Electrochemical and spectroelectrochemical characterization of the phthalocyanines with pentafluorobenzyloxy substituents

The solution redox properties and spectroelectrochemical investigation of the novel metal-free, zinc, nickel and cobalt phthalocyanines with tetra-pentafluorobenzyloxy substituents at the periphery were studied using various electrochemical and spectroelectrochemical measurements. Cyclic voltammetry and differential pulse voltammetry studies show that while Ni(II), Zn(II) and free-phthalocyanines give up to two reduction and two oxidation processes having ligand-based diffusion controlled reversible one-electron electron transfer characters, Co(II) phthalocyanine represents one ligand-based oxidation, one metal-based reduction and one ligand-based reduction processes having diffusion controlled reversible one-electron transfer characters. Assignments of the redox couples are also confirmed by spectroelectrochemical measurements. Reduction potentials of all complexes shift to positive potentials due to the electron withdrawing tetra-pentafluorobenzyloxy substituents compared with those of the phthalocyanines bearing phenoxy derivatives. A linear variation of the first reduction and oxidation potentials versus ze/r has been obtained for zinc and nickel phthalocyanines.