Synthesis and Late‐Stage Diversification of BN‐Embedded Dibenzocorannulenes as Efficient Fluorescence Organic Light‐Emitting Diode Emitters.

We report the synthesis and late-stage diversification of a new class of hetero-buckybowl, BN-embedded dibenzocorannulenes ( B 2 N 2 -DBC s). The synthesis is achieved via one-shot halogenative borylation, comprising the nitrogen-directed haloboration of alkyne and an intramolecular bora-Friedel–Crafts reaction, which provides BN-embedded dibenzocorannulene possessing two bromo substituents ( B 2 N 2 -DBC-Br ). B 2 N 2 -DBC-Br undergoes diversification via coupling reactions to provide a variety of arylated derivatives ( B 2 N 2 -DBC-R ), exhibiting strong blue fluorescence. An organic light-emitting diode (OLED) employing one of the derivatives as an emitter exhibited a high external quantum efficiency of 6.6% and long operational lifetime of 907 h at an initial luminance of 1000 cd m –2 , indicating the significant potential for the development of efficient and stable hetero-buckybowl-based OLED materials.