High-efficiency blue thermally activated delayed fluorescence from donor–acceptor–donor systems via the through-space conjugation effect

The photophysical optimization of donor (D)–acceptor (A) molecules is a real challenge because of the intrinsic limitation of their charger transfer (CT) excited states. Herein, two D–A–D molecules featuring blue thermally activated delayed fluorescence (TADF) are developed, in which a homoconjugated acceptor 5,10-diphenyl-5,10-dihydrophosphanthrene oxide (DPDPO2A) is incorporated to bridge four carbazolyl or 3,6-di-t-butyl-carbazolyl groups for D–A interaction optimization without immoderate conjugation extension. It is shown that the through-space conjugation effect of DPDPO2A can efficiently enhance intramolecular CT (ICT) and simultaneously facilitate the uniform dispersion of the frontier molecular orbitals (FMO), which remarkably reduces the singlet–triplet splitting energy (ΔE(ST)) and increases FMO overlaps for radiation facilitation, resulting in the 4–6 fold increased rate constants of reverse intersystem crossing (RISC) and singlet radiation. The maximum external quantum efficiency beyond 20% and the state-of-the-art efficiency stability from sky-blue TADF OLEDs demonstrate the effectiveness of the “conjugation modulation” strategy for developing high-performance optoelectronic D–A systems.