Structural studies of partially oxidized one-dimensional bis(oxalato)-platinate salts containing bivalent cations: Ni0.84(Pt(C2O4)2)6H2O.

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概要

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• Fundamental structure, <I>k</I><SUB>F</SUB> and 2<I>k</I><SUB>F</SUB> satellite reflections, and electrical properties of Ni<SUB>0.84</SUB>[Pt(C<SUB>2</SUB>O<SUB>4</SUB>)2]·6H<SUB>2</SUB>O (Ni–OP) were determined. Complex Ni–OP crystallizes in the orthorhombic space group Pccn with cell parameters of <I>a</I>=14.296(2), <I>b</I>=16.387(3), and <I>c</I>=5.671(1) Å and <I>Z</I>=4. Ni–OP is essentially isostructural with Mg–OP (Mg<SUB>0.82</SUB>[Pt(C<SUB>2</SUB>O<SUB>4</SUB>)2]·5.3H<SUB>2</SUB>O) and Co–OP (Co<SUB>0.83</SUB>[Pt(C<SUB>2</SUB>O<SUB>4</SUB>)<SUB>2</SUB>]·6H<SUB>2</SUB>O). The space group of Mg–OP and Co–OP is Cccm. Owing to the change in the space group, there are two independent Pt chains in Ni–OP. X-Ray studies of M–OP (M=Co, Ni) show that there exist strong <I>k</I><SUB>F</SUB> satellite spots and weak 2<I>k</I><SUB>F</SUB> spots. One M<SUP>2+</SUP> cation is vacant per period of the lattice modulation wave of the platinum chain, λ<SUB>2<I>k</I><SUB>F</SUB></SUB>. The periodic cation defect induces the <I>k</I><SUB>F</SUB> modulation waves. The 2<I>k</I><SUB>F</SUB> waves do not have a Peierls origin but are induced by the <I>k</I><SUB>F</SUB> modulation wave. A second order phase transition is observed at about 305 K above which the 2<I>k</I><SUB>F</SUB> spots disappear.

• 公益社団法人 日本化学会の論文

著者

• Kondo Hidetaka

  Department Of Hygiene Nagoya University School Of Medicine

• Kobayashi Hayao

  Department Of Chemistry Faculty Of Science Toho University

• Kobayashi Akiko

  Department Of Biopharmaceutics Meiji Pharmaceutical University

• Sasaki Yukiyoshi

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

• Underhill Allan

  School of Physical and Molecular Sciences, University College of North Wales

• Watkins David

  School of Physical and Molecular Sciences, University College of North Wales

• Sasaki Yukiyoshi

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

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