Journal of Physical Chemistry B, Vol.103, No.21, 4440-4446, 1999
Mediated electrocatalysis with polyanthraquinone-functionalized monolayer-protected clusters
This paper describes the reduction of 1,1-dinitrocyclohexane by electrogenerated anthraquinone radical anions that are ligated to monolayer-protected gold clusters. Each cluster bears multiple (ca. 18) anthraquinone units. The clusters are prepared by place-exchange of a fraction of the cluster's original octanethiolate ligands with 1-(1,3-dithiapropyl)anthracene-9,10-dione. The electrocatalytic reduction currents are compared to those observed for anthraquinone monomer at an equivalent concentration. The electrocatalytic efficiency is larger for cluster-bound anthraquinone. The results are analyzed by digital simulation and by a discrete mathematical approach so as to determine the rate constant for electron transfer between the substrate and anthraquinone radical anion (cluster-bound and free). The rate constant is slightly larger for the free anthraquinone monomer. The enhancement in catalytic efficiency for cluster-bound anthraquinone arises from the smaller diffusion coefficient of cluster-bound anthraquinone, relative to that of the monomer, resulting in spatial compression of the reaction zone next to the electrode.
Keywords:HOMOGENEOUS REDOX CATALYSIS;STABILIZED GOLD CLUSTERS;ELECTROCHEMICAL REACTIONS;3-DIMENSIONAL MONOLAYERS;ELECTRON-TRANSFER;3 DIMENSIONS;MOLECULES;VOLTAMMETRY;REDUCTION;STATIONARY