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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...
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