Journal of Electroanalytical Chemistry, Vol.523, No.1-2, 126-135, 2002
Voltammetric and impedance study of the binding of ferrocene derivatives to a sulfonated calix[6]arene host in aqueous solutions
This report describes the effect of host-guest complexation on the thermodynamic and kinetic parameters of ferrocene redox reactions in aqueous media. The formal potentials of the ferrocene/ferrocenium couples examined shifted to less positive values with increasing calixarene concentration. because of the formation of a 1:1 inclusion compound. The order of binding constants was cationic ferrocene much greater than non-charged ferrocene > anionic ferrocene. The oxidized form with a higher positive charge was bound more strongly to the host than was the corresponding reduced form. The result was contrary to that observed for beta-cyclodextrin. The inclusion compounds formed by sulfonated calix[6]arene were greatly stabilized by an electrostatic interaction between the negatively charged host and cationic guest. Fast-scan voltammetric behavior suggested that inclusion-ejection processes practically attain equilibrium in the scan-rate range below 2 V s(-1), Randles plots for the Faradaic impedance of the electrode reaction virtually comprised two nearly parallel straight lines with a small separation over the frequency range of 10(2) - 10 (3).Hz, indicating negligible chemical reaction impedance. As the host concentration increased, the mean diffusion coefficient of the (ferrocenyl-methyl) trimethylammonium cation decreased inversely proportionally from 6.0 x 10 (6) cm(2) s (1) of the free ion to (2.1 +/- 0.2) x 10(-6) cm(2) s(-1) of the corresponding inclusion complex. The result of the impedance analysis suggests that the included guest exchanges no electrons directly with the electrode.
Keywords:calix[6]arene-p-hexasulfonate;ferrocene derivatives;inclusion compound;host-guest interaction;redox-switchable supramolecular system