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Figure 8. Supramolecular association of acceptors with TTF donors
immobilized on the surface of a gold electrode.
donors (orange) when they approach the electrode surface. As
a result, the heterogeneous electron transfer to the acceptors is
slowed dramatically and RCT increases. Concomitantly, the TTF
donors associated with the acceptors lose their electroactive
character and only the TTFs (yellow in Figure 8) not involved
in donor/acceptor interactions produce a detectable electro-
chemical response. The consequence is a significant drop in
current for the TTF redox waves. In agreement with this model,
control experiments with hexadecanethiolate monolayers con-
firm that the heterogeneous electron transfer to the acceptors is
slowed significantly only in the presence of TTF donors on the
electrode surface. Thus, our results demonstrate that the as-
sociation of TTF donors immobilized on gold electrodes with
acceptors in the electrolyte solution has a drastic effect on
interfacial electron transfer.
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Acknowledgment. We thank the National Science Founda-
tion (CAREER Award CHE-0237578) and the University of
Miami for financial support.
Supporting Information Available: Experimental proce-
dures for the synthesis of 1; cyclic voltammograms of the TTF
monolayers; cyclic voltammograms and impedance response of
Ru(NH3)6Cl3 at bare and hexadecanethiolate-coated gold;
impedance response of ferrocene, benzyl viologen, TCNQ, and
TCNE at bare gold; cyclic voltammograms of benzyl viologen,
TCNQ, and TCNE at bare gold; determination of RCT from the
impedance plots. This material is available free of charge via
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