Pendant engineering in multiple-resonance thermally activated delayed fluorescence to yield charge-transfer and locally excited-state characteristics

Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials can exhibit narrow-spectrum characteristics owing to the inhibition of rotation within the molecules. However, the excited states of these MR-TADF materials, which influence the spin-orbit couplings (SOCs) and device efficiencies of organic light-emitting diodes (OLEDs), have not been investigated to date. In this study, we synthesized MR-TADF materials tDABNA-TP, tDABNA-DN, and tDABNA-DOB by incorporating characteristic neutral, donor, and acceptor pendants into 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (tDABNA). To determine the effect of pendant engineering, we investigated the excited states of the MR-TADF materials, including their singlet and triplet excited states, calculated the SOCs for their optimal reverse intersystem crossing pathways, and determined their maximum external quantum efficiencies (EQE_max) in OLEDs. The OLED with the emitter bearing the neutral pendant (tDABNA-TP) exhibited the highest EQE_max of 20.7% among those with the emitters bearing the donor (16.6%) and acceptor (12.4%) pendants, with a narrow emission range of 472-492 nm. Furthermore, the device with the tDABNA-TP emitter exhibited an operating lifetime of 196 h, which was 1.42- and 1.92-fold longer than those of the devices with the tDABNA-DN and tDABNA-DOB emitters, respectively. Our findings will promote research on the pendant engineering of MR-TADF-based OLEDs.