Triarylimidazole Redox Catalysts: Electrochemical Analysis and Empirical Correlations

A series of triarylimidazoles was synthesized and characterized electrochemically. The synthetic route is general, providing a pathway to 30 redox mediators that exhibit a > 700 mV range of accessible potentials. Most of the triarylimidazoles display three oxidation peaks where the first redox couple is quasi-reversible. The electronic character of the substituents affects the oxidation potential. This is exemplified by a linear correlation between the first oxidation potential and the sum of the Hammett sigma(+) substituent constants, as well as with a series of calculated ionization potentials. We close by putting forward a rule of thumb stating that for a given mediator, the upper limit of accessible potentials can be extended by at least 500 mV beyond the largest recorded value. A rationale, the conditions under which the rule is likely to apply, and an example are provided.