Mixed-Valence BN-Doped Corannulene Trimer Radical Cations

Mixed-valence (MV) dimers have been extensively investigated, however, the structure and properties of purely organic MV trimers based on open-shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN-doped corannulene radical cations [BN-Cor1]₃ ⋅⋅²⁺  ⋅ 2[BAryl^F ₄ ]^- and [BN-Cor2]₃ ⋅⋅²⁺  ⋅ 2[BAryl^F ₄ ]^- were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single-crystal X-ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BAryl^F ₄ ]^- anions, and three corannulene motifs [BN-Cor1]₃ ⋅⋅²⁺ and [BN-Cor2]₃ ⋅⋅²⁺ in the unit cell exhibit a trimer structure with a slipped π-stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self-assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of a forbidden transition (Δm_s =±2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π-trimers and the MV characteristic of these two species. Variable-temperature EPR and conductivity measurements suggested that the BN-doped π-trimers exhibited antiferromagnetic coupling and conductivity properties.