Type-II Clathrate Na24-δGe136 from a Redox-Preparation Route

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Xian Juan Feng - , Max Planck Institute for Chemical Physics of Solids (Author)
  • Matej Bobnar - , Max Planck Institute for Chemical Physics of Solids, J. Stefan Institute (Author)
  • Swantje Lerch - , Chair of Physical Organic Chemistry, TUD Dresden University of Technology (Author)
  • Harry Biller - , Chair of Physical Organic Chemistry, TUD Dresden University of Technology (Author)
  • Marcus Schmidt - , Max Planck Institute for Chemical Physics of Solids (Author)
  • Michael Baitinger - , Max Planck Institute for Chemical Physics of Solids (Author)
  • Thomas Strassner - , Chair of Physical Organic Chemistry, TUD Dresden University of Technology (Author)
  • Yuri Grin - , Max Planck Institute for Chemical Physics of Solids (Author)
  • Bodo Böhme - , Max Planck Institute for Chemical Physics of Solids (Author)

Abstract

The metastable type-II clathrate Na24-δGe136 was obtained from Na12Ge17 by applying a two-step procedure. At first, Na12Ge17 was reacted at 70 °C with a solution of benzophenone in the ionic liquid (IL) 1,3-dibutyl-2-methylimidazolium-bis(trifluoromethylsulfonyl) azanide. The IL was inert towards Na12Ge17, but capable of dissolving the sodium salts formed in the redox reaction. By annealing at 340 °C under an argon atmosphere, the X-ray amorphous intermediate product was transformed to crystalline Na24-δGe136 (δ≈2) and α-Ge in an about 1 : 1 mass ratio. The product was characterized by X-ray powder diffraction, chemical analysis, and 23Na solid-state NMR spectroscopy. Metallic properties of Na24-δGe136 were revealed by a significant Knight shift of the 23Na NMR signals and by a Pauli-paramagnetic contribution to the magnetic susceptibility. At room temperature, Na24-δGe136 slowly ages, with a tendency to volume decrease and sodium loss.

Details

Original languageEnglish
Pages (from-to)12776-12787
Number of pages12
JournalChemistry - A European Journal
Volume27
Issue number50
Publication statusPublished - 6 Sept 2021
Peer-reviewedYes

External IDs

PubMed 34270132

Keywords

Keywords

  • intermetallic clathrates, ionic liquids, metastable compounds, redox chemistry, Zintl phases