Abstract: | Aromatic difluoroboronated β‐diketone ( BF2DK ) derivatives are a widely known class of luminescent organic materials that exhibit high photoluminescent quantum efficiency and unique aggregation‐dependent fluorescence behavior. However, there have been only a few reports on their use in solid‐state electronic devices, such as organic light‐emitting devices (OLEDs). Herein, we investigated the solid‐state properties and OLED performance of a series of π‐extended BF2DK derivatives that have previously been shown to exhibit intense fluorescence in the solution state. The BF2DK derivatives formed exciplexes with a carbazole derivative and exhibited thermally activated delayed fluorescence (TADF) behavior to give orange electroluminescence with a peak external quantum efficiency of 10 % that apparently exceeds the theoretical efficiency limit of conventional fluorescent OLEDs (7.5 %), assuming a light out‐coupling factor of 30 %. |