Tuning Magnetism of [MnSb4]9- Cluster in Yb14MnSb11 through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation

Yufei Hu, Chih Wei Chen, Huibo Cao, F. Makhmudov, Jason H. Grebenkemper, M. N. Abdusalyamova, Emilia Morosan, Susan M. Kauzlarich

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29 Scopus citations


Single crystals of Yb14-xRExMnSb11 (0 < x < 0.6, RE = Pr, Nd, Sm, and Gd) were synthesized by Sn flux. The compounds are iso-structural with Ca14AlSb11 (I41/acd), and their compositions were determined by wavelength-dispersive spectroscopy. Yb14MnSb11 is described as a partially screened d-metal Kondo system with the isolated [MnSb4]9- tetrahedral cluster having a d5 + hole configuration that results in four unpaired electrons measured in the ferromagnetically ordered phase. All of the Yb atoms in Yb14MnSb11 are present as Yb2+, and the additional RE in Yb14-xRExMnSb11 is trivalent, contributing one additional electron to the structure and altering the magnetic properties. All compounds show ferromagnetic ordering in the range of 39-52 K attributed to the [MnSb4]9- magnetic moment. Temperature-dependent DC magnetization measurements of Yb14-xPrxMnSb11 (0.44 ≤ x ≤ 0.56) show a sharp downturn right below the ferromagnetic transition temperature. Single-crystal neutron diffraction shows that this downturn is caused by a spin reorientation of the [MnSb4]9- magnetic moments from the ab-plane to c-axis. The spin reorientation behavior, caused by large anisotropy, is also observed for similar x values of RE = Nd but not for RE = Sm or Gd at any value of x. In Pr-, Nd-, and Sm-substituted crystals, the saturation moments are consistent with ∼4 unpaired electrons attributed to [MnSb4]9-, indicating that local moments of Pr, Nd, and Sm do not contribute to the ferromagnetic order. In the case of RE = Pr, this is confirmed by neutron diffraction. In contrast, the magnetic measurements of RE = Gd show that the moments of Gd ferromagnetically order with the moments of [MnSb4]9-, and reduced screening of moments on Mn2+ is evident. The sensitive variation of magnetic behavior is attributed to the various RE substitutions resulting in different interactions of the 4f-orbitals with the 3d-orbitals of Mn in the [MnSb4]9- cluster conducted through 5p-orbitals of Sb.

Original languageEnglish (US)
Pages (from-to)12422-12431
Number of pages10
JournalJournal of the American Chemical Society
Issue number38
StatePublished - Sep 28 2016

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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