Electrochemistry of redox-active self-assembled monolayers

Amanda L. Eckermann, Daniel J. Feld, Justine A. Shaw, Thomas J. Meade*

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

476 Scopus citations


Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redox-activated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C60). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs.

Original languageEnglish (US)
Pages (from-to)1769-1802
Number of pages34
JournalCoordination Chemistry Reviews
Issue number15-16
StatePublished - Aug 2010


  • AC voltammetry
  • Chronoamperometry
  • Cyclic voltammetry
  • Electrochemical impedance spectroscopy
  • Electrochemistry
  • Electron transfer
  • Self-assembled monolayers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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