Structural studies of commensurate Peierls state of Rb1.67[Pt(C2O4)2] 1.5H2O.

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概要

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• X-Ray examination, chemical analyses and electrical conductivity measurements have been conducted on the partially oxidized platinum complex Rb<SUB>1.67</SUB>[Pt(C<SUB>2</SUB>O<SUB>4</SUB>)<SUB>2</SUB>]·1.5H<SUB>2</SUB>O (RbDOX). The cell constants are <I>a</I>=12.690(10), <I>b</I>=17.108(14), <I>c</I>=11.357(3) Å; α=102.04(4), β=115.17(3), γ=43.58(4)°, and the space group is P\bar1. The planar bis(oxalato)platinate ions stack along the crystallographic b axis and the Pt atoms form a sixfold distorted chain. RbDOX is the first example of a sixfold structure. Three independent Pt–Pt distances are 2.717(3), 2.830(3), and 3.015(3) Å. The Pt–Pt distance of 2.717 Å is the shortest spacing so far observed in partially oxidized platinate salts and shorter than the 2.77 Å interatomic separation in Pt metal itself. The oxalate ligands are staggered (46°, 55°, 80°) with respect to the ligands directly above and below them along the chain. Sixfold modulated superstructure of RbDOX is confirmed as the newly found commensurate Peierls structure based on agreement with the period of the Peierls distorted superlattice determined by the degree of partial oxidation. The calculation of Coulomb energy shows that RbDOX has a crystal lattice in which the interchain Coulomb energies are at a minimum indicating the strong tendency of the anti-phase ordering of the nearest-neighbour Pt chains.

• 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

• Sasaki Yukiyoshi

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

• Kobayashi Akiko

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

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