The ESR spectrum of a .PI. cation radical trapped in a single crystal of chloro(tetraphenylporphyrinato)cobalt(III).

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概要

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• The electron-spin-resonance (ESR) spectra of three paramagnetic species trapped in single crystals of chloro(tetraphenylporphyrinato)cobalt(III) have been observed at 77 K. Using the ESR parameters obtained, one of them has been identified as the [Co<SUP>III</SUP>(tpp)]<SUP>2+·</SUP>(Cl<SUP>−</SUP>)<SUB>2</SUB> π cation radical, and the other two species, as [Co<SUP>II</SUP>(tpp)] which are influenced by axial ligation. From the angular variations in the hfcc due to the <SUP>59</SUP>Co, <SUP>14</SUP>N, and <SUP>35</SUP>Cl in the π cation radical, it has been found that the unpaired electron resides on the a<SUB>2u</SUB> porphyrin π orbital and polarizes the Co and Cl atomic orbitals through a spin-polarization mechanism. Finally, the radical formation mechanisms in solution are briefly discussed, based on the results obtained from the single-crystalline measurements.

• 公益社団法人 日本化学会の論文

著者

• SAKURAI Tosio

  The Institute of Physical and Chemical Research

• Kohno Masahiro

  JEOL Ltd.

• Yamamoto Kiyoko

  The Institute of Physical and Chemical Research

• Ohya-Nishiguchi Hiroaki

  Department of Chemistry, Faculty of Science, Kyoto University

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