Triarylporphyrin meso-Oxy Radicals: Remarkable Chemical Stabilities and Oxidation to Oxophlorin π-Cations

Daiki Shimizu, Juwon Oh, Ko Furukawa, Dongho Kim, Atsuhiro Osuka

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50 Citations (Scopus)


5-Hydroxy-10,15,20-triarylporphyrin (oxophlorin) and its Ni(II) and Zn(II) complexes were oxidized with PbO2 to give the corresponding porphyrin meso-oxy radicals as remarkably stable species. These radicals were fully characterized with X-ray diffraction analysis, UV/vis/NIR absorption and ESR spectroscopies, magnetic susceptibility measurement, electrochemical studies, and theoretical calculations. Free-base radical and its Ni(II) complex have been shown to exist as a monoradical in solution, while the Zn(II) complex exists in an equilibrium between monomer (doublet monoradical) and dimer (a non-Kekulé singlet biradicaloid) with a dimerization constant of KD = 3.0 × 105 M-1 in noncoordinating CH2Cl2 but becomes a pyridine-coordinated monoradical upon addition of pyridine. Variable temperature magnetic susceptibility measurements of these radicals revealed different magnetic interactions in the solid-states, which has been interpreted in terms of their different packing structures in a microscopic sense. These radicals undergo one-electron oxidation and reduction in a reversible manner within narrow potential windows of 0.57-0.82 V. Finally, one-electron oxidation of Ni(II) and Zn(II) porphyrin meso-oxy radicals with tris(4-bromophenyl)aminium hexachloroantimonate furnished oxophlorin π-cations, which displayed nonaromatic closed-shell character, NIR absorption, and significant double bond character of the C-O bond.

Original languageEnglish
Pages (from-to)15584-15594
Number of pages11
JournalJournal of the American Chemical Society
Issue number49
Publication statusPublished - 2015 Dec 16

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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