Diazadimethano[8]circulene: Synthesis, structure, properties, and isolation of stable radical cation

Abstract

Hetero[8]circulenes have emerged as novel heteroatom-doped polycyclic aromatic hydrocarbons whose properties depend on the constituent aromatic units. Herein we report a C-doped variant, diazadimethano[8]circulene 3, in which two diphenylcyclopentadiene units are installed into the core of [8]circulene that may prevent effective conjugation. The structure of 3 has been revealed to have two longer C–C bonds in the central eight-membered ring, while the absorption and emission profiles are quite similar to those of tetraaza[8]circulene. Stable radical cation 3⁺ was easily obtained by facile oxidation of 3. X-ray diffraction analysis of 3⁺ showed a slipped dimer arrangement with negligible intermolecular interaction. Interestingly, the lowest-energy absorption of 3⁺ reaches around 2500 nm, while that of 3 is 447 nm.