Electron transfer reaction of porphyrin and porphycene complexes of Cu(II) and Zn(II) in acetonitrile

Kaori Aoki, Toshimitsu Goshima, Yohei Kozuka, Yukiko Kawamori, Noboru Ono, Yoshio Hisaeda, Hideo D. Takagi, Masahiko Inamo

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Abstract

The outer-sphere one-electron oxidation reaction of the Cu(ii) and Zn(ii) complexes of nonplanar 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20- tetraphenylporphyrin and planar porphycenes as well as those of 2,3,7,8,12,13,17,18-octaethylporphyrin and 5,10,15,20-tetraphenylporphyrin by Cu2+ giving corresponding π-cation radicals was investigated spectrophotometrically in acetonitrile. The electron self-exchange rate constants between the parent porphyrin and porphycene complexes and their π-cation radicals were determined using the Marcus cross relation for the electron transfer reaction. The obtained rate constants are in the order of 109 to 1011 M-1 s-1 for the planar porphyrin and porphycene complexes and 104 to 106 M -1 s-1 for the nonplanar OETPP complexes at T = 25.0 °C. The relatively slow self-exchange reaction of the distorted porphyrin complexes, as compared with those for the planar porphyrin and porphycene complexes, was ascribed to the significant deformation of the complex associated with the oxidation reaction from the parent complex to the corresponding π-cation radical.

Original languageEnglish
Pages (from-to)119-125
Number of pages7
JournalDalton Transactions
Issue number1
DOIs
Publication statusPublished - Jan 1 2009

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Porphyrins
Cations
Electrons
Rate constants
Oxidation
porphycene
acetonitrile
5,10,15,20-tetraphenylporphyrin

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Electron transfer reaction of porphyrin and porphycene complexes of Cu(II) and Zn(II) in acetonitrile. / Aoki, Kaori; Goshima, Toshimitsu; Kozuka, Yohei; Kawamori, Yukiko; Ono, Noboru; Hisaeda, Yoshio; Takagi, Hideo D.; Inamo, Masahiko.

In: Dalton Transactions, No. 1, 01.01.2009, p. 119-125.

Research output: Contribution to journalArticle

Aoki, Kaori ; Goshima, Toshimitsu ; Kozuka, Yohei ; Kawamori, Yukiko ; Ono, Noboru ; Hisaeda, Yoshio ; Takagi, Hideo D. ; Inamo, Masahiko. / Electron transfer reaction of porphyrin and porphycene complexes of Cu(II) and Zn(II) in acetonitrile. In: Dalton Transactions. 2009 ; No. 1. pp. 119-125.
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