Regulation of Multiple Resonance Delayed Fluorescence via Through‐Space Charge Transfer Excited State towards High‐Efficiency and Stable Narrowband Electroluminescence.

B‐ and N‐embedded multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters usually suffer from slow reverse intersystem crossing (RISC) process and aggregation‐caused emission quenching. Here, we report the design of a sandwich structure by placing the B−N MR core between two electron‐donating moieties, inducing through‐space charge transfer (TSCT) states. The proper adjusting of the energy levels brings about a 10‐fold higher RISC rate in comparison with the parent B−N molecule. In the meantime, a high photoluminescence quantum yield of 91 % and a good color purity were maintained. Organic light‐emitting diodes based on the new MR emitter achieved a maximum external quantum efficiency of 31.7 % and small roll‐offs at high brightness. High device efficiencies were also obtained for a wide range of doping concentrations of up to 20 wt % thanks to the steric shielding of the B−N core. A good operational stability with LT95 of 85.2 h has also been revealed. The dual steric and electronic effects resulting from the introduction of a TSCT state offer an effective molecular design to address the critical challenges of MR‐TADF emitters. [ABSTRACT FROM AUTHOR]