Internally BN‐Doped Coronene

Abstract We present the first synthesis of internally BN‐doped coronenes ( B2N2‐C , H‐B2N2‐C , and 2H‐B2N2‐C ) with two covalent B─N units embedded on the central axis of coronene. The B─N doping leads to unique electronic structures with distinct charge distribution, conjugation, aromaticity, and photophysical properties. The structures were successfully identified by the single‐crystal X‐ray scattering. B2N2‐C without sidechains retains the structure of coronene but exhibits stronger π–π stacking, higher electronic coupling, and a narrowed solid‐state bandgap. Driven by the B─N dipole–dipole interaction, all B2N2‐coronene derivatives exhibit more ordered assembly with excimer emission in solution, which is absent in coronene. Notably, two stable polymorphs emerge in single crystals of 2H‐B2N2‐C with two hexyl chains: a kinetically stable rod phase and a thermodynamically stable plate phase, where variations in processing conditions direct the formation of different phases.