Binding of Sulfate-Terminated Surfactants with Different Alkyl Chain Lengths to Viologen Sites Covalently Embedded in the Interior of a Self-Assembled Monolayer on a Au Electrode.

We investigated the binding of anionic surfactants of lower concentrations than their critical micelle concentrations (cmcs) to the cationic redox-active viologen site in the interior of a self-assembled monolayer (SAM) on a polycrystalline Au electrode. We embedded the viologen site in the midway of the alkyl chain to facilitate the ion-pairing binding, which depends on the oxidation state of the viologen. We found that the binding of anionic surfactants and inorganic anions causes a negative shift of the formal potential of the redox couple of the viologen radical cation/viologen dication in line with the binding equilibrium. In contrast, the anion binding was weak and trivial when viologens are located at the SAM surface, indicative of the enhancement of the binding by the electrostatic interaction in the microenvironment with the low dielectric constant. The negative shift of the formal potential of viologen in the interior was greater for the surfactants with longer alkyl chain lengths, indicative of the efficacy of the alkyl chain-chain interaction. The chain-length-dependent potential shift followed the linear Traube rule but with a smaller slope than that in the original rule. We also demonstrated that the conjugated layer of the viologen SAM with dodecyl sulfate at a lower concentration than the cmc completely blocks the direct electron transfer (ET) from the Au electrode to solution-phase Fe(CN) 6 3- but allows mediated ET around the formal potential of the viologen.