A new class of soluble unsymmetrically substituted metallophthalocyanines (M = Zn, Ni, Co) bearing a crown ether and six alkylthio substituents was synthesized and their electrochemical and spectroelectrochemical properties studied. Cyclic and square wave voltammetry revealed well-defined ligand-based oxidation and reduction processes within the complexes. Assignment of the redox processes was performed by in-situ spectroelectrochemical measurements. The disappearance of the redox processes for the monomeric species and the observation of new waves indicated that intermolecular dimer formation occurred during the potentiometric titration of the complexes with K+ and Na+ ions. (C) 2010 Elsevier Ltd. All rights reserved.