Motion of CF3 groups and phase transition in (Cu4(CF3COO)4)2C6H6 as studied by 1H and 19F NMR techniques.
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概要
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The temperature variation of <SUP>1</SUP>H and <SUP>19</SUP>F nuclear spin-lattice relaxation times <I>T</I><SUB>1</SUB> in [Cu<SUB>4</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>]·2C<SUB>6</SUB>H<SUB>6</SUB> was observed at different resonance frequencies. From the NMR experiments, it was found that this complex undergoes a first order phase transition at 130 K, which was confirmed by DTA measurements. In the room-temperature phase, <SUP>1</SUP>H gave normal exponential magnetization recovery curves and log<I>T</I><SUB>1</SUB> linearly decreased with increasing 10<SUP>3</SUP><I>T</I><SUP>－1</SUP> whereas <SUP>19</SUP>F gave nonexponential magnetization recovery curves, from which long- and short-<I>T</I><SUB>1</SUB> components could be derived. This indicates that the <I>C</I><SUB>3</SUB> reorientation of CF<SUB>3</SUB> groups about their respective symmetry axis is responsible for <SUP>19</SUP>F <I>T</I><SUB>1</SUB> and for <SUP>1</SUP>H <I>T</I><SUB>1</SUB> as well through <SUP>1</SUP>H-<SUP>19</SUP>F cross relaxation. This was confirmed from the coincidence of the log<I>T</I><SUB>1</SUB> <I>vs.</I> 10<SUP>3</SUP><I>T</I><SUP>－1</SUP> curve of the long component and that of <SUP>1</SUP>H <I>T</I><SUB>1</SUB>. A very small activation energy of 5.5 kJ mol<SUP>－1</SUP> was obtained for the CF<SUP>3</SUP> reorientation. For the low-temperature phase, both <SUP>1</SUP>H and <SUP>19</SUP>F yielded nonexponential magnetization decay curves.
著者
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Kubo Atsushi
Department Of Applied Chemistry And Biochemistry Faculty Of Engineering Kumamoto University
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Ikeda Ryuichi
Department Of Chemistry Faculty Of Engineering Gifu University
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Nakamura Daiyu
Department of Chemistry Faculty of Science Nagoya University
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Inoue Motomichi
CIPM, Universidad de Sonora
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Sampedro Jose
CIPM, Universidad de Sonora
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