Here, a facile and selective synthesis method for cationic azatriphenylene derivatives was established by electrochemical intramolecular cyclization, where atom-economical C-H pyridination without a transition-metal catalyst or an oxidant is a key step. The proposed protocol is a practical strategy for the late-stage introduction of cationic nitrogen () into π-electron systems and broadens the scope of molecular design of -doped polycyclic aromatic hydrocarbons.
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