Influence of the Phase State of Self-Assembling Redox Mediators on their Electrochemical Activity.

Self-assembling redox mediators have the potential to be broadly useful in a range of interfacial electrochemical contexts because the oxidation state and state of assembly of the mediator are closely coupled. In this paper, we report an investigation of the self-assembly of single- and double-tailed ferrocenyl amphiphiles (FTMA and BFDMA, respectively) at the surfaces of Pt electrodes and the impact of the dynamic assembled state of the amphiphiles on their rate of oxidation. We conclude that frozen aggregates of BFDMA adsorb to the surfaces of the Pt electrodes, and that slow dynamics of reorganization BFDMA within these aggregates limits the rate of electrooxidation of BFDMA. In contrast, FTMA, while forming assemblies on the surfaces of Pt electrodes, is characterized by fast reorganization dynamics and a corresponding rate of oxidation that is an order of magnitude greater than BFDMA.