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

Research output: Contribution to journalArticle

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Abstract

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
Volume138
Issue number38
DOIs
StatePublished - Sep 28 2016

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Magnetism
Neutron Diffraction
Substitution reactions
Tuning
Electrons
Neutron diffraction
Magnetic moments
Wavelength dispersive spectroscopy
Single crystals
Transition Temperature
Anisotropy
Magnetic variables measurement
Superconducting transition temperature
Magnetization
Spectrum Analysis
Magnetic properties
Screening
Metals
Fluxes
Atoms

ASJC Scopus subject areas

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

Cite this

Tuning Magnetism of [MnSb4]9- Cluster in Yb14MnSb11 through Chemical Substitutions on Yb Sites : Appearance and Disappearance of Spin Reorientation. / Hu, Yufei; Chen, Chih Wei; Cao, Huibo; Makhmudov, F.; Grebenkemper, Jason H.; Abdusalyamova, M. N.; Morosan, Emilia; Kauzlarich, Susan M.

In: Journal of the American Chemical Society, Vol. 138, No. 38, 28.09.2016, p. 12422-12431.

Research output: Contribution to journalArticle

Hu, Y, Chen, CW, Cao, H, Makhmudov, F, Grebenkemper, JH, Abdusalyamova, MN, Morosan, E & Kauzlarich, SM 2016, 'Tuning Magnetism of [MnSb4]9- Cluster in Yb14MnSb11 through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation', Journal of the American Chemical Society, vol. 138, no. 38, pp. 12422-12431. https://doi.org/10.1021/jacs.6b05636
Hu, Yufei ; Chen, Chih Wei ; Cao, Huibo ; Makhmudov, F. ; Grebenkemper, Jason H. ; Abdusalyamova, M. N. ; Morosan, Emilia ; Kauzlarich, Susan M. / Tuning Magnetism of [MnSb4]9- Cluster in Yb14MnSb11 through Chemical Substitutions on Yb Sites : Appearance and Disappearance of Spin Reorientation. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 38. pp. 12422-12431.
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abstract = "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.",
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T2 - Appearance and Disappearance of Spin Reorientation

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AU - Chen, Chih Wei

AU - Cao, Huibo

AU - Makhmudov, F.

AU - Grebenkemper, Jason H.

AU - Abdusalyamova, M. N.

AU - Morosan, Emilia

AU - Kauzlarich, Susan M.

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N2 - 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.

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