Quantitative generation of cation radicals and dications using aromatic oxidants: effect of added electrolyte on the redox potentials of aromatic electron donors

Redox titrations using robust aromatic oxidants allow for a quantitative analysis of redox and optical properties of organic electron donors in their oxidized states. Unlike spectroelectrochemistry, redox titrations can be performed without added electrolyte in relatively nonpolar solvents, affording quick access to the redox and optical properties of a given electron donor without the need of a complex electrochemical setup. However, the redox potentials obtained by the two methods are not the same. To establish the direction and magnitude of this discrepancy, we have performed a systematic case study using a set of tetraarylethylene donors and a tetrasubstituted hydroquinone ether cation radical (^THEO^+?) as a stable aromatic oxidant. We show that redox potentials (especially second and higher oxidation potentials) measured by electrochemical methods are systematically lower compared with the redox potentials obtained by redox titrations in the absence of electrolyte, because of the enhanced stabilization of dications and polycations by electrolyte. We have also uncovered that the smaller cation radicals (e.g., a para‐hydroquinone or ortho‐hydroquinone ether cation radicals) are much more effectively stabilized when compared with the cation radicals in which charge is delocalized over larger area (e.g., tetraarylethylene cation radicals) in the presence of electrolyte because of increased ionic strength of the solution. Copyright © 2015 John Wiley & Sons, Ltd.