Evidence and mechanism of efficient thermally activated delayed fluorescence promoted by delocalized excited states

The design of organic compounds with nearly no gap between the first excited singlet (S(1)) and triplet (T(1)) states has been demonstrated to result in an efficient spin-flip transition from the T(1) to S(1) state, that is, reverse intersystem crossing (RISC), and facilitate light emission as thermally activated delayed fluorescence (TADF). However, many TADF molecules have shown that a relatively appreciable energy difference between the S(1) and T(1) states (~0.2 eV) could also result in a high RISC rate. We revealed from a comprehensive study of optical properties of TADF molecules that the formation of delocalized states is the key to efficient RISC and identified a chemical template for these materials. In addition, simple structural confinement further enhances RISC by suppressing structural relaxation in the triplet states. Our findings aid in designing advanced organic molecules with a high rate of RISC and, thus, achieving the maximum theoretical electroluminescence efficiency in organic light-emitting diodes.