Space‐Confined Donor‐Acceptor Strategy Enables Fast Spin‐Flip of Multiple Resonance Emitters for Suppressing Efficiency Roll‐Off

Multi-resonance boron-nitrogen-containing thermally activated delayed fluorescence (MR-TADF) emitters have experienced great success in assembling narrowband organic light-emitting diodes (OLEDs). However, the slow reverse intersystem crossing rate (kRISC ) of MR-emitters (103 -105 s-1 ) that will lead to severe device efficiency roll-off has received extensive attention and remains a challenging issue. Herein, we put forward a "space-confined donor-acceptor (SCDA)" strategy to accelerate RISC process. The introduction of SCDA units onto the MR-skeleton induces intermediate triplet states, which leads to a multichannel RISC process and thus increases kRISC . As illustrated examples, efficient MR-emitters have been developed with a sub-microsecond delayed lifetime and a high kRISC of 2.13×106 s-1 , which enables to assemble high-performance OLEDs with a maximum external quantum efficiency (EQEmax ) as high as 32.5 % and an alleviated efficiency roll-off (EQE1000 : 22.9 %).