Dibenzodiazapyracylenes: Doubly N‐Doped Cyclopenta‐Fused Polycyclic Molecules That Exhibit High Carrier Mobility

Pyracylene is a unique cyclopenta‐fused polycyclic aromatic hydrocarbon (CP‐PAH) that exhibits dual aromatic characteristics. Herein we report the synthesis of doubly N‐doped benzannulated pyracylenes, namely dibenzodiazapyracylenes, by oxidative N−N linking reaction of [2.2](2,5)pyrrolophane‐type precursors. Dibenzodiazapyracylenes displayed well‐ordered π‐stacked molecular packing in the solid state, which were feasible for effective hole‐transporting along the stacking direction. High carrier mobility was estimated by microwave conductivity measurements as compared to dibenzoullazine. The high HOMO level of dibenzodiazapyracylene was verified by electrochemistry and its persistent radical cation species has been detected. A novel nitrogen‐doped CP‐PAH, dibenzodiazapyracylene, was successfully synthesized and characterized. The aromatic and antiaromatic resonance hybrid characters have been verified by comparing their 1H NMR spectra to those of reference molecules. Their condensed packing structures in the solid state allowed for the effective hole transporting.