A spin-flip from a triplet to a singlet excited state, that is, reverse intersystem crossing (RISC), is an attractive route for improving light emission in organic light-emitting diodes, as shown by devices using thermally activated delayed fluorescence (TADF). However, device stability and efficiency roll-off remain challenging issues that originate from a slow RISC rate (kRISC). Here, we report a TADF molecule with multiple donor units that form charge-resonance-type hybrid triplet states leading to a small singlet–triplet energy splitting, large spin–orbit couplings, and a dense manifold of triplet states energetically close to the singlets. The kRISC in our TADF molecule is as fast as 1.5 × 107 s−1, a value some two orders of magnitude higher than typical TADF emitters. Organic light-emitting diodes based on this molecule exhibit good stability (estimated T90 about 600 h for 1,000 cd m−2), high maximum external quantum efficiency ('29.3%) and low efficiency roll-off ('2.3% at 1,000 cd m−2).
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