Achieving Submicrosecond Thermally Activated Delayed Fluorescence Lifetime and Highly Efficient Electroluminescence by Fine-Tuning of the Phenoxazine–Pyrimidine Structure

Thermally activated delayed fluorescence (TADF) materials, combining high fluorescence quantum efficiency and short delayed emission lifetime, are highly desirable for application in organic light-emitting diodes (OLEDs) with negligible external quantum efficiency (EQE) roll-off. Here, we present the pathway for shortening the TADF lifetime of highly emissive 4,6-bis­[4-(10-phenoxazinyl)­phenyl]­pyrimidine derivatives. Tiny manipulation of the molecular structure with methyl groups was applied to tune the singlet–triplet energy-level scheme and the corresponding coupling strengths, enabling the boost of the reverse intersystem crossing (rISC) rate (from 0.7 to 6.5) × 10⁶ s^–1 and shorten the TADF lifetime down to only 800 ns in toluene solutions. An almost identical TADF lifetime of roughly 860 ns was attained also in solid films for the compound with the most rapid TADF decay in toluene despite the presence of inevitable conformational disorder. Concomitantly, the boost of fluorescence quantum efficiency to near unity was achieved in solid films due to the weakened nonradiative decay. Exceptional EQE peak values of 26.3–29.1% together with adjustable emission wavelength in the range of 502–536 nm were achieved in TADF OLEDs. Reduction of EQE roll-off was demonstrated by lowering the TADF lifetime.