Spectroelectrochemical and ESR studies of highly substituted copper corroles

Zhongping Ou, Jianguo Shao, Hui Zhao, Kei Ohkubo, Ingar H. Wasbotten, Shunichi Fukuzumi, Abhik Ghosh, Karl M. Kadish

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Electrochemical and spectroelectrochemical studies are presented for nine copper corroles with electron-withdrawing or electron-donating substituents on the three meso-phenyl rings of the compounds or on the eight β-pyrrole positions of the macrocycle. Up to three reversible oxidations can be seen for each Cu(III) corrole in CH2Cl2 containing 0.1 M TBAP. Unlike the case of (OEC)Cu, no dimer is electrochemically detected upon the first oxidation of these compounds at room temperature. However, a dimer forms at low temperature (< -50 ′C) for compounds having strong electron-donating groups. Two reductions are observed for all nine corroles at low temperature in CH2Cl2, 0.1 M TBAP, but only one reduction is detected at room temperature for four of these compounds which have weak electron-withdrawing or electron-donating groups. The neutral, reduced or oxidized Cu corroles were also characterized by thin-layer UV-visible spectroelectrochemistry and ESR. The resulting data indicates that eight of the nine neutral complexes contain a Cu(III) center while only one complex, [Br 8(C6F5)3Cor]Cu, exists in its Cu(II) form in CH2Cl2 containing 0.2 M TBAP.

Original languageEnglish
Pages (from-to)1236-1247
Number of pages12
JournalJournal of Porphyrins and Phthalocyanines
Issue number10
StatePublished - 2004


  • Copper corroles
  • ESR
  • Electrochemistry
  • Spectroelectrochemistry


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