Optical and ESR spectra for high-spin tetrahedral complexes of Co(III) and Co(II) in Keggin-structure heteropolytungstate.

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概要

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• The ligand-field spectra for the cobalt complexes in the single crystals of K<SUB>3</SUB>H<SUB>2</SUB>[Co<SUP>III</SUP>W<SUB>12</SUB>O<SUB>40</SUB>]·16H<SUB>2</SUB>O and K<SUB>4</SUB>H<SUB>2</SUB>[(CO<SUP>II</SUP>, Zn<SUP>II</SUP>)W<SUB>12</SUB>O<SUB>40</SUB>]·<I>n</I>H<SUB>2</SUB>O have been observed at several temperatures above 1.4 K and assigned under D<SUB>2</SUB> site symmetry. In the spectrum of the elongated Co<SUP>III</SUP>O<SUB>4</SUB> complex, two absorption bands of 8250 and 8953 cm<SUP>−1</SUP> strengthen with increasing temperature by vibronic mechanism. The X-band ESR spectra of both complexes have also been measured at 77 K. The signal from the Co(III) complex is not observed. The signal of the high-spin Co(II) complex of tetrahedral symmetry is unequivocally observed even at relatively high temperature of 77 K. From the analysis of the ESR spectrum, it is concluded that the Co<SUP>II</SUP>O<SUB>4</SUB> tetrahedron of D<SUB>2</SUB> symmetry is flattened and deviated slightly from axial symmetry.

• 公益社団法人 日本化学会の論文

著者

• Tsujikawa Ikuji

  Department Of Chemisity Faculty Of Science Kyoto University

• Kojima Norimichi

  Department Of Basic Science Graduate School Of Arts And Science The University Of Tokyo

• Ban Toshiro

  Department Of Chemisity Faculty Of Science Kyoto University

• Kojima Kazuo

  Department Of Applied Chemistry College Of Life Sciences Ritsumeikan University

• BAN Toshiro

  Department of Chemistry, Faculty of Science, Kyoto University

• Matsuda Jiro

  Department of Chemistry, Faculty of Science and Engineering, Ritsumeikan University

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