Intramolecular Electron Transfer between Terminal 1,4‐Dimethoxybenzene Units in Radical Cations with a [2.2](1,4)Naphthalenophane, [2.2](1,4)Anthracenophane, and Pentacene Skeleton

Various radical cations, in which two terminal 1,4-dimethoxybenzene units are anellated to [2.2]paracyclophane (2b•+, 3b•+), [2.2](1,4)naphthalenophane (4d•+), and anthracene bridges (5•+), have been studied by ESR and ENDOR spectroscopy. In the syn- and anti-naphthalenophane radical cations 2b•+ and 3b•+ the delocalization of the unpaired electron over both π-moieties and the distinct difference between the first and second oxidation potentials, ΔE = E20 – E10, are evidence for a substantial intramolecular electronic interaction between the two electrophores. Extension of the bridge in 4d•+ and 5 by benzo anellation results in a localized radical cation. Strong intramolecular electronic interaction between the two electrophores is found in the 1,4,8,11-tetramethoxy-pentacene radical cation (5•+). The syntheses of 4d are described.