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Journal of Cluster Science

, Volume 24, Issue 4, pp 979–988 | Cite as

Systematic Study of the Interaction Between VIV Centres and LnIII Ions in Well Defined {V 2 IV LnIII}{AsIIIW9O33}2 Sandwich-Type Clusters: Part 2

  • Alice Merca
  • Jürgen Schnack
  • Joris van Slageren
  • Thorsten Glaser
  • Hartmut Bögge
  • Veronika Hoeke
  • Mechtild Läge
  • Achim Müller
  • Bernt KrebsEmail author
Original Paper

Abstract

The gadolinium (Gd) member of a new type of heteropolytungstates that contain one lanthanide and two transition metal ions in a triangular arrangement is reported. The compound NaK6Gd0.33 [((VO)2Gd(H2O)4K2(H2O)2(Na)(H2O)2)(α-B-AsW9O33)2]·24H2O (1) was prepared from acidified aqueous solutions of Na2WO4·2H2O, As2O3 and VOSO4·5H2O to which Gd3+ ions were added. The single crystal X-ray structure analysis (monoclinic, space group P21/m) shows that the anion consists of two [α-B-AsIIIW9O33]9− trilacunary Keggin-type units linked by two VO2+, one Gd3+ as well as weakly by two K+ and one Na+ ions, resulting in a sandwich-type structure with idealized C 2v symmetry. The problem of positioning crystal lattice and special polyoxometalate sites with different cations is discussed also in connection with supramolecular chemistry aspects and as an option for further research. A fit of the magnetic susceptibility yielded exchange coupling constants of J VV = −2.55 cm−1 (anti-ferromagnetic) between the vanadium ions and J GdV = 0.6 cm−1 (ferromagnetic) between the Gd and each of the two vanadium ions. The complete magnetochemical analysis also revealed a partial occupancy of the Na+ sites in the counter-cation–water system by Gd3+ ions (0.33 Gd3+ ions in total).

Keywords

Gadolinium Keggin ions Magnetic properties Polyoxometalates Supramolecular chemistry 

Notes

Acknowledgments

The authors thank the Deutsche Forschungsgemeinschaft for financial support. Furthermore, we acknowledge valuable comments of Prof. E. Coronado and of Dr. A. J. M. Al-Karawi.

Supplementary material

10876_2013_588_MOESM1_ESM.doc (32 kb)
Supplementary material 1 (DOC 32 kb)

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Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Alice Merca
    • 1
  • Jürgen Schnack
    • 2
  • Joris van Slageren
    • 3
  • Thorsten Glaser
    • 1
  • Hartmut Bögge
    • 1
  • Veronika Hoeke
    • 1
  • Mechtild Läge
    • 4
  • Achim Müller
    • 1
  • Bernt Krebs
    • 4
    Email author
  1. 1.Fakultät für ChemieUniversität BielefeldBielefeldGermany
  2. 2.Fakultät für PhysikUniversität BielefeldBielefeldGermany
  3. 3.Institut für Physikalische ChemieUniversität StuttgartStuttgartGermany
  4. 4.Institut für Anorganische und Analytische ChemieUniversität MünsterMünsterGermany

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