One‐Pot Synthesis of Boron‐Doped Polycyclic Aromatic Hydrocarbons via 1,4‐Boron Migration

Abstract Herein, we demonstrate a novel one‐pot synthetic method towards a series of boron‐doped polycyclic aromatic hydrocarbons (B‐PAHs, 1 a – 1 o ), including hitherto unknown B‐doped zethrene derivatives, from ortho ‐aryl substituted diarylalkynes with high atom efficiency and broad substrate scopes. A reaction mechanism is proposed based on the experimental investigation together with the theoretical calculations, which involves a unique 1,4‐boron migration process. The resultant benchtop‐stable B‐PAHs are thoroughly investigated by X‐ray crystallography, cyclic voltammetry, UV/Vis absorption, and fluorescence spectroscopies. The blue and green organic light‐emitting diode (OLED) devices based on 1 f and 1 k are further fabricated, demonstrating the promising application potential of B‐PAHs in organic optoelectronics.