Axially Chiral TADF‐Active Enantiomers Designed for Efficient Blue Circularly Polarized Electroluminescence

The use of a chiral, emitting skeleton for axially chiral enantiomers showing activity in thermally activated delayed fluorescence (TADF) with circularly polarized electroluminescence (CPEL) is proposed. A pair of chiral stable enantiomers, (?)‐(S)‐Cz‐Ax‐CN and (+)‐(R)‐Cz‐Ax‐CN, was designed and synthesized. The enantiomers, both exhibiting intramolecular π‐conjugated charge transfer (CT) and spatial CT, show TADF activities with a small singlet–triplet energy difference (ΔE_ST) of 0.029 eV and mirror‐image circularly polarized luminescence (CPL) activities with large g_lum values. Notably, CP‐OLEDs based on the enantiomers feature blue electroluminescence centered at 468 nm with external quantum efficiencies (EQEs) of 12.5 and 12.7 %, and also show intense CPEL with g_EL values of ?1.2×10^?2 and +1.4×10^?2, respectively. These are the first CP‐OLEDs based on TADF‐active enantiomers with efficient blue CPEL.