How Do Redox Groups Behave around a Rigid Molecular Platform? Hexa(ferrocenylethynyl)benzenes and Their “Electrostatic” Redox Chemistry

A new family of hexakis(ferrocenylethynyl)benzenes was synthesized by Negishi coupling from ethynylferrocenes and C(6)Br(6) and can be reversibly oxidized to stable hexaferrocenium salts (see picture, Ar(F)=[3,5-C(6)H(3)(CF(3))(2)]). Their cyclic voltammograms show a single six-electron wave, three distinct two-electron waves, or a cascade of six single-electron waves, depending on the electrolyte counterion and number of methyl substituents on the ferrocenyl groups.