Collect. Czech. Chem. Commun. 2001, 66, 338-354

Electrochemistry and Spectroelectrochemistry of Strongly Electron-Withdrawing Metallated Octanitrophthalocyanines

Yu-Hong Tsea, Nagao Kobayashib and A. B. P. Levera,*

a Department of Chemistry, York University, 4700 Keele St., North York, Ontario, Canada, M3J-1P3
b Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan


The spectral and electrochemical properties of metallated octanitrophthalocyanines, [MII{(NO2)8pc}] where M = Zn, Cu or Co, were studied by electrochemical and spectroelectrochemical methods as well as electronic absorption and magnetic circular dichroism spectroscopy. Aggregation is observed for several species. The octanitrophthalocyanines are easier to reduce and more difficult to oxidize than most other metallophthalocyanines. Indeed, the first ring-localized reduction potential observed with these phthalocyanine species, is the most positive of the metallated, neutral phthalocyanines in the literature. These data are added to existing Hammett free energy relationship database to extend design protocols for substituted metallophthalocyanines. Optical spectra for several redox series are presented and related to the existing literature.

Keywords: Phthalocyanines; Electrochemistry; Electronic absorption spectroscopy; Zinc; Copper; Cobalt; Metallophthalocyanines; Substituents effects.

References: 56 live references.