@article{oai:kanazawa-u.repo.nii.ac.jp:00010909,
 author = {飯島, 隆広 and 水野, 元博 and 須原, 正彦 and 遠藤, 一央},
 issue = {3},
 journal = {分析化学 = Japan analyst},
 month = {Mar},
 note = {固体NMR法は,物質中の分子やイオンの静的・動的局所構造や常磁性イオンの電子スピンのダイナミクスを調べるのに有効な手法である.本研究では,反磁性化合物と常磁性化合物及び変調構造を有する化合物のNMR解析を可能にし,一般式[M(H_2O)_6][AB_6] (M = Mg^<2+>, Mn^<2+>, Fe^<2+>, Co^<2+>, Ni^<2+>; AB_6 = PtCl_6, SiF_6)で表される一連の化合物について,固体NMR法によりH_2O分子や[M(H_2O)_6]^<2+>イオンの静的・動的局所構造及び常磁性M^<2+>イオンの電子スピンのダイナミクスを調べた.分子運動と構造相転移との相関や[M(H_2O)_6]^<2+>イオンの構造と運動性との相関を明らかにした.[M(H_2O)_6]^<2+>イオンのdynamic disorder構造や変調構造も解析された. 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 T_1 of NMR in solids were measured for [M(H_2O)_6][AB_6] crystals to investigate the static and dynamic structure of H_2O and [M(H_2O)_6]^<2+> as well as the dynamics of the electron spin in the paramagnetic M^<2+> ion. The physical properties of [M(H_2O)_6][AB_6] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M^<2+> in [M(H_2O)_6][SiF_6] (M^<2+> = Fe^<2+>, Co^<2+>, Ni^<2+>) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin of Cu^<2+> in [Cu(H_2O)_6][PtCl_6] is caused by jumping between the Jahn-Teller configurations. (2) In [Cu(H_2O)_6][PtCl_6], H_2O and [Cu(H_2O)_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(H_2O)_6][SiF_6], H_2O and [M(H_2O)_6]^<2+> undergo 180°flips and reorientation about the C_3 axis, respectively. The order-disorder transition is closely related to a freezing of this reorientation. (4) By elongation of [M(H_2O)_6]^<2+> along the C_3 axis, the mobility becomes higher. (5) The disorder of [Fe(H_2O)_6]^<2+> in the high-temperature phase of [Fe(H_2O)_6][SiF_6] is dynamic. Rotational modulation of [Mg(H_2O)_6]^<2+> along the C_3 axis exists in the incommensurate phase of [Mg(H2_O)_6][SiF_6].},
 pages = {157--163},
 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},
 volume = {52},
 year = {2003}
}