Anthraquinone-based intramolecular charge-transfer compounds: computational molecular design, thermally activated delayed fluorescence, and highly efficient red electroluminescence.

Red fluorescent molecules suffer from large, non-radiative internal conversion rates (k(IC)) governed by the energy gap law. To design efficient red thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs), a large fluorescence rate (k(F)) as well as a small energy difference between the lowest singlet and triplet excited states (ΔE(ST)) is necessary. Herein, we demonstrated that increasing the distance between donor (D) and acceptor (A) in intramolecular-charge-transfer molecules is a promising strategy for simultaneously achieving small ΔE(ST) and large k(F). Four D-Ph-A-Ph-D-type molecules with an anthraquinone acceptor, phenyl (Ph) bridge, and various donors were designed, synthesized, and compared with corresponding D-A-D-type molecules. Yellow to red TADF was observed from all of them. The k(F) and ΔE(ST) values determined from the measurements of quantum yield and lifetime of the fluorescence and TADF components are in good agreement with those predicted by corrected time-dependent density functional theory and are approximatively proportional to the square of the cosine of the theoretical twisting angles between each subunit. However, the introduction of a Ph-bridge was found to enhance k(F) without increasing ΔE(ST). Molecular simulation revealed a twisting and stretching motion of the N-C bond in the D-A-type molecules, which is thought to lower ΔE(ST) and k(F) but raise k(IC), that was experimentally confirmed in both solution and doped film. OLEDs containing D-Ph-A-Ph-D-type molecules with diphenylamine and bis(4-biphenyl)amine donors demonstrated maximum external quantum efficiencies of 12.5% and 9.0% with emission peaks at 624 and 637 nm, respectively.