Electrochemically Assisted Grafting of Asymmetric Alkynyl(aryl)iodonium Salts on Glasy Carbon with Focus on the Alkynyl/Aryl Grafting Ratio

Nicola Florini, Marco Michelazzi, Francesca Parenti, Adele Mucci, Marco Sola, Carla Baratti, Valentina De Renzi, Kim Daasbjerg, Steen Uttrup Pedersen and Claudio Fontanesi


Glassy carbon (GC) surfaces are functionalized exploiting the electrochemical reduction of asymmetric iodonium salts of the general formula [4-Z-C6H4I+CC(CH2)4Cl, Z = NO2, Br, F, H, or CH3]. The range of Z groups was selected aiming to examine the Caryl-I bond energy as a function of the “electron withdrawing/electron donating” ability of the Z-group, with the ultimate purpose of controlling the alkynyl/aryl grafting ratio. The electroreduction mechanism and the characteristics of the grafted surface are studied by means of cyclic voltammetry and X-ray photoelectron spectroscopy. It is shown that the alkynyl/aryl grafting ratio decreases with the increasing electron withdrawing nature of Z, which induces a weakening of the Caryl-I bond. Ab initio DFT vertical electron affinities (EAv) allowed to rationalize the electroreduction potentials of both the bulk and surface functionalised redox couples. Moreover, the alkynyl/aryl grafting ratio is assessed, at a molecular level, on the basis of ab initio DFT potential energy surfaces.