Counter Anion Effect on the Spin-crossover Behaviors of Two-dimensional Fe(II) Complexes with a Tripod Ligand Containing Three Imidazoles

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著者

    • IIJIMA S.
    • National Institute of Advanced Industrial Science and Technology (AIST)

抄録

<SUP>57</SUP>Fe Mössbauer spectroscopy has provided detailed information about the low-spin/high-spin transition in two types of two-dimensional Fe (II) complexes, [Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>][Fe<SUP>II</SUP>L<SUP>Me</SUP>]X (X<SUP>-</SUP>=BF<SUB>4</SUB><SUP>-</SUP>, ClO<SUB>4</SUB><SUP>-</SUP>, PF<SUB>6</SUB><SUP>-</SUP>, NO<SUB>3</SUB><SUP>-</SUP>) 1-4 and [Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>] Cl·X (X<SUP>-</SUP>=PF<SUB>6</SUB><SUP>-</SUP>, AsF<SUB>6</SUB><SUP>-</SUP>, SbF<SUB>6</SUB><SUP>-</SUP>) 5-7, where H<SUB>3</SUB>L<SUP>Me</SUP> denotes a hexadentate N<SUB>6</SUB> tripod-like ligand containing three imidazole groups, tris [2- ( ( (2-methylimidazol-4-yl) methylidene) amino) ethyl] amine. The molar fraction of high-spin Fe<SUP>II</SUP> versus total Fe<SUP>II</SUP> (γ<SUB>HS</SUB>) was estimated from Mössbauer area intensities of each compound in different temperatures. The γ<SUB>HS</SUB>-T plots for 1-4 indicated that these compounds exhibit a two-step spin crossover corresponding to (LS-[Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>]<SUP>2+</SUP> + LS-[Fe<SUP>II</SUP>L<SUP>Me</SUP>]<SUP>-</SUP>) ↔ (HS-[Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>]<SUP>2-</SUP> + LS-[Fe<SUP>II</SUP>L<SUP>Me</SUP>]<SUP>-</SUP>) ↔ (HS-[Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>]<SUP>2+</SUP> + HS-[Fe<SUP>II</SUP>L<SUP>Me</SUP>]<SUP>-</SUP>). The larger size of the counter anion separated the first and second spin crossover transitions in the [Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>] [Fe<SUP>II</SUP>L<SUP>Me</SUP>]X system well. A variety of γ<SUB>HS</SUB>-T curves depending on the counter anion was observed for [Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>] Cl·X. It was suggested that a smaller counter anion stabilizes the 1/2 (LS-[Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>]<SUP>2+</SUP> + HS-[Fe<SUP>II</SUP>H<SUB>3</SUB>L<SUP>Me</SUP>]<SUP>2+</SUP>) state in this system.

収録刊行物

  • Journal of Nuclear and Radiochemical Sciences  

    Journal of Nuclear and Radiochemical Sciences 8(2), 85-88, 2007-12-01 

    The Japan Society of Nuclear and Radiochemical Sciences

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各種コード

  • NII論文ID(NAID)
    10021101953
  • NII書誌ID(NCID)
    AA11948402
  • 本文言語コード
    ENG
  • 資料種別
    REV
  • ISSN
    13454749
  • データ提供元
    CJP書誌  J-STAGE 
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