Temperature and Overpotential Dependence of Long‐Range Electron Transfer across a Self‐Assembled Monolayer with Pendant Ruthenium Redox Centers

Mixed monolayers containing an electroactive thiol, HS(CH2)15CONHCH2pyRu(NH3)52+/3+, and a diluent thiol, HS(CH2)15COOH, on gold electrodes are examined in acetonitrile electrolyte (0.1 M LiClO4) as a function of overpotential and temperature. Kinetic and thermodynamic parameters from ca. −45 to +20 °C are obtained by cyclic voltammetry and chronoamperometry. Reorganization energies obtained from Tafel plots and Arrhenius plots both yield a reorganization energy of 0.8 eV for the redox centers.