Accelerating Radiative Decay in Blue Through‐Space Charge Transfer Emitters by Minimizing the Face‐to‐Face Donor–Acceptor Distances

Thermally activated delayed fluorophors (TADF) featuring through-space charge transfers (TSCT) suffer from low radiative decay rates (kr s), especially for blue emitters. Here, a xanthene bridge is adopted to construct space-confined face-to-face donor-acceptor alignment and minimize their distances down to 2.7-2.8 Å, even shorter than the interlayer distance of graphite and thus strengthening the electronic interactions. The resulting blue TSCT-TADF emitters exhibit peaks around ≈460 nm, photoluminescence quantum yields of >90 %, and kr s of nearly 107 s-1 , almost 2-10 times higher than previously observed values with comparable reverse intersystem crossing rates. The corresponding blue organic light-emitting diodes show maximum external quantum efficiencies of 27.8 % and 34.7 % with Commission Internationale de L'Eclairage y coordinates of 0.29 and 0.15 using those molecules as emitters and sensitizers, respectively.