SYNTHESIS OF ADSORBABLE REDOX-ACTIVE OSMIUM THIOL MONOLAYERS AND THE EFFECTS OF THE WORKING ELECTRODE POTENTIAL DURING DEPOSITION

A new series of redox-active transition metal complexes of the type [O s(bpy)(2)Cl(Py-(CH2)(n)-SH)](PF6), with n = 4, 6, or 9, capable of for ming adsorbed monolayers on gold, platinum and silver electrodes has b een synthesized and the effect of the working electrode potential duri ng deposition on the amount of material deposited onto the electrode s urface has been studied using cyclic voltammetry. The amount of materi al deposited onto the working electrode at potentials negative of the potential of zero charge E(pzc) for a given metal electrode depended o n the potential applied during deposition, but at potentials positive of E(pzc), the amount deposited was much smaller and virtually indepen dent of the applied potential. The interaction most dominant in the ad sorption process of these redox-active species appears to be electrost atic attraction and repulsion. In addition, this method provides for a facile way to determine E(pzc) for solid electrodes.