Voltammetric, chronocoulometric and spectroelectrochemical studies of electropolymerized films based on Co(III/II)- and Zn(II)-4,9,16,23-tetraaminophthalocyanine: effect of high pH

Electropolymerized thin films of Co(III/II)- and Zn(II)-4,9,16,23-tetraaminophthalocyanine, immersed in solutions of relatively high pH, have been studied electro- and spectroelectrochemically. Cyclic voltammetry and chronocoulometry were used to characterize films deposited on glassy carbon electrodes. Spectroelectrochemistry and ellipsometry measurements were performed on indium tin oxide (ITO) surfaces coated with the zinc and cobalt complexes and correlated to the electrochemical information collected using glassy carbon electrodes. Studies at high pH are motivated by the efficient increase in luminol chemiluminescence at high OH⁻ concentration, and by potential application in luminescence sensors. Although the films are not removed, some structural changes occur when they are exposed to solutions of high pH. In addition, an estimation of the number of monolayers has also been calculated. The atomic diameters of cobalt and zinc are very close in value, but the estimated number of monolayers, based on cyclic voltammetric data, for a given number of electropolymerization cycles is approximately four-fold higher in the zinc-based film. This would correspond to three-fold thicker films when zinc is the central metal ion. Ellipsometry measurements have been correlated with cyclic voltammetric data to confirm that film thickness varies among the different complexes, even though the conditions of electropolymerization are the same.