Oligomeric ferrocene rings

Research output: Contribution to journalArticlepeer-review

Authors

  • Michael S. Inkpen
  • Stefan Scheerer
  • Michael Linseis
  • Andrew J. P. White
  • Rainer F. Winter
  • Nicholas J. Long

Colleges, School and Institutes

External organisations

  • Imperial College London

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 (∼107 s−1), these molecules can be considered as uniformly charged nanorings (diameter ∼1–2 nm).

Details

Original languageEnglish
Pages (from-to)825-830
JournalNature Chemistry
Volume8
Issue number9
Publication statusPublished - 27 Jun 2016