BaGe₆ and BaGe_6‑x: Incommensurately Ordered Vacancies as Electron Traps

We report the high-pressure high-temperature synthesis of the germanium-based framework compounds BaGe₆ (<i>P</i> = 15 GPa, <i>T</i> = 1073 K) and BaGe_6–<i>x</i> (<i>P</i> = 10 GPa, <i>T</i> = 1073 K) which are metastable at ambient conditions. In BaGe_6‑<i>x</i>, partial fragmentation of the BaGe₆ network involves incommensurate modulations of both atomic positions and site occupancy. Bonding analysis in direct space reveals that the defect formation in BaGe_6–<i>x</i> is associated with the establishment of free electron pairs around the defects. In accordance with the electron precise composition of BaGe_6‑<i>x</i> for <i>x</i> = 0.5, physical measurements evidence semiconducting electron transport properties which are combined with low thermal conductivity