Synthesis and electrochemical characterization of tetra-(5-chloro-2-(2,4-dichlorophenoxy)phenol) substituted Ni(II), Fe(II) and Cu(II) metallophthalocyanines

The synthesis and characterization of novel nitrile compound (3) and peripherally tetra 5-chloro-2-(2,4-dichlorophenoxy)phenol substituted nickel(II) (4), iron(II) (5) and copper(II) (6) phthalocyanines were accomplished for the first time in this study. Electrochemical characterizations of the complexes were carried out with voltammetric and in situ spectroelectrochemical measurements. CuPc and NiPc showed common Pc based electron transfer reactions. Small potential differences were observed between the redox responses of these complexes due to the different effective nuclear charges of the metal centers. [Cl^1--Fe^IIIPc^2-] complex gave metal and Pc based electron transfer reactions. While [Cl^1--Fe^IIIPc^2-] reduced to [Cl^1--Fe^IIPc^2-]^1-, [Cl^1--Fe^IPc^2-]^2-, and [Cl^1--Fe^IPc^3-]^3- during reduction reactions, a metal based ([Cl^1--Fe^IIIPc^2-]/[Cl^1--Fe^IVPc^2-]¹⁺) and then a Pc based ([Cl^1--Fe^IVPc^2-]¹⁺/[Cl^1--Fe^IVPc^1-]²⁺) oxidation reaction was observed the cathodic potential scans. Determination of the spectra, color of the electrogenerated MPc species and peak assignments of the complexes were determinated with in situ spectroelectrochemical measurements.