Charge Transfer Excited State Promoted Multiple Resonance Delayed Fluorescence Emitter for High-Performance Narrowband Electroluminescence

Multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising candidates for narrowband organic light-emitting diodes, but their electroluminescent performance is typically hindered by the slow reverse intersystem crossing rate (k_RISC). Herein, we present an effective strategy to introduce a multichannel reverse intersystem crossing (RISC) pathway with large spin-orbit coupling by orthogonally linking an electron-donating unit to the MR framework. Through delicate manipulation of the excited-state energy levels, an additional intersegmental charge transfer triplet state could be "silently" induced without perturbing the MR character of the lowest excited singlet state. The proof-of-concept emitter CzBN3 not only affords 23-fold increase of k_RISC compared with its prototypical MR skeleton but also realizes close-to-unity photoluminescence quantum yield, large radiative rate constant, and very narrow emission spectrum. These merits enable high maximum external quantum efficiency (EQE_max) of up to 37.1% and alleviated efficiency roll-off in the sensitizer-free device (EQE₁₀₀₀ = 30.4%), and a further boost of efficiency (EQE_max/1000 = 42.3/34.1%) is realized in the hyperfluorescent device. The state-of-the-art electroluminescent performance validates the superiority of our molecular design strategy.