Dynamic disorder of Bi82+ clusters in the plastic phase (Bi8)3Bi[InI4]9

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Aron Wosylus - , TUD Dresden University of Technology, Max Planck Institute for Chemical Physics of Solids (Author)
  • Vitaly Dubenskyy - , TUD Dresden University of Technology (Author)
  • Ulrich Schwarz - , Max Planck Institute for Chemical Physics of Solids (Author)
  • Michael Ruck - , Chair of Inorganic Chemistry II, TUD Dresden University of Technology (Author)

Abstract

Black, air-insensitive crystals of the bismuth-rich tetra-iodido- indate(III) (Bi8)3Bi[InI4]9 have been prepared from melts of the contributing elements. X-ray diffraction on a single crystal at 293 K and 220 K revealed a cubic structure with [InL 4]- tetrahedra, isolated Bi3+ ions and rotationally disordered Bi82+ square anti-prisms ace group Fm3̄c; a = 20.162(2) Å at T = 293(1)]. The principal arrangement of the complex ions corresponds to the AuCu3 type. The small bulk modulus Bo = 12(1) GPa and its large pressure derivative B o' = 11(1) as well as the low Debye temperature θD = 52 K are in accordance with a plastic behavior. Cooling below 148(1) K induces the first order transition into an ordered phase with 0.43 % higher density but much larger unit cell and lower crystallographic point group. The transition enthalpy AH ≈ 3.8 kJ-mol-1 and transition entropy AS ≈ 3 R were determined from specific heat data. A similar reversible phase transition into a lower symmetric structure is observed at a pressure of approximately 5 GPa. (Bi8)3Bi[InI4]9 is a diamagnetic semiconductor.

Details

Original languageEnglish
Pages (from-to)1030-1035
Number of pages6
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume635
Issue number6-7
Publication statusPublished - May 2009
Peer-reviewedYes

External IDs

ORCID /0000-0002-2391-6025/work/159171902

Keywords

ASJC Scopus subject areas

Keywords

  • Bismuth, Cluster compounds, Order disorder transition, Plastic phase, Polycations