Simultaneously Enhanced Reverse Intersystem Crossing and Radiative Decay in Thermally Activated Delayed Fluorophors with Multiple Through‐space Charge Transfers

Thermally activated delayed fluorescence (TADF) materials with through-space charge transfers (CT) have attracted particularly interest recently. However, the slow reverse intersystem crossing (RISC) and radiative decay always limit their electroluminescence performances. Herein, TADF molecules with ortho-linked multiple donors-acceptor (ortho-D_n -A) motif are developed to create near-degenerate excited states for the reinforcement of spin-orbit coupling. The incorporation of both through-bond and through-space CT enlarges oscillator strength. The optimal ortho-D₃ -A compound exhibits a photoluminescence quantum yield of ca. 100 %, a high RISC rate of 2.57×10⁶ s^-1 and a high radiative decay rate of 1.00×10⁷ s^-1 simultaneously. With this compound as the sensitizer, a TADF-sensitized-fluorescent organic light-emitting diode shows a maximum external quantum efficiency of 31.6 % with an ultrapure green Commission Internationale de L'Eclairage y coordinate value of 0.69.