Tuning the redox profile of the 6,6′-biazulenic platform through functionalization along its molecular axis.

The E_1/2 potential associated with reduction of the linearly-functionalized 6,6′-biazulenic scaffold is accurately correlated to the combined σ_p Hammett parameters of the substituents over >600 mV range. X-ray crystallographic analysis of the 2,2′-dichloro-substituted derivative revealed unexpectedly short C–Cl bond distances, along with other metric changes, suggesting a non-trivial cycloheptafulvalene-like structural contribution. [ABSTRACT FROM AUTHOR]