Metallo (Mn, Co, VO) phthalocyanines bearing peripheral 2-naphthoxy groups were synthesized by cyclotetramerisation of the corresponding phthalonitrile derivative. The phthalocyanine compounds were characterized by elemental analyses, mass, FT-IR and UV-vis spectral data. Three intense bands in the electronic spectra clearly indicate the absorptions resulting from naphthyl groups along with the Q and B bands of the phthalocyanines. Electrochemical and spectroelectrochemical measurements exhibit that incorporation of redox active metal ions, Co-II and Mn-III. into the phthalocyanine core extends the redox capabilities of the Pc ring including the metal-based reduction and oxidation couples of the metal. Presence of molecular oxygen in the electrolyte system affects the voltammetric and spectroelectrochemical responses of the cobalt and manganese phthalocyanines due to the interaction between the complexes and molecular oxygen. Interaction reaction of oxygen with CoPc occurs via an "inner sphere" chemical catalysis process. While CoPc gives the intermediates [O-2(-)-(CoPc-2)-Pc-II](-) and [O-2(2)-(CoPc-2)-Pc-II](2-), MnPc forms mu-oxo MnPcspecies. An in situ electrocolorimetric method has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for possible electrochromatic applications. (C) 2011 Elsevier Ltd. All rights reserved.