High‐Efficiency Solution‐Processable OLEDs by Employing Thermally Activated Delayed Fluorescence Emitters with Multiple Conversion Channels of Triplet Excitons

The state‐of‐the‐art luminescent materials are gained widely by utilizing thermally activated delayed fluorescence (TADF) mechanism. However, the feasible molecular designing strategy of fully exploiting triplet excitons to enhance TADF properties is still in demand. Herein, TADF emitters with multiple conversion channels of triplet excitons are designed by concisely halogenating the electron acceptors containing carbonyl moiety. Compared with the chlorinated and brominated analogues, the fluorinated emitter exhibits distinguishing molecular stacking structures, participating in the formation of trimers through integrating CH···F and C═O···H hydrogen bonds together. It is also demonstrated that the multiple channels can be involved synergistically to accelerate the spin‐flip of triplet excitons, and to take charge of the relatively superior reverse intersystem crossing constant rate of 6.20 × 105 s–1, and thus excellent photoluminescence quantum yields over 90% can easily be achieved. Then the solution‐processable organic light emitting diode based on fluorinated emitter can achieve a record‐high external quantum efficiency value of 27.13% and relatively low efficiency roll‐off with remaining 24.74% at 1000 cd m−2. This result manifests the significance of enhancing photophysical properties through constructing multiple conversion channels of triplets excitons for high‐efficiency TADF emitters and provides a guideline for the future study. The multiple conversion channels of triplet excitons are involved in fluorinated thermally activated delayed fluorescence emitters to accelerate the spin‐flip of triplet excitons and reverse intersystem crossing process. Eventually, the photoluminescence quantum yields can surpass over 90%, and the solution‐processable organic light emitting diodes can achieve a record‐high external quantum efficiency of 27.13% and relatively low efficiency roll‐off.