Journal of Cluster Science

, Volume 19, Issue 1, pp 259–273 | Cite as

Mixed-Valence 24-Vanadophosphate Decorated with Six RuII(dmso)3 Groups: [{RuII 3(dmso)9PVV 11VIVRuIIIO37(OH)3}2]8−

  • Li-Hua Bi
  • Sib Sankar Mal
  • Nadeen H. Nsouli
  • Michael H. Dickman
  • Ulrich Kortz
  • Saritha Nellutla
  • Naresh S. Dalal
  • Manuel Prinz
  • Georg Hofmann
  • Manfred Neumann
Original Paper


The mixed-valence 24-vanadophosphate \( {\left[ {{\left\{ {{\text{Ru}}^{{{\text{II}}}}_{3} (dmso)_{9} {\text{PV}}^{{\text{V}}}_{{11}} {\text{V}}^{{{\text{IV}}}} {\text{Ru}}^{{{\text{III}}}} {\text{O}}_{{37}} {\text{(OH)}}_{3} } \right\}}_{2} } \right]}^{{8 - }} \) (1) has been synthesized and characterized in the solid state by IR, magnetism, EPR, XPS, and elemental analysis. Single-crystal X-ray analysis was carried out on \( {\text{Na}}_{8} {\left[ {{\left\{ {{\text{Ru}}^{{{\text{II}}}}_{3} (dmso)_{9} {\text{PV}}^{{\text{V}}}_{{11}} {\text{V}}^{{{\text{IV}}}} {\text{Ru}}^{{{\text{III}}}} {\text{O}}_{{37}} {\text{(OH)}}_{3} } \right\}}_{2} } \right]} \cdot 46{\text{H}}_{2} {\text{O}} \) (Na-1), which crystallizes in the triclinic system, space group \( \hbox{P}\overline{1} \), with a = 17.168(3) Å, b = 18.1971(14) Å, c = 20.1422(13) Å, α = 114.753(3)°, β = 99.390(4)°, γ = 95.124(4)°, and Z = 2. Polyanion 1 has an unusual, open structure composed of 2 RuIIIO6 octahedra, 2 VIVO6 octahedra, 14 VVO5 square-pyramids, 8 VVO4 tetrahedra, and 2 PO4 tetrahedra which are all directly linked via edges and corners. The outer surface of 1 is decorated with six RuII(dmso)3 groups. XPS studies on Na-1 confirm the presence of 2 RuIII and 6 RuII as well as 22 VV and 2 VIV centers. Magnetic susceptibility data on Na-1 show that the VIV–RuIII pairs are coupled antiferromagnetically, with J 1 = −13 K and J 2 ∼ −3 K. We did not detect any peak in our EPR measurements on Na-1, thus supporting the conclusion that Na-1 is diamagnetic in its ground state.


Polyoxovanadate Mixed-valence cluster Self-assembly Ruthenium X-ray crystallography NMR XPS 



U.K. thanks Jacobs University and the German Research Council (DFG) for research support (DFG-KO-2288/3-2 and DFG-KO-2288/4-1). S.N. thanks Johan van Tol at the National High Magnetic Field Laboratory for helpful discussions. S.N. and N.S.D. acknowledge funding via the State of Florida and NSF Cooperative Agreement Grant DMR-0084173 and the NSF grant DMR-0520481. M.P. acknowledges financial support of the Ph.D. program of Lower Saxony (Germany). Figures 1 and 2 were generated by Diamond Version 3.1e (copyright Crystal Impact GbR).

Supplementary material

10876_2007_180_MOESM1_ESM.doc (1.5 mb)
Supporting Information Available: Room temperature NMR spectra (13C, 1H, 51V) for Na-1 redissolved in H2O/D2O. (DOC 111 kb)


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Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  • Li-Hua Bi
    • 1
    • 2
  • Sib Sankar Mal
    • 1
  • Nadeen H. Nsouli
    • 1
  • Michael H. Dickman
    • 1
  • Ulrich Kortz
    • 1
  • Saritha Nellutla
    • 3
    • 4
  • Naresh S. Dalal
    • 3
    • 4
  • Manuel Prinz
    • 5
  • Georg Hofmann
    • 5
  • Manfred Neumann
    • 5
  1. 1.School of Engineering and ScienceJacobs University BremenBremenGermany
  2. 2.College of ChemistryJilin UniversityChangchunChina
  3. 3.Department of Chemistry and BiochemistryFlorida State UniversityTallahasseeUSA
  4. 4.National High Magnetic Field Laboratory and Center for Interdisciplinary Magnetic ResonanceTallahasseeUSA
  5. 5.Department of PhysicsUniversity of OsnabrückOsnabruckGermany

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