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Molecular and electron-spin dynamics in [M(H2O)6][AB6] as studied by solid state NMR.

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  • IIJIMA Takahiro
    Department of Chemistry, Faculty of Science, Kanazawa University Present address, Nanomaterials Laboratory, National Institute for Materials Science (NIMS)
  • MIZUNO Motohiro
    Department of Chemistry, Faculty of Science, Kanazawa University
  • SUHARA Masahiko
    Department of Chemistry, Faculty of Science, Kanazawa University
  • ENDO Kazunaka
    Department of Chemistry, Faculty of Science, Kanazawa University

Bibliographic Information

Other Title
  • 固体ＮＭＲ法による［Ｍ（Ｈ２Ｏ）６］［ＡＢ６］結晶における分子及び電子スピンのダイナミクスの研究
  • コタイ NMRホウ ニ ヨル M H2O 6 AB6 ケッショウ ニ オケル ブンシ オヨビ デンシ スピン ノ ダイナミクス ノ ケンキュウ

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Abstract

A method using the 2H-NMR spectra was shown to be useful to study the solid state physics in diamagnetic and paramagnetic compounds and in crystals having a modulated structure. The spectra and T1 of NMR in solids were measured for [M(H2O)6][AB6] crystals to investigate the static and dynamic structure of H2O and [M(H2O)6]2+ as well as the dynamics of the electron spin in the paramagnetic M2+ ion. The physical properties of [M(H2O)6][AB6] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M2+ in [M(H2O)6][SiF6] (M2+=Fe2+, Co2+, Ni2+) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin of Cu2+ in [Cu(H2O)6][PtCl6] is caused by jumping between the Jahn-Teller configurations. (2) In [Cu(H2O)6][PtCl6], H2O and [Cu(H2O)6]2+ undergo 180° flips and jumping between the different Jahn-Teller configurations, respectively. A weakening of the hydrogen bond O-H…Cl upon deuteration results in a lowering of the transition temperature. (3) In [M(H2O)6][SiF6], H2O and [M(H2O)6]2+ undergo 180° flips and reorientation about the C3 axis, respectively. The order-disorder transition is closely related to a freezing of this reorientation. (4) By elongation of [M(H2O)6]2+ along the C3 axis, the mobility becomes higher. (5) The disorder of [Fe(H2O)6]2+ in the high-temperature phase of [Fe(H2O)6][SiF6] is dynamic. Rotational modulation of [Mg(H2O)6]2+ along the C3 axis exists in the incommensurate phase of [Mg(H2O)6][SiF6].<br>

Journal

  • BUNSEKI KAGAKU

    BUNSEKI KAGAKU 52 (3), 157-163, 2003

    The Japan Society for Analytical Chemistry

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