Syntheses and investigation of the effects of position and nature of substituent on the spectral, electrochemical and spectroelectrochemical properties of new cobalt phthalocyanine complexes

The syntheses of new cobalt phthalocyanine (CoPc) complexes, tetra-substituted with diethylaminoethanethio at the peripheral (complex 3a) and non-peripheral (complex 3b) positions, and with benzylmercapto at the non-peripheral position (complex 5), are reported. The effects of the nature and position of substituent on the spectral, electrochemical and spectroelectrochemical properties of these complexes are investigated. Solution electrochemistry of complex 3a showed three distinctly resolved redox processes attributed to CoIIIPc−2/CoIIPc−2 (E½ = +0.64 V versus Ag|AgCl), CoIIPc−2/CoIPc−2 (E½ = −0.24 V versus Ag|AgCl) and CoIPc−2/CoIPc−3 (E½ = −1.26 V versus Ag|AgCl) species. No ring oxidation was observed in complex 3a. Complex 3b showed both ring-based oxidation, attributed to CoIIIPc−1/CoIIIPc−2 species (Ep = +0.86 V versus Ag|AgCl), and ring-based reduction associated with CoIPc−2/CoIPc−3 species (E½ = −1.46 V versus Ag|AgCl), with the normal metal-based redox processes in CoPc complexes: CoIIIPc−2/CoIIPc−2 (Ep = +0.41 V versus Ag|AgCl) and CoIIPc−2/CoIPc−2 (E½ = −0.38 V versus Ag|AgCl). Solution electrochemistry of complex 5 showed the same type and number of species observed in complex 3a: CoIIIPc−2/CoIIPc−2 (Ep = +0.59 V versus Ag|AgCl), CoIIPc−2/CoIPc−2 (E½ = −0.26 V versus Ag|AgCl) and CoIPc−2/CoIPc−3 (E½ = −1.39 V versus Ag|AgCl) species. These processes were confirmed using spectroelectrochemistry.

New cobalt phthalocyanine (CoPc) complexes, tetra-substituted with diethylaminoethanethio at the peripheral and non-peripheral positions show three well resolved redox processes whose potentials depended on the point of substitution.Figure optionsDownload as PowerPoint slide