Diphenyl viologen on an HOPG electrode surface: less sharp redox wave than dibenzyl viologen.

Redox behavior of diphenyl viologen (dPhV) on a basal plane of a highly oriented pyrolytic graphite (HOPG) electrode was described using the results of voltammetric and electroreflectance measurements. Its characteristics were compared to those of dibenzyl viologen (dBV), which undergoes the first-order faradaic phase transition. Unlike dBV, dPhV-dication (dPhV(2+)) was found to take a strongly adsorbed state on an HOPG surface. This is due to much stronger π-π interaction between phenyl rings of dPhV(2+) and HOPG surface than between benzyl groups of dBV(2+) and the surface. The participation of this strongly adsorbed dPhV(2+) in the redox process can be avoided by (1) a shorter than ∼3 min time period elapsing from touching a freshly cleaved HOPG surface to dPhV solution until the start of potential scan, (2) complete equilibration at the electrode potentials at which superficial dPhV molecules are fully reduced, or (3) multiple cyclic potential scanning to repeat oxidation-reduction of adsorbed species. Even in such conditions, although voltammograms of thin-layer electrochemistry for the surface-confined dPhV(•+)/dPhV(2+) couple are obtained with peak widths being as narrow as those of dBV, it is not the first-order phase transition. The participation of strongly adsorbed dPhV(2+) molecules results in another new voltammetric feature with a broader peak. The film formed by strongly adsorbed dPhV(2+) was hydrophilic, whereas dBV(2+) does not form such a film but only a gas-like layer. Measurements using X-ray photoelectron spectroscopy confirmed that the film consists of dPhV(2+) with coexistent water. These results reveal a typical case that delicate interaction balance among V(2+), V(•+), and electrode surface determines whether the two-dimensional first-order transition takes place or not.