title: Activation energies for oxidation of porphyrin monolayers anchored to Au(111).
abstract: The activation energy for the oxidation of porphyrin monolayers anchored to gold surfaces is determined via measurement of the temperature dependence of the electron-transfer rates. The activation energy (1) increases with increasing surface concentration of the porphyrin and (2) is significantly lower (8.1-17 versus 37-49 kJ mol(-1)) when smaller, more mobile counterions (Cl(-) versus PF(6)(-)) are used as the supporting electrolyte. Regardless, the lower activation energies do not result in radically different electron-transfer rates for the different types of counterions owing to compensating entropic effects.
authors.affiliation: Department of Chemistry, University of California, Riverside, California 92521-0403, USA.
authors.forename: Jieying
authors.initials: J
authors.lastname: Jiao
authors.forename: Masahiko
authors.initials: M
authors.lastname: Taniguchi
authors.forename: Jonathan S
authors.initials: JS
authors.lastname: Lindsey
authors.forename: David F
authors.initials: DF
authors.lastname: Bocian