Type-II Clathrate Na 24-δ Ge 136 from a Redox-Preparation Route.

The metastable type-II clathrate Na _24-δ Ge ₁₃₆ was obtained from Na ₁₂ Ge ₁₇ by applying a two-step procedure. At first, Na ₁₂ Ge ₁₇ 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 Na ₁₂ Ge ₁₇ , 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 Na _24-δ Ge ₁₃₆ (δ≈2) and α-Ge in an about 1 : 1 mass ratio. The product was characterized by X-ray powder diffraction, chemical analysis, and ²³ Na solid-state NMR spectroscopy. Metallic properties of Na _24-δ Ge ₁₃₆ were revealed by a significant Knight shift of the ²³ Na NMR signals and by a Pauli-paramagnetic contribution to the magnetic susceptibility. At room temperature, Na _24-δ Ge ₁₃₆ slowly ages, with a tendency to volume decrease and sodium loss.
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