Selective Anodic Desorption for Assembly of Different Thiol Monolayers on the Individual Electrodes of an Array

The close proximity of two individually addressable electrodes in an interdigitated array provides a unique platform for electrochemical study of multicatalytic processes. Here, we report a “plug-and-play” approach to control the underlying self-assembled monolayer and the electroactive species on each individually addressable electrode of an interdigitated array. The method presented here uses selective anodic desorption of a monolayer from one of the individually addressable electrodes and rapid formation of a different self-assembled monolayer on the freshly cleaned electrode. We illustrate this strategy by introducing variations in the length of the linker to the electroactive species in the self-assembled monolayer, which determines the rate of electron transfer. In order to separate the assembly of the monolayer from the choice of the electroactive species, we use Cu<sup>I</sup>-catalyzed triazole formation (“click” chemistry) to covalently attach an acetylene-terminated electroactive species to an azide-terminated thiol monolayer selectively on each electrode. The resulting variations in the electron-transfer rate to surface-attached ferrocene and in the rate of catalytic oxidation of ascorbate by the ferrocenium/ferrocene couple demonstrate an application of this approach.