Electrochemical and spectroelectrochemical characterization of newly synthesized manganese, cobalt, iron and copper phthalocyanines

• Published in: Electrochimica acta Vol. 87; pp. 554 - 566
• Main Authors: Arıcı, Mürsel, Arıcan, Duygu, Uğur, Ahmet Lütfi, Erdoğmuş, Ali, Koca, Atıf
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 01-01-2013; Elsevier
• Subjects: Chemistry; Cobalt; Color; Copper; Couples; Electrochemistry; Electron transfer; Exact sciences and technology; General and physical chemistry; Iron; Manganese; Non-peripheral substitution; Reduction (electrolytic); Spectroelectrochemistry; Thiol-substituted metallophthalocyanines; Electrochemistry; Iron; Thiol-substituted metallophthalocyanines; Non-peripheral substitution; Spectroelectrochemistry; Manganese; Thiol; Transition metal; Transition metal Complexes; Cobalt; Copper Complexes; Characterization; Metallophthalocyanine; Chemical synthesis
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2012.09.045

► Metallo-phthalocyanines, tetra-substituted with dimethoxyphenylthiowere synthesized and characterized. ► Incorporating redox active metal centers into the phthalocyanine core extends the redox richness of the phthalocyanine. ► In situ electrocolorimetric measurements allow quantification of color coordinates of the each electrogenerated species. ► Presence of O2 in the electrolyte influences the redox couples of the complexes due to the interaction with O2.
Manganese, cobalt, iron, and copper phthalocyanines, tetra-substituted with 3,4-(dimethoxyphenylthio) moieties at peripheral positions, were synthesized and characterized by FT-IR, mass spectroscopy, and electronic spectroscopy. Electrochemical and spectroelectrochemical measurements exhibit that while copper phthalocyanine gives only ring-based electron transfer reactions, incorporating redox active metal centers, CoII, FeIIIAc, and MnIIIAc, into the phthalocyanine core extends the redox richness of the phthalocyanine ring with the metal-based reduction and oxidation couples of the metal centers in addition to the common phthalocyanine ring-based electron transfer processes. In situ electrocolorimetric measurements of the complexes allow quantification of color coordinates of the each electrogenerated anionic and cationic redox species. Presence of O2 in the electrolyte system influences the redox couples of the complexes due to the interaction between O2 and metallophthalocyanines having redox active metal center.