Excited state modulation in Donor-Substituted Multi-resonant Thermally Activated Delayed Fluorescence Emitters

Examples of multi-resonant thermally activated delayed fluorescence (MR-TADF) emitters that emit at longer wavelengths remain rare. To reach that goal, we decorate different numbers and types of electron-donors about a central MR-TADF core, DiKTa. Depending on the identity and number of donor groups, the excited state either remains short range charge transfer (SRCT) and thus characteristic of an MR-TADF emitter or becomes a long-range charge transfer (CT) that is typically observed in donor-acceptor TADF emitters. The impact is that in three examples, Cz-DiKTa, Cz-Ph-DiKTa and 3Cz -DiKTa, which emit from a SRCT state, the emission remains narrow, while in four examples, TMCz-DiKTa, DMAC-DiKTa, 3TMCz-DiKTa and 3DMAC-DiKTa, which emit via a CT state, the emission broadens significantly. Through this strategy, the organic light-emitting diodes fabricated with the three MR-TADF emitters show maximum electroluminescence emission wavelengths, EL, of 511, 492 and 547 nm with moderate full-width at half maxima (FWHM) of 62, 61 and 54 nm, respectively. Importantly, each of these devices show high maximum external quantum efficiencies (EQEmax) of 24.4%, 23.0% and 24.4%, which are amongst the highest reported with ketone-based MR-TADF emitters. OLEDs with D-A type emitters, DMAC-DiKTa and TMCz-DiKTa, also show high efficiencies, with EQEmax of 23.8% and 20.2%, but accompanied by broad emission at EL of 549 and 527 nm, respectively. Noteworthy is that the DMAC-DiKTa-based OLED shows very small efficiency roll-off, and its EQE remains 18.5% at 1000 cd m-2. Therefore, this work demonstrates that manipulating the nature and numbers of donor groups decorating a central MR-TADF core is a promising strategy for both red-shifting the emission and improving the performance of the OLEDs.