron coupling by the A-D-A molecular configuration.

The weak spin-orbit coupling (SOC) in metal-free organic molecules poses a challenge in achieving phosphorescence emission. To attain pure phosphorescence in RTP organic emitters, a promising molecular design concept has been proposed. This involves incorporating n → π* transitions and leveraging the heavy atomic effect within the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC) mechanism of bipolar molecules. Following this design concept, two bipolar metal-free organic molecules (PhSeB and PhSeDB) with donor-acceptor (D-A) and acceptor-donor-acceptor (A-D-A) configurations have been synthesized. When the molecular configuration changes from D-A to A-D-A, PhSeDB exhibits stronger electron coupling and n → π* transitions, which can further enhance the spin-orbit coupling (SOC) together with the heave atom effect from the selenium atom. By the advanced synergism among enhanced n → π* transitions, heavy atom effect and magnified electron coupling to efficiently promote phosphorescence emission, PhSeDB can achieve pure RTP emission in both the solution and doped solid film. Thanks to the higher spin-orbit coupling matrix elements (SOCMEs) for T 1 ↔ S 0 , PhSeDB attains the highest phosphorescence quantum yield ( ca. 0.78) among all the RTP organic emitters reported. Consequently, the purely organic phosphorescent light-emitting diodes (POPLEDs) based on PhSeDB achieve the highest external quantum efficiencies of 18.2% and luminance of 3000 cd m -2 . These encouraging results underscore the significant potential of this innovative molecular design concept for highly efficient POPLEDs.