1. Max-Planck-Institut für Chemische Physik fester Stoffe, 01187 Dresden, Germany
2. Department of Chemistry and the Texas Center for Superconductivity, University of Houston, Houston, Texas 77204-5003, USA

Correspondence to: Arnold M. Guloy^1,2Yuri Grin¹ Correspondence and requests for materials should be addressed to Yu.G. (Email: grin@cpfs.mpg.de) and A.M.G. (Email: aguloy@uh.edu).

Abstract

The challenges associated with synthesizing expanded semiconductor frameworks with cage-like crystal structures continue to be of interest^{1, 2}. Filled low-density germanium and silicon framework structures have distinct properties that address important issues in thermoelectric phonon glass–electron crystals³, superconductivity⁴ and the possibility of Kondo insulators⁵. Interest in empty framework structures of silicon and germanium is motivated by their predicted wide optical bandgaps of the same magnitude as quantum dots and porous silicon, making them and their alloys promising materials for silicon-based optoelectronic devices^{6, 7}. Although almost-empty Na_1-xSi₁₃₆ has already been reported^{8, 9}, the synthesis of guest-free germanium clathrate has so far been unsuccessful. Here we report the high-yield synthesis and characteristics of germanium with the empty clathrate-II structure through the oxidation of Zintl anions in ionic liquids under ambient conditions. The approach demonstrates the potential of ionic liquids as media for the reactions of polar intermetallic phases.

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