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Temperature and Overpotential Dependence of Long‐Range Electron Transfer across a Self‐Assembled Monolayer with Pendant Ruthenium Redox Centers
Author(s) -
Finklea Harry O.,
Ravenscroft Melissa S.
Publication year - 1997
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199700022
Subject(s) - chemistry , overpotential , chronoamperometry , cyclic voltammetry , tafel equation , electron transfer , redox , monolayer , ruthenium , arrhenius equation , acetonitrile , inorganic chemistry , activation energy , photochemistry , electrochemistry , electrode , organic chemistry , catalysis , biochemistry
Mixed monolayers containing an electroactive thiol, HS(CH 2 ) 15 CONHCH 2 pyRu(NH 3 ) 5 2+/3+ , and a diluent thiol, HS(CH 2 ) 15 COOH, on gold electrodes are examined in acetonitrile electrolyte (0.1 M LiClO 4 ) 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.