Highly Efficient Thermally Activated Delayed Fluorescence via an Unconjugated Donor–Acceptor System Realizing EQE of Over 30

In this work, two novel thermally activated delayed fluorescence (TADF) emitters, 2tDMG and 3tDMG, are synthesized for high‐efficiency organic light‐emitting diodes (OLEDs), The two emitters have a tilted face‐to‐face alignment of donor (D)/acceptor (A) units presenting intramolecular noncovalent interactions. The two TADF materials are deposited either by an evaporation‐process or by a solution‐process, both of them leading to high OLED performance. 2tDMG used as the emitter in evaporation‐processed OLEDs achieves a high external quantum efficiency (EQE) of 30.8% with a very flat efficiency roll‐off of 7% at 1000 cd m−2. The solution‐processed OLEDs also display an interesting EQE of 16.2%. 3tDMG shows improved solubility and solution processability as compared to 2tDMG, and thus a high EQE of 20.2% in solution‐processed OLEDs is recorded. The corresponding evaporation‐processed OLEDs also reach a reasonably high EQE of 26.3%. Encouragingly, this work provides a novel strategy to address the imperious demands for OLEDs with high EQE and low roll‐off. A thermally activated delayed fluorescence emitter, 2tDMG, is designed and synthesized based on the donor (D)/acceptor (A) spatially intramolecular noncovalent interaction. The D/A units are connected via a rigid linker, thereby confining them into a close‐packed coplanar configuration for small singlet–triplet splitting energy. 2tDMG achieves a high external quantum efficiency of 30.8% with a low efficiency roll‐off in evaporation‐processed organic light‐emitting diodes (OLEDs).