Exploring Robust Delayed Fluorescence Materials via Structural Rigidification for Realizing Organic Light‐Emitting Diodes with High Efficiencies and Small Roll‐Offs

Thermally activated delayed fluorescence (TADF) materials have been widely studied for the fabrication of high-performance organic light-emitting diodes (OLEDs), but the serious efficiency roll-offs still remain unsolved in most cases. Herein, it is wish to report a series of robust green TADF compounds containing rigid xanthenone acceptor and acridine-based spiro donors. The enhancement in molecular rigidity not only endows the compounds with improved thermal stability but also results in reduced geometric vibrations and thus lowered reorganization energies. These compounds exhibit distinct merits of high thermal stabilities, excellent photoluminescence quantum efficiencies (96%-97%), large horizontal dipole orientation ratios (87.4%-92.1%) and fast TADF rates (1.4-1.5 × 10⁶ s^-1 ). The OLEDs using them as emitters furnish superb electroluminescence performances with outstanding external quantum efficiencies (η_ext s) of up to 37.4% and very small efficiency roll-offs. Moreover, highly efficient hyperfluorescence OLEDs are obtained by using them as sensitizers for the green mutilresonance TADF emitter BN2, delivering excellent η_ext s of up to 34.2% and improved color purity. These results disclose the high potential of these TADF compounds as emitters and sensitizers for OLEDs.