“…For electrochemical measurements a BAS-100B workstation was used, with a three-electrode setup, consisting of a glassy carbon working, a Pt-wire auxiliary, and, for MeCN solutions, an Ag/AgNO 3 reference electrode (0.01 M AgNO 3 , 0.1 M (Bu 4 N)(PF 6 ), degassed CH 3 CN), solutions of the complexes in MeCN/0.1 M (Bu 4 N)(PF 6 ); for H 2 O solutions, an Ag/AgCl reference electrode (3 M NaCl, degassed and deionized H 2 O), solutions of the complexes in H 2 O, 0.1 M KNO 3 ; the potential of the Fc + /Fc-couple for the MeCN setup had a value of +91 mV (MeCN, scan rate of 100 mV/s); the potential of the Fc + /Fc-couple for the H 2 O setup had a value of +195 mV, (H 2 O, scan rate of 100 mV/s). Potentiometric titrations were performed on 20 mL of samples (0.1 M KCl for p K a values, 0.2 M NaClO 4 for complex stabilities, 0.1 mol/L of the respective metal ion, 0.1 mol/L ligand) in various dioxane-water mixtures (50%, 55%, 60%), − T = 298 K; HCl was used to adjust the initial pH for p K a titration, HClO 4 for complex stabilities; 0.1 mol/L KOH (CO 2 -free, titration with potassium hydrogen phthalate); all solutions were kept under Ar. The measurements were done with a pH meter equipped with a 6.0202.100 combined electrode (Metrohm), a 665 Dosimat automatic buret (Metrohm).…”