Novel biferrocenyl complexes of s- and as-dihydroindacenes have been prepared and the charge transfer properties of their mono- and dicationic derivatives, selectively generated by one-electron and two-electron oxidation, have been investigated. Mixed-valence cations are generated by chemical oxidation using acetylferricinium as an oxidant agent and monitored in the visible, IR, and near-IR regions. The IT bands in the near-IR spectra are rationalized in the framework of Marcus Hush theory. The rigid and planar indacene platform bonded to two terminal redox groups displays a redox chemistry that can be switched from single two-electron transfers to two successive one-electron transfers by changing the supporting electrolyte from nBu(4)NPF(6) to nBu(4)NB(C(6)F(5))(4).
Single Two-Electron Transfers and Successive One-Electron Transfers in Biferrocenyl-Indacene Isomers
DONOLI, ALESSANDRO;BISELLO, ANNALISA;CARDENA, ROBERTA;CECCON, ALBERTO;SANTI, SAVERIO
2011
Abstract
Novel biferrocenyl complexes of s- and as-dihydroindacenes have been prepared and the charge transfer properties of their mono- and dicationic derivatives, selectively generated by one-electron and two-electron oxidation, have been investigated. Mixed-valence cations are generated by chemical oxidation using acetylferricinium as an oxidant agent and monitored in the visible, IR, and near-IR regions. The IT bands in the near-IR spectra are rationalized in the framework of Marcus Hush theory. The rigid and planar indacene platform bonded to two terminal redox groups displays a redox chemistry that can be switched from single two-electron transfers to two successive one-electron transfers by changing the supporting electrolyte from nBu(4)NPF(6) to nBu(4)NB(C(6)F(5))(4).
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