Sterically Tuned <i>Ortho</i>-Phenylene-Linked Donor–Acceptor Benzothiazole-Based Boron Difluoride Complexes as Thermally-Activated Delayed Fluorescence Emitters for Organic Light-Emitting Diodes

Two donor-acceptor dyes with an <i>ortho</i>-phenylene-linked carbazole electron donor and a benzothiazole-fused boron heterocyclic acceptor were designed, synthesized, and spectroscopically investigated. Due to the steric effects of boron heterocyclic units, the dyes demonstrate different conformations in the crystalline state. The presence of numerous hydrogen-bonding intermolecular interactions and the very weak π-π stacking in the molecular packing results in intense solid-state emission with photoluminescence quantum yields of 40 and 18% for crystals and 50 and 42% for host-based light-emitting layers. The compounds show aggregation-induced emission and thermally activated delayed fluorescence (TADF). The received ionization potential and electron affinity values suggested good charge-injecting ability and bipolar charge-transporting properties of the developed dyes. Transport of holes and electrons was detected in layers of one dye by the time-of-flight measurements. The benzothiazole-based boron difluoride complexes showed high electron mobility of 1.5 × 10^-4 and 0.7 × 10^-4 cm² V^-1 s^-1 at an electric field of 1.35 × 10⁶ V cm^-1. Therefore, these dyes were successfully applied as emitters in organic light-emitting diodes with external quantum efficiencies of 15 and 13%, respectively. Our study marks a critical advancement in the area of solid-state emissive boron difluoride dyes, which can be applied as TADF emitters into organic light-emitting diodes. The obtained results reveal that the orientation of the acceptor unit in the <i>ortho</i>-phenylene-linked donor-acceptor dyes makes a significant impact on the TADF activity.