Dual Sulfone‐Bridged Triphenylamine Heteroaromatics for High‐Performance Blue Organic Electroluminescence

Abstract Polycyclic heteroaromatics (PHAs) are a highly versatile class of functional materials, especially applicable as efficient luminophores in organic light‐emitting diodes (OLEDs). Those constructed by tethered phenyl surrounding the main group center attract extensive attention due to their excellent OLED device performance. However, the development of such a class of emitters is often limited to boron, nitrogen‐doped π‐conjugated heterocycles. Herein, we proposed a novel kind of blue emitter by constructing a donor‐acceptor molecular configuration, utilizing a dual sulfone‐bridged triphenylamine (BTPO) core and mono/di‐diphenylamine (DPA) substituents. The twisted D−A molecular structures and appropriate donor strength facilitate the effective separation of natural transition orbitals, endowing the emitters with charge‐transfer dominant hybridized local and charge‐transfer characteristics for the excited states. Both BTPO‐DPA and BTPO‐2DPA own small S 1 –T 1 splitting energy, thus demonstrating blue thermally activated delayed fluorescence. The more symmetrical structure and enhanced CT features brought by additional DPA moiety confer BTPO‐2DPA with a shorter delayed fluorescence lifetime, a higher fluorescence quantum yield and narrower emission. Therefore, BTPO‐2DPA based OLED devices exhibit superior blue electroluminescence performance, with external quantum efficiencies reaching 12.31 %.