An Ab-initio theoretical study of the electrochemical grafting process of alkynil(aryl)iodonium salts on glassy carbon surfaces

The behaviour of alkynil(aryl)iodonium salts upon electrochemical reduction, on glassy carbon electrodes, is here studied by comparing both theoretical and experimental results. In particular, experimental results are obtained by means of cyclic voltammetry and chronocoulometric measurements as well as by collecting XPS spectra, while the standard electrode potential and different dissociation paths (I-C, arylic, compared to the I-C, alkynil, bond cleavage) have been characterized theoretically at the B3LYP/3-21g** level of the theory (the solvation free Gibbs energy of the cation and of the neutral radical species have been calculated by using the CPCM method).