A theoretical study on the spectral and electrochemical properties of Ferrocene in different solvents

Ferrocene electronic spectra are calculated in solution with an original methodology. Results, in good agreement with experimental data, indicate that solvent nature does not heavily affect UV-spectra but is relevant for redox potential.Figure optionsDownload as PowerPoint slideHighlights
• The UV–Vis spectra of Ferrocene in different solvents have been calculated.
• The Ferrocene/Ferricinium couple redox potential in the same solvents.
• Change of the solvent only affect the redox potential.

A theoretical–computational study based on Molecular Dynamics simulations and Perturbed Matrix Method (MD–PMM) calculations was carried out for evaluating some properties of solvated Ferrocene including the UV–Vis spectrum and the redox potential. The results, in rather good agreement with the experimental values, display that Ferrocene low-lying excited states are scarcely affected by the change of solvent polarity. On the other hand, the Ferrocene/Ferricinum redox potential show a sharp, although not dramatic, dependency on the nature of the solvent essentially because of the sensitivity of the charged Ferricinium species to the solvent electric field fluctuation. The present study is the first one theoretically addressing, with the use of explicit solvent calculations, the Ferrocene UV spectrum and the Ferricinium/Ferrocene couple redox potential, a quantity proposed by the IUPAC Electrochemical Commission as reference electrode potential for non-aqueous solutions.