Dense Local Triplet States and Steric Shielding of a Multi‐Resonance TADF Emitter Enable High‐Performance Deep‐Blue OLEDs

Abstract Multi‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules based on boron and nitrogen atoms are emerging as next‐generation blue emitters for organic light‐emitting diodes (OLEDs) due to their narrow emission spectra and triplet harvesting properties. However, intermolecular aggregation stemming from the planar structure of typical MR‐TADF molecules that leads to concentration quenching and broadened spectra limits the utilization of the full potential of MR‐TADF emitters. Herein, a deep‐blue MR‐TADF emitter, pBP‐DABNA‐Me, is developed to suppress intermolecular interactions effectively. Furthermore, photophysical investigation and theoretical calculations reveal that adding biphenyl moieties to the core body creates dense local triplet states in the vicinity of S₁ and T₁ energetically, letting the emitter harvest excitons efficiently. OLEDs based on pBP‐DABNA‐Me show a high external quantum efficiency (EQE) of 23.4% and a pure‐blue emission with a Commission Internationale de L'Eclairage (CIE) coordinate of (0.132, 0.092), which are maintained even at a high doping concentration of 100 wt%. Furthermore, by incorporating a conventional TADF sensitizer, deep‐blue OLEDs with a CIE value of (0.133, 0.109) and an extremely high EQE of 30.1% are realized. These findings provide insight into design strategies for developing efficient deep‐blue MR‐TADF emitters with fast triplet upconversion and suppressed self‐aggregation.