A multi-resonance emitter with five-membered thiophene as the π-core enables efficient, narrowband and reduced efficiency roll-off OLEDs.

Efficient, narrowband multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters have recently sparked significant interest in high-resolution organic light-emitting diode (OLED) displays. However, almost all the progress in MR-TADF materials has been accomplished using a six-membered ring as the π-core to date. Herein, we present the first example of a five-membered ring π-core-based MR-TADF emitter named Th-BN developed by introducing thiophene instead of hexagonal benzene as the π-core. The introduction of thiophene significantly enhances intramolecular charge transfer intensity and the spin-orbit coupling matrix elements but does not change the intrinsic MR properties. As a result, Th-BN exhibits a narrowband green emission at 512 nm, with a high luminous efficiency of 97%, a narrow full-width at half maximum of 41 nm/0.20 eV, and a rapid reverse intersystem crossing rate of 18.7 × 10 s, which is 10 times higher than that of its benzenoid counterpart DtBuCzB. The corresponding green OLEDs based on Th-BN achieve excellent electroluminescence performance with an external quantum efficiency (EQE) of 34.6% and a reduced efficiency roll-off with an EQE of 26.8% at a high luminance of 1000 cd m.