title: Oligomeric ferrocene rings.
abstract: Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category-differently sized rings comprising only 1,1'-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e(-) waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼10(7) s(-1)), these molecules can be considered as uniformly charged nanorings (diameter ∼1-2 nm).
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Michael S
authors.identifier: 0000-0001-7339-8812
authors.initials: MS
authors.lastname: Inkpen
authors.affiliation: Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78457 Konstanz, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Scheerer
authors.affiliation: Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78457 Konstanz, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Linseis
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.affiliation: Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78457 Konstanz, Germany.
authors.forename: Rainer F
authors.initials: RF
authors.lastname: Winter
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Tim
authors.identifier: 0000-0001-6085-3206
authors.initials: T
authors.lastname: Albrecht
authors.affiliation: Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
authors.forename: Nicholas J
authors.identifier: 0000-0002-8298-938X
authors.initials: NJ
authors.lastname: Long