Tetrazole and Oxadiazole Derivatives as Thermally Activated Delayed Fluorescence Emitters

Organic light‐emitting diodes (OLEDs) are promising lighting solutions for sustainability and energy efficiency. Incorporating thermally activated delayed fluorescence (TADF) molecules enables OLEDs to achieve internal quantum efficiency (IQE), in principle, up to 100 %; therefore, new classes of promising TADF emitters and modifications of existing ones are sought after. This study explores the TADF emission properties of six designed TADF emitters, examining their photophysical responses using experimental and theoretical methods. The design strategy involves creating six distinct types of a donor‐acceptor (D−A) system, where tert‐butylcarbazoles are used as donors, while the acceptor component incorporates three different functional groups: nitrile, tetrazole and oxadiazole, with varying electron‐withdrawing character. Additionally, the donor‐acceptor distance is adjusted using a phenylene spacer, and its influence on TADF functionality is examined. The clear dependency of an additional spacer, inhibiting TADF, could be revealed. Emitters with a direct donor‐acceptor connection are demonstrated to exhibit TADF moderate emissive behavior. The analysis emphasizes the impact of charge transfer, singlet‐triplet energy gaps (ΔEST), and other microscopic parameters on photophysical rates, permitting TADF. Among the emitters, TCz‐CN shows optimal performance as a blue‐green emitter with an 88 % photoluminescence quantum yield (PLQY) and fast rate of reversible intersystem crossing of 2×106 s−1 and 1×107 s−1, obtained from time‐resolved photoluminescence (TRPL) experiment in PMMA matrix and quantum mechanical calculations, respectively. This comprehensive exploration identifies molecular bases of superior TADF emitters and provides insights for future designs, advancing the optimization of TADF properties in OLEDs. This article explores the thermally activated delayed fluorescence (TADF) properties of six specially designed emitters for OLEDs, focusing on how structural variations like donor‐acceptor distances and functional groups influence TADF efficiency. One standout emitter, TCz‐CN, shows excellent performance as a blue‐green emitter, demonstrating the potential for optimizing OLED properties through precise molecular design.