Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine

The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.

Graphical abstractManganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituents show that the central metal plans a significant role in the aggregation behavior, with Mn phthalocyanine derivatives showing the presence of μ oxo dimers.Figure optionsDownload full-size imageDownload as PowerPoint slide