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Syntheses, Crystal Structures, and Solid State Properties of Halogen-bridged mixed-valence siplatinum complexes PtィイD22ィエD2(RCSィイD22ィエD2)ィイD24ィエD2I

Research Project

Project/Area Number 09440232
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionHimeji Institute of Technology

Principal Investigator

TORIUMI Koshiro  Himeji Inst. of Tech., Fac. of Science, Professor, 理学部, 教授 (90124221)

Co-Investigator(Kenkyū-buntansha) MITSUMI Minoru  Himeji Inst. of Tech., Fac. of Science, Research Associate, 理学部, 助手 (20295752)
OZAWA Yoshiki  Himeji Inst. of Tech., Fac. of Science, Associate Professor, 理学部, 助教授 (40204200)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥9,500,000 (Direct Cost: ¥9,500,000)
Fiscal Year 1998: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1997: ¥6,300,000 (Direct Cost: ¥6,300,000)
Keywordsdiplatinum complex / mixed-valence / one-dimensional compound / X-ray diffuse scattering / valence ordering / M-I transition / crystal structure analysis / 分子振動
Research Abstract

Halogen-bridged mixed-valence diplatinum complexes PtィイD22ィエD2(RCSィイD22ィエD2)ィイD24ィエD2I (R= CHィイD23ィエD2 (1), CィイD22ィエD2HィイD25ィエD2 (2), n-CィイD23ィエD2HィイD27ィエD2 (3), n-CィイD24ィエD2HィイD29ィエD2(4)) with linear chain structures of repeating units {-I-Pt-Pt-} are particular interest because they are possible to take a variety of valence ordering. The crystals of 1 which was first reported by Bellitto et al. exhibit anomalous electrical conducting behavior (T < 300K, semiconductor ; 300 K < T < 340 K, metallic). The variable temperature crystal structure analyses revealed dynamic disorder of the ligands.
In order to elucidate the relation between the solid state behavior and the valence ordering of Pt atoms on the linear chain, the compounds 2 - 4 were synthesized and their crystal structure analyses and electrical conducting measurements were carried out. The M-I transitions were observed for 2 and 4.
Since the crystal structure analyses provided only the averaged structures, we tried to measure the diffuse scattering corresponding to low-dimensional valence ordering of Pt atoms. Single crystal X-ray photographs of the compounds 1 and 2 were taken at variable temperatures by using the vacuum type X-ray camera and SPring-8. It was revealed that although the diffuse scattering corresponding to the valence alternation along the linear chain have been observed for 2 above 200 K (metallic state), but changed to the Bragg spots below 100 K (semiconductive state).

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (5 results)

All Other

All Publications (5 results)

  • [Publications] H. Kitagawa: "The Metallic State in a MMX-Chain Complex, Pt2(dta)4I"Synthetic Metals. 86. 1931-1932 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Mitsumi: "Synthesis and Synchrotron Radiation Structure Analysisof Tetra-Dithiopropanato-Diplatinum(II) with Infinite Linear Chain Structure"Mol. Cryst. Liq. Cryst.. (in press.).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H. Kitagawa, N. Onodera, J.-S. Ahn, T. Mitani, K. Toriumi, and M. Yamashita: "The Metallic State in a MMX-Chain Complex, PtィイD22ィエD2(dta)ィイD24ィエD2I"Synthetic Metals. 86. 1931-1932 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Mitsumi, T. Yoshinari, Y. Ozawa, and K. Toriumi: "Synthesis and Synchrotron Radiation Structure Analysis of Tetra-Dithiopropanato-Diplatinum(II) with Infinite Linear Chain Structure"Mol. Cryst. Liq. Cryst.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Kitagawa: "The Metallic State in a MMX-Chain Complex, Pt_2(dta)_4I" Synthetic Metals. 86. 1931-1932 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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