Moessbauer spectroscopic studies of the chemical effects associated with 57Co(electron capture)57Fe decay in tris-.BETA.-diketonatocobalt(III) compounds.

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概要

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• Magnetic hyperfine structures (hfs) were found in the absorption Mössbauer spectra at 78 K of a paramagnetic iron(III) complex diluted in a diamagnetic cobalt(III) or aluminium(III) complex, such as <SUP>57</SUP>Fe(acac)<SUB>3</SUB> in Co(acac)<SUB>3</SUB>, <SUP>57</SUP>Fe(oxin)<SUB>3</SUB> in Al(oxin)<SUB>3</SUB>, and <SUP>57</SUP>Fe(dbm)<SUB>3</SUB> in Co(dbm)<SUB>3</SUB> (acac=acetylacetonato, oxin=8-quinolinolato, and dbm=dibenzoylmethanato), showing that the magnetic hfs is caused by the spin-spin relaxation through the surrounding diamagnetic species. In the emission Mössbauer experiments, magnetic hfs was observed at 78 K in <SUP>57</SUP>Co-labelled Co(dbm)<SUB>3</SUB>, Co(oxin)<SUB>3</SUB>, and polystyrene-diluted Co(acac)<SUB>3</SUB>, while it was not observed in <SUP>57</SUP>Co-labelled Co(acac)<SUB>3</SUB> and Co(dpm)<SUB>3</SUB> (dpm=dipivaloylmethanato). The former possess π-conjugated systems to a greater extent than the latter, either in the ligands or in the vicinity of the <SUP>57</SUP>Co-labelled Co(III) species. These results were explained in terms of the radiolytic stabilities of the matrices as well as those of <SUP>57</SUP>Co-labelled compounds by showing that the paramagnetic radicals produced in a diamagnetic matrix quench the magnetic hfs because of the increased spin-spin interaction, as a consequence of the local radiolysis by EC-decay.

• 公益社団法人 日本化学会の論文

著者

• Endo Kazutoyo

  Department Of Physical Chemistry Showa Pharmaceutical University

• Sakai Yoichi

  Department Of Bio- And Geosciences Graduate School Of Science Osaka City University

• SANO Hirotoshi

  Department of Chemistry, Faculty of Science, Tokyo Metropolitan University

• Sano Hirotoshi

  Deparment of Chemistry, Faculty of Science, Tokyo Metropolitan University

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