Ln3MBi5 (Ln=Pr, Nd, Sm; M=Zr, Hf): Intermetallics with Hypervalent Bismuth Chains

Jason F. Khoury, Xiaoyu Song, Leslie M. Schoop

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We report five new isostructural compounds in the Ln3MBi5 (Ln=Pr, Nd, Sm; M=Zr, Hf) family, and compare them to the recently reported Sm3ZrBi5 analogue. Ln3MBi5 crystallizes in the P63/mcm space group, hosting the anti-Hf5Sn3Cu structure type. The one-dimensional structure consists of hypervalent Bi2− chains and face-sharing MBi6 octahedra that form chains along the c axis. A framework of Ln3+ cations charge balances and separates the two motifs. The Bi−Bi and M−Bi bond lengths decrease as the Ln cation becomes smaller across the period, but there is almost no difference in either bond length when the identity of M changes, as expected because Zr and Hf have the exact same radii due to lanthanide contraction. We present a structural stability map showing the limits of cation stability in the structure, with La3+ and U3+ as the largest cations and Sm3+ as the smallest cation. X-ray photoelectron spectra suggest ambiguous valence states in the Ln3MBi5 structure depending on the identity of the M atom. This work further expands the Ln3MBi5 family and sheds new light on how their bonding behavior may vary based on chemical composition.

Original languageEnglish (US)
Article numbere202200123
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Issue number15
StatePublished - Aug 12 2022

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry


  • 1D chains
  • bismuthide intermetallics
  • hypervalent bonding
  • single crystal x-ray diffraction
  • topological Materials
  • x-ray photoelectron spectroscopy


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