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Issue 31, 2007
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Exploring the formation of 3D ferromagnetic cyano-bridged CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2xyH2O networks

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Two novel non-stoichiometric 3D cyano-bridged coordination networks of general formula CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2xyH2O were obtained according to two different synthetic strategies. The heterogeneous reaction between solid 2D cyano-bridged network (dienH3){CuII[WV(CN)8]}3·4H2O (1) (dienH33+ = protonated diethylenetriamine) and an aqueous solution of DyIII(NO3)3 results in the removal of dienH33+ cations and the formation of a 3D cyano-bridged CuII2.44{CuII4[WV(CN)8]3.12[WIV(CN)8]0.88}·5H2O (2) network. The direct combination of [CuII(H2O)6]2+ and [WV(CN)8]3− in aqueous media leads to the structurally related CuII2.97{CuII4[WV(CN)8]2.06[WIV(CN)8]1.94}·4H2O (3) assembly. The assemblies 2 and 3 were characterised by X-ray powder diffraction along with IR, X-ray absorption spectroscopy (XAS), proton induced X-ray emission (PIXE) and magnetic measurements. 2 and 3 crystallise in a tetragonal system, space group I4/mmm with cell parameters a = b = 7.2695(9) Å; c = 28.268(5) Å; Z = 2 (2) and a = b = 7.2858(9) Å, c = 28.282(5) Å, Z = 2 (3). Both networks are characterised by the increase of TC from 33 K to 40 K and coercivity from 0.2 to 2–2.5 kOe compared to 1. Despite their general structural and magnetic similarity, 2 and 3 reveal significant differences in magnetic dimensionality: compound 2 exhibits the features of a metamagnet with a threshold field of 1.8 kOe at 4.2 K, while compound 3 resembles a classical magnet with 3D ordering. This difference is discussed in terms of non-stoichiometry of the networks accompanied by the appearance of different numbers of non-magnetic “defects” due to the formation of diamagnetic W(IV) centres.

Graphical abstract: Exploring the formation of 3D ferromagnetic cyano-bridged CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2x}·yH2O networks

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Supplementary files

Article information

12 Mar 2007
04 May 2007
First published
16 May 2007

J. Mater. Chem., 2007,17, 3308-3314
Article type

Exploring the formation of 3D ferromagnetic cyano-bridged CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2xyH2O networks

R. Podgajny, N. P. Chmel, M. Bałanda, P. Tracz, B. Gaweł, D. Zając, M. Sikora, C. Kapusta, W. Łasocha, T. Wasiutyński and B. Sieklucka, J. Mater. Chem., 2007, 17, 3308
DOI: 10.1039/B703640J

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