Journal of Cluster Science

, Volume 17, Issue 2, pp 291–302 | Cite as

Inducing Molecular Growth in an {Mo57Fe6}-type Nanocluster: Synthesis, Structure, and Properties of \(\{\hbox{Mo}_{57}\hbox{(Mo)}_{2}\hbox{Fe}^{\rm III}_{6}\}\)*

  • John Fielden
  • Yurii L. Malaestean
  • Arkady Ellern
  • Ricardo García-Serres
  • Leroy Cronin
  • Paul KögerlerEmail author

The reaction of the polyoxomolybdate anion \([\hbox{Mo}_{32}^{\rm VI}\hbox{(MoNO)}_{4}\hbox{O}_{108}(\hbox{H}_{2}\hbox{O})_{16}]^{12-} =\{\hbox{Mo}_{36}\hbox{(NO)}_{4}\}\) with FeII salts and hydrazine sulfate yields the cluster anion \([\hbox{Mo}^{\rm V/VI}_{51}(\hbox{Mo}^{\rm VI}\hbox{O})_{2}\hbox{Fe}^{\rm III}_{6}\hbox{(MoNO)}_{6}\hbox{O}_{176}\hbox{(OH)}_{3} (\hbox{H}_{2}\hbox{O})_{22}]^{15-}\) (1a), isolated as its corresponding ammonium salt (NH4)15 1a · 36H2O (1) (space group P63/mmc, a=b=23.607(5) Å, c=26.767(6) Å, 4076 unique reflections, 293 parameters). Despite the absence of oxygen and the reducing conditions the product comprises only FeIII centers as determined by a combination of spectroscopic, magnetic and crystallographic analysis. Reduction of peripheral Mo centers causes the aggregation of two additional [MoVIO]4+ groups onto the archetypal {Mo57M6} structure. The single-crystal X-ray determined structure of 1 is reported.


Polyoxometalates polyoxomolybdates iron(III) self-assembly molecular magnetism Mössbauer spectroscopy 



Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. W-7405-Eng-82. Y.L.M. thanks MRDA/CRDF for a travel fellowship (award no. MTFP-04–03). We thank Professor B. H. Huynh for the 57Fe Mössbauer data.


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Copyright information

© Springer Science+Business Media, Inc. 2006

Authors and Affiliations

  • John Fielden
    • 1
  • Yurii L. Malaestean
    • 1
  • Arkady Ellern
    • 2
  • Ricardo García-Serres
    • 3
  • Leroy Cronin
    • 4
  • Paul Kögerler
    • 1
    Email author
  1. 1.Ames LaboratoryIowa State UniversityAmesUSA
  2. 2.Department of ChemistryIowa State UniversityAmesUSA
  3. 3.Department of PhysicsEmory UniversityAtlantaUSA
  4. 4.Department of ChemistryUniversity of GlasgowGlasgowUK

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