Octanuclear Rare-Earth Clusters

Christopher G. Pernin, James A Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticle

18 Scopus citations

Abstract

The polyoxo rare-earth core Ln84-O)(μ3-OH)12 10+ (Ln = Y, Gd, and Yb) has been synthesized from the appropriate rare-earth chloride hydrate and K2Se and Se in dmf (dimethylformamide). The cluster core is ligated with a variety of polyselenido chains in addition to a number of dmf molecules. The structure of the Gd8(dmf)134-O)(μ3-OH) 12(Se3)(Se4)2(Se5) 2 cluster, 1, was determined by X-ray diffraction methods. It is similar to an Eu cluster previously characterized. Two new clusters, Yb8(dmf)114-O)(μ3-OH) 12(Se4)2(Se5)2Cl 2 · dmf, 2, and Y8(dmf)124-O)(μ3-OH) 12(Se4)4Cl2 · 6 dmf, 3, have also been synthesized and characterized. Clusters 2 and 3 have the same octanuclear core of rare-earth atoms as the Gd cluster but contain two chloro ligands in two isomeric conformations in place of the Se3 2- ring in the Gd cluster. The geometry of the Ln8 core is described as a triangulated dodecahedron with μ3-OH groups capping the 12 faces. A μ4-O atom centers the cluster with close contacts to four Ln atoms in an approximate tetrahedral arrangement. Pertinent crystallographic data are: Compound 1, monoclinic, C2h 5-P21/n, a = 14.410(3) A, b = 24.439(5) A, c = 28.927(6) A, β = 101.05(3)°, V = 9998(3)A3, T = 106(2) K, Z = 4; Compound 2, orthorhombic, D2h 15-Pbca, a = 17.049(9) A, b = 24.68(1) A, c = 45.03(2) A, V = 18,945(16) A3, T = 153(2) K, Z = 8; Compound 3, monoclinic, C2h 5-P21/c, a = 18.728(1) A, b = 29.263(1) A, c = 20.548(1) A, β = 90.144(1)°, V = 11,261(1) A3, T = 153(2) K, Z = 4.

Original languageEnglish (US)
Pages (from-to)71-90
Number of pages20
JournalJournal of Cluster Science
Volume10
Issue number1
DOIs
StatePublished - Jan 1 1999

Keywords

  • Chalcogenide
  • Cluster
  • Polyoxo
  • Polyselenido
  • Rare-earth

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Materials Science(all)
  • Condensed Matter Physics

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