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The temperature dependence on the electron transfer rate constant (k app ) for hydroquinone redox center in H 2 Q(CH 2 ) n SH-SAMs (n = 1, 4, 6, 8, 10, and 12) on gold electrode was investigated to obtain reorganization energy (λ) using Laviron's formalism and Arrhenius plot of In [k app /T 1/2 ] vs. T -1 based on the Marcus density-of-states model. All the symmetry factors measured for the SAMs were relatively close to unity and rarely varied to temperature change as expected. The electron tunneling constant (β) determined from the dependence of the k app on the distance between the redox center and the electrode surface gives almost the same β values which are quite insensitive to temperature change. Good linear relationship of Arrhenius plot for all H 2 Q(CH 2 ) n SH-SAMs on gold electrode was obtained in the temperature range from 273 to 328 K. The slopes in Arrhenius plot deduced that λ of hydroquinone moiety is ca. 1.3-1.4 eV irrespectively of alkyl chain length of the electroactive SAM.

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Determination of Reorganization Energy from the Temperature Dependence of Electron Transfer Rate Constant for Hydroquinone-tethered Self-assembled Monolayers (SAMs)