The nuclear quadrupole spin-lattice relaxation of 35Cl in methylammonium hexachlorostannate(IV) and hexachloroplatinate(IV).

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概要

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• The <SUP>35</SUP>Cl nuclear quadrupole spin-lattice relaxation time, <I>T</I><SUB>1</SUB> in (CH<SUB>3</SUB>NH<SUB>3</SUB>)<SUB>2</SUB>MCl<SUB>6</SUB> (M=Sn and Pt) was measured from 4.2 to 434 K in order to clarify the dynamic aspect of the phase transitions at 156 and 125 K respectively. The relaxation process in both low-temperature phases is dominated by the rotational vibration of the octahedral [MCl<SUB>6</SUB>]<SUP>2−</SUP> ions. Far above the transition point, <I>T</I><SUB>tr</SUB>, the <I>T</I><SUB>1</SUB> decreases very rapidly with an increase in the temperature. This indicates that each octahedron reorients about its threefold axis, with the activation energies of 77±3 for [SnCl<SUB>6</SUB>]<SUP>2−</SUP> ions and 95±10 kJ mol<SUP>−1</SUP> for [PtCl<SUB>6</SUB>]<SUP>2−</SUP> ions. At <I>T</I><SUB>tr</SUB> the log(<I>T</I><SUB>1</SUB>⁄s) <I>vs.</I> kK/<I>T</I> curve shows a distinct minimum, as in some K<SUB>2</SUB>PtCl<SUB>6</SUB>-type compounds. This anomalous behavior can be explained in terms of a soft rotary mode of the [MCl<SUB>6</SUB>]<SUP>2−</SUP> ions. The softening is estimated to be about 60%, according to Armstrong's approach.

• 公益社団法人 日本化学会の論文

著者

• Ikeda Ryuichi

  Department Of Chemistry Faculty Of Engineering Gifu University

• Furukawa Yoshihiro

  The Institute of Scientific and Industrial Research, Osaka University

• Kiriyama Hideko

  The Institute of Scientific and Industrial Research, Osaka University

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