Peierls structure of (H3O)0.33Li0.8(Pt(mnt)2)1.67H2O.

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概要

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• The crystal structure determination of the title compound (abbreviated as α-LiPt(mnt) has been performed at room temperature and 153 K. The [Pt(mnt)<SUB>2</SUB>]<SUP><I>n</I>−</SUP> (mnt=1,2-dicyano-1,2-ethylenedithiolato, C<SUB>4</SUB>N<SUB>2</SUB>S<SUB>2</SUB><SUP>2−</SUP>) anions stack face-to-face along the c-axis with Pt···Pt distance of 3.6 Å. The room temperature structure and the average structure of the 153 K superstructure are almost the same. The room temperature conductivity of α-LiPt(mnt) is about 200 S cm<SUP>−1</SUP>, and the compound undergoes a metal-insulator transition (Peierls transition) at 220 K. In α-LiPt(mnt) the conduction pathway is through the ligand-centered π-system which is composed of predominantly S 3p<SUB>z</SUB> orbitals. Oscillation photographs about the c-axis show strong satellite spots on the layerlines of (0.41+<I>n</I>)c<SUP>*</SUP> and (0.59+<I>n</I>)c<SUP>*</SUP> (<I>n</I>=0, ±1, ±2, ···) The content of Li cation reveals that these satellite spots can be described as 2<I>k</I><SUB>F</SUB> spots. The regular appearance of characteristic satellite reflections indicates that α-LiPt(mnt) has a sinusoidally modulated lattice. The wave vector of the lattice modulation wave is <B>k</B>=0.15<B>b</B><SUP>*</SUP>+0.59<B>c</B><SUP>*</SUP> and the amplitude of the lattice modulation wave is 0.045 <B>a</B>⁄<I>a</I>+0.13<B>b</B>⁄<I>b</I>+0.060<B>c</B>⁄<I>c</I> Å. The overlap integrals along face-to-face stacking directions are much larger than the interstack overlap integrals and the resulting large anisotropy indicates that α-LiPt(mnt) is a one-dimensional metal.

• 公益社団法人 日本化学会の論文

著者

• Kobayashi Hayao

  Department Of Chemistry Faculty Of Science Toho University

• Kobayashi Akiko

  Department Of Biopharmaceutics Meiji Pharmaceutical University

• Mori Takehiko

  Department of Chemistry and Materials Science, Tokyo Institute of Technology, Meguro, Tokyo 152-8552, Japan

• Sasaki Yukiyoshi

  Department of Chemistry and The Research Centre for Spectrochemistry, Faculty of Science, The University of Tokyo

• Ahmad M.

  Department of Chemistry, University College of North Wales

• Underhill A.

  Department of Chemistry, University College of North Wales

• Ahmad M.

  Department of Chemistry, Faculty of Science, University of Cairo

• Mori Takehiko

  Department of Chemistry, Faculty of Science, The University of Tokyo

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