Interpenetrated Three-Dimensional MnIIMIII Ferrimagnets, [Mn(4dmap)4]3[M(CN)6]2⋅10 H2O (M=Cr, Mn): Structures, Magnetic Properties, and Pressure-Responsive Magnetic Modulation

Authors

  • Wakako Kaneko,

    1. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615–8510, Japan, Fax: (+75) 383-2732
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  • Masaki Mito Dr.,

    1. Department of Electronics, Faculty of Engineering, Kyushu Institute of Technology, Sensui-cho, Tobata-ku, Kitakyushu, 804–8550, Japan
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  • Susumu Kitagawa Prof.,

    1. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615–8510, Japan, Fax: (+75) 383-2732
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  • Masaaki Ohba Dr.

    1. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615–8510, Japan, Fax: (+75) 383-2732
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Abstract

Two novel cyanide-bridged ferrimagnets, [Mn(4dmap)4]3[M(CN)6]2- ⋅10 H2O (4dmap=4-dimethylaminopyridine, M=Cr (1) and Mn (2)), have been prepared from the reaction of MnCl2⋅4 H2O, a monodentate coligand (4dmap), with K3[M(CN)6]. X-ray crystallographic results show that these are isomorphous, and form a unique twofold interpenetrated three-dimensional framework with a triconnected 6.102 net. The framework contains two types of one-dimensional channel: hexagonal channels based on a cyanide-bridged Mn6M6 hexagon, and triangle channels segmented by CN-Mn-NC linkages, which are filled with lattice water molecules. The dimethylamino groups of the 4dmap coligands are located around a pore and form the basic inner space. Variable-temperature X-ray powder diffraction and thermogravimetric analysis results show that the frameworks of both compounds are susceptible to dehydration through the loss of strongly hydrogen-bonded lattice water molecules. Magnetic measurements on both compounds show a ferrimagnetic ordering occurs at low temperature, TC=17 K for 1 and 6 K for 2. Application of hydrostatic pressure showed a positive effect on the magnetic ordering. Both values of TC increased linearly, to 25 K for 1 and 15 K for 2 at 1.0 GPa. The magnetic properties of both compounds were reversibly modulated by the external stress.

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