Light-Induced Mixed-Valence State of Fe^II[Fe(CN)_5NO]・xH_2O

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Abstract

A long-living metastable state is produced in Fe<sup>II</sup>[Fe(CN)<sub>5</sub>NO]·<i>x</i>H<sub>2</sub>O by an irradiation of 488 nm light at 200 K. A strong near-infrared band of about 10000 cm<sup>−1</sup> and a <i>ν</i>(CN) band at 2070 cm<sup>−1</sup> that newly appear in the metastable state point to development of the mixed-valence state analogous to Prussian blue. An iron-to-nitrosyl charge transfer in pentacyanonitrosylferrate(2−), [Fe(CN)<sub>5</sub>NO]<sup>2−</sup>, explains the formation of the mixed-valence state, because the charge transfer causes a pair of iron(II) and iron(III) atoms bridged by CN<sup>−</sup> that has the same local structure as Prussian blue. In addition to the formation of the metastable state, the prolonged irradiation causes an irreversible change of Fe<sup>II</sup>[Fe(CN)<sub>5</sub>NO]·<i>x</i>H<sub>2</sub>O and leads to the formation of a photoproduct. The photoproduct also has infrared spectra characteristic of the mixed-valence state. Mössbauer spectra of the photoproduct show that a low-spin iron ion in pentacyanonitrosylferrate(2−) is divalent and a high-spin iron outside of pentacyanonitrosylferrate(2−) is trivalent. Therefore, the charge-transfer between the two non-equivalent iron ions is thought to follow the intra-molecular charge transfer in pentacyanonitrosylferrate(2−).

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 71(4), 837-844, 1998-04-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10008930503
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4462525
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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