Use of Selective Redox Cross-Inhibitors for the Control of Organic Layer Formation Obtained via Diazonium Salt Reduction

The controlled electrochemical deposition of a series of four diazonium salts (4-bromobenzene, 4-iodobenzene, 4-methoxybenzene, and 4-diethylaminobenzene diazonium) on carbon surfaces has been achieved by exploiting the use of three redox mediators: 2,2-dipheny1-1-picrylhydrazyl, chloranil, and dichlone. The efficiency of the method rests on a fast redox cross-reaction in the diffusion layer between the diazonium compound and the reduced form of the selected inhibitor, characterized by an outer-sphere electron transfer. The effect of the inhibitor addition in the deposition solution was characterized using electrochemical techniques, X-ray photoelectron spectroscopy, and atomic force microscopy. Nearmonolayers are obtained when the potential of the redox mediator is at least 100 mV lower than the reduction potential of the diazonium salt concerned. A judicious choice of the redox entity can allow, via a fine control of the experimental conditions, to modulate the thickness of organic layers by varying the grafting potential.