Rational Molecular Design of Highly Efficient Yellow-Red Thermally Activated Delayed Fluorescent Emitters: A Combined Effect of Auxiliary Fluorine and Rigidified Acceptor Unit

Molecular design strategies are crucial to develop highly efficient and long-wavelength thermally activated delayed fluorescent (TADF) emitters because the inherent limitation of the energy gap law degrades the efficiency of the red or orange TADF emitters. To resolve the low efficiency issue, we designed and synthesized two TADF emitters, 4,4'-(6-(9,9-dimethylacridin-10(9H)-yl)-7-fluoroquinoxaline-2,3-diyl)dibenzonitrile (FDQCNAc) and 11-(9,9-dimethylacridin-10(9H)-yl)-12-fluorodibenzo[a,c]phenazine-3,6-dicarbonitrile (FBPCNAc), by utilizing fluorine and peripheral cyano-substituted quinoxaline and phenazine acceptors of 4,4'-(6-fluoroquinoxaline-2,3-diyl)dibenzonitrile (FDQCN) and 11-fluorodibenzo[a,c]phenazine-3,6-dicarbonitrile (FBPCN), respectively. A fluorine atom at the ortho position of the acridine donor acts as an auxiliary acceptor to minimize the singlet-triplet energy gap (ΔE_ST) below 0.1 eV and promotes the reverse intersystem crossing (RISC) process. Organic light-emitting diodes (OLEDs) fabricated with FDQCNAc and FBPCNAc emitters demonstrated high external quantum efficiencies (EQEs) of 27.6 and 23.8% in the yellow-red TADF OLEDs, respectively. In particular, the combination of the F auxiliary acceptor unit and the rigidified FBPCN acceptor unit enabled red-shifted emission by about 58 nm without much sacrifice of the EQE in the red region.