Boron, sulfur-doped polycyclic aromatic hydrocarbon emitters with multiple-resonance-dominated lowest excited states for efficient narrowband deep-blue emission

Different from boron, nitrogen-based multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters, boron (B), sulfur (S)-doped polycyclic aromatic hydrocarbons (PAHs) containing 5,9-dithia-13b-boranaphtho[3,2,1-de]anthracene (BSS) skeleton and arylamine moieties in para-positions of boron atoms are developed as a novel kind of MR-TADF emitters for narrowband deep-blue electroluminescence. The molecular design not only utilizes heavy-atom effect of sulfur atoms in BSS skeleton to enhance spin-orbital coupling and promote reverse intersystem crossing, but also uses arylamines as peripheral substituents to modify excited state characteristics. By decreasing electron-donating ability and downshifting HOMO level of arylamines, the lowest excited state for resultant emitter is converted from intersegmental charge transfer state to multiple resonance state localized on BSS skeleton, leading to blue-shifted and narrowed emissions. The B,S-doped PAH emitter bearing carbazole moiety exhibits deep-blue electroluminecence with full-width at half maximum of 29 nm, Commission Internationale de l'Éclairage color coordinates of (0.13, 0.09), and the maximum external quantum efficiency of 21.8 %, representing a new approach toward efficient narrowband deep-blue emission beyond boron, nitrogen-based MR-TADF emitters.