Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 11, Issue 2, Pages 712-718Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200400774
Keywords
carbonate; cluster compounds; lanthanides; polyoxometalates; self-assembly
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Carbonate-assisted hydrolysis of Y or Yb-III ions in the presence of the trivacant Wells-Dawson polyoxo-anion, alpha-[P2W15O56](12-), produced two polyoxometalate-supported Y- or Yb-III-hydroxo/oxo clusters, which have been characterized by single-crystal Xray structure determination. The structure of the Y complex consists of a distorted Y-4(OH)(4) cubane cluster encapsulated by two lacunary alpha-[P2W15O56](12-) units, while the Yb cluster features a hexametallic core centered around a mu(6)-oxo atom with each Yb-3(III) triangular face capped by an oxo or a hydroxo group. Magnetization measurements of the ytterbium(III) derivative suggested that intermolecular dipolar exchange is present at low temperatures (below 15 K). Despite its absence in the structures themselves, control experiments show that carbonate not only functions in the hydrolysis, it also influences the structure of the complexes by complexation to yttrium and the f-block elements.
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