Syntheses and Physical Properties of Cationic BN-Embedded Polycyclic Aromatic Hydrocarbons

Cationic BN-embedded polycyclic aromatic hydrocarbons (BN-PAH⁺ s) were synthesized from a nitrogen-containing macrocycle via pyridine-directed tandem C-H borylation. Incorporating BN into PAH⁺ resulted in a remarkable hypsochromic shift due to an increase in the LUMO energy and the symmetry changes of the HOMO and LUMO. Electrophilic substitution or anion exchange of BN-PAH⁺ possessing tetrabromoborate as a counter anion (BN⁺ [BBr₄ ^- ]) afforded air-stable BN-PAH/PAH⁺ s. Of these, BN⁺ [TfO^- ] allowed reversible two-electron reduction and the formation of two-dimensional brickwork-type π-electronic ion pair with 1,2,3,4,5-pentacyanocyclopentadienyl anion, demonstrating the potential application of BN-PAH⁺ as electronic materials.