Highly Efficient Thermally Activated Delayed Fluorescence via J‐Aggregates with Strong Intermolecular Charge Transfer

The development of high-efficiency and low-cost organic emissive materials and devices is intrinsically limited by the energy-gap law and spin statistics, especially in the near-infrared (NIR) region. A novel design strategy is reported for realizing highly efficient thermally activated delayed fluorescence (TADF) materials via J-aggregates with strong intermolecular charge transfer (CT). Two organic donor-acceptor molecules with strong and planar acceptor are designed and synthesized, which can readily form J-aggregates with strong intermolecular CT in solid states and exhibit wide-tuning emissions from yellow to NIR. Experimental and theoretical investigations expose that the formation of such J-aggregates mixes Frenkel excitons and CT excitons, which not only contributes to a fast radiative decay rate and a slow nonradiative decay rate for achieving nearly unity photoluminescence efficiency in solid films, but significantly decreases the energy gap between the lowest singlet and triplet excited states (≈0.3 eV) to induce high-efficiency TADF even in the NIR region. These organic light-emitting diodes exhibit external quantum efficiencies of 15.8% for red emission and 14.1% for NIR emission, which represent the best result for NIR organic light-emitting diodes (OLEDs) based on TADF materials. These findings open a new avenue for the development of high-efficiency organic emissive materials and devices based on molecular aggregates.