Paramagnetic Prussian Blue Analogues CsMII[MIII(CN)6]. The Quest for Spin on Cesium Ions by Use of 133Cs MAS NMR Spectroscopy

被引：16

作者：

Koehler, Frank H. ^{[1
]}

Storcheva, Oksana ^{[1
]}

机构：

[1] Tech Univ Munich, Dept Chem, D-85748 Garching, Germany

来源：

INORGANIC CHEMISTRY | 2015年 / 54卷 / 14期

关键词：

POLARIZED NEUTRON-DIFFRACTION; TRANSFERRED HYPERFINE INTERACTION; MAGNETIC-ORDERING TEMPERATURE; NEGATIVE THERMAL-EXPANSION; INDUCED ELECTRON-TRANSFER; MOLECULE-BASED MAGNET; DENSITY DISTRIBUTION; CATHODE MATERIALS; CRYSTAL-STRUCTURE; CHARGE-TRANSFER;

D O I：

10.1021/acs.inorgchem.5b00711

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The Cs-133 magic-angle spinning NMR. spectra of the paramagnetic compounds CsMII[M-III(CN)(6)], M-II = Ni, Co, Fe, Mn; = Co, Fe, yield unusually large and temperature-dependent signal shifts (up to -950 ppm relative to CsCl at 298 K). Comparison with the spectra of the diamagnetic analogues CsM[Co(CN)(6)], M = Zn, Cd, shows that the shifts are largely due to the unpaired electrons. This is ascribed to through-bond transfer of spin to the Cs+ ions, while the through-space effect of the magnetic moments on the signal shifts is shown to be virtually negligible. The mechanism inducing negative spin at Cs+ is discussed. The magnitude of the spin density (average: vertical bar 5.8 X 10(-3)vertical bar (a.u.) (-3)) suggests that Cs+ is involved in magnetic exchange interactions of corresponding Prussian blue derivatives.

引用

页码：6801 / 6806

页数：6

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