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Hydrothermal syntheses, structures and magnetic properties of coordination frameworks of divalent transition metals

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Abstract

The hydrothermal syntheses, single-crystal X-ray structures and magnetic properties of [Co(C4O4)(H2O)2] (1), [Co3(OH)2(C4O4)2] · 3H2O (2) and [Fe(OH)2(C4O4)] (3) are described. Pale yellow cubes of 1 and brown red crystals of 2 were obtained from the reaction of Co(OH)2 and squaric acid at 200 °C. Brown needle of 3 were obtained similarly from Fe(SO4) · 7H2O, squaric acid and NaOH. 1 consists of a cubic sodalite arrangement with empty cavities where the Co atoms are connected by μ4-squarate and two trans-water molecules each, while 2 and 3 contain metal-hydroxide double-chains of edge-sharing octahedral, brucite-type for 2 and goethite for 3, connected by μ6-squarate. 2 contains water molecules in the channels which can be removed and re-inserted repeatedly without loss of crystallinity. All three compounds possess 3D frameworks made up of coordination and hydrogen bonds. 1 behaves as a paramagnet while 2 and 3 are antiferromagnets and 2 transforms to a ferromagnet reversibly upon dehydration and rehydration. The structures of two one-dimensional polymers employing 2,5-pyridinedicarboxylate, [Co2(H2O)6(2,5-pydc)2] · 2H2O (4) and Cu(2,5-pydc)2 (5), are also reported.

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Acknowledgement

This work was funded by the CNRS-France, Ministry of Education, Science, Sports, and Culture, Japan. H.K. thanks the JSPS for a Young Scientist Fellowship.

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Authors and Affiliations

  1. Toyota Central R and D Labs. Inc., 41-1 Yokomichi, Nagakute, Aichi-gun, Aichi, 480-1131, Japan

    Hitoshi Kumagai & Hideo Sobukawa

  2. Laboratoire de Chimie de Coordination Organique, UMR7140, CNRS Université Louis Pasteur, Institut Le Bel, 4 rue Blaise Pascal, Strasbourg Cedex, 67000, France

    Mohamedally Kurmoo

Authors
  1. Hitoshi Kumagai
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  2. Hideo Sobukawa
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  3. Mohamedally Kurmoo
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Correspondence to Hitoshi Kumagai.

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Kumagai, H., Sobukawa, H. & Kurmoo, M. Hydrothermal syntheses, structures and magnetic properties of coordination frameworks of divalent transition metals. J Mater Sci 43, 2123–2130 (2008). https://doi.org/10.1007/s10853-007-2033-8

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  • DOI: https://doi.org/10.1007/s10853-007-2033-8

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