Through-Space Charge-Transfer Emitters Developed by Fixing the Acceptor for High-Efficiency Thermally Activated Delayed Fluorescence

Through-space charge-transfer (TSCT) emitters have been extensively explored for thermally activated delayed fluorescence (TADF), but arranging various donors and acceptors into rigid cofacial conformations for various efficient TSCT TADF emitters has remained challenging. Here, we report a "fixing acceptor" design to reach various efficient TSCT TADF emitters. By chemically fixing the acceptor (benzophenone) with a rigid spiro-structure and cofacially aligning various donors with the fixed acceptor, a series of efficient TSCT TADF emitters have been developed. Single-crystal structures and theoretical calculations have verified closely packed cofacial donor/acceptor conformations and favorable TSCT in the emitters. In doped films, the emitters afford sky blue to yellow TADF emission, with high photoluminescence efficiencies up to 0.92 and reverse intersystem crossing rates up to 1.0 × 10⁶ s^-1. Organic light-emitting diodes using the emitters afford sky blue to yellow electroluminescence with high external quantum efficiencies up to 20.9%. The work opens a new avenue toward a wide variety of efficient TSCT TADF emitters.