Journal of Materials Science

, Volume 43, Issue 7, pp 2123–2130

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


    • Toyota Central R and D Labs. Inc.
  • Hideo Sobukawa
    • Toyota Central R and D Labs. Inc.
  • Mohamedally Kurmoo
    • Laboratoire de Chimie de Coordination Organique, UMR7140CNRS Université Louis Pasteur, Institut Le Bel
Novel Routes of Advanced Materials Processing and Applications

DOI: 10.1007/s10853-007-2033-8

Cite this article as:
Kumagai, H., Sobukawa, H. & Kurmoo, M. J Mater Sci (2008) 43: 2123. doi:10.1007/s10853-007-2033-8


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.

Copyright information

© Springer Science+Business Media, LLC 2007