シアン化物イオン架橋環状四核錯体における分子内電子移動に基づく多段階相転移  [in Japanese] Multi-Step Phase Transition Based on Intramolecular Electron Transfers in a Cyanide-Bridged Tetranuclear Molecular Square  [in Japanese]

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Abstract

Controlled intramolecular electron transfers were demonstrated in a series of cyanide-bridged Fe-Co molecular squares, [Co<sub>2</sub>Fe<sub>2</sub>(CN)<sub>6</sub>(L1)<sub>2</sub>(L2)<sub>4</sub>](PF<sub>6</sub>)<sub>2</sub>. The electronic structures of the molecular squares can be varied between [Fe<sup>III</sup><sub>LS2</sub>Co<sup>II</sup><sub>HS2</sub>] and [Fe<sup>II</sup><sub>LS2</sub>Co<sup>III</sup><sub>LS2</sub>] state by intramolecular electron transfers, which were significantly affected by the redox potential differences between metal ions. Chemical modifications of the capping ligands allowed the systematic control of the electronic states, and the occurrence of a novel two-step thermal electron transfer-coupled spin transition (ETCST). The two-step ETCST was originating from three thermodynamically stable phases, LT, IM, and HT phases. The electronic structure of each phase was investigated by X-ray structural analyses, and the IM phase showed long-range order of [Fe<sup>III</sup><sub>LS2</sub>Co<sup>II</sup><sub>HS2</sub>] and [Fe<sup>II</sup><sub>LS2</sub>Co<sup>III</sup><sub>LS2</sub>] species. In addition, novel thermal and protonation-induced ETCST in the solution state were found using variable temperature UV-vis absorption spectroscopy.

Journal

  • Nihon Kessho Gakkaishi

    Nihon Kessho Gakkaishi 54(6), 319-324, 2012-12-31

    The Crystallographic Society of Japan

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Codes

  • NII Article ID (NAID)
    10031144597
  • NII NACSIS-CAT ID (NCID)
    AN00188364
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    03694585
  • NDL Article ID
    024224467
  • NDL Call No.
    Z15-138
  • Data Source
    CJP  NDL  J-STAGE 
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