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 (P = 15 GPa, T = 1073 K) and BaGe(6-x) (P = 10 GPa, T = 1073 K) which are metastable at ambient conditions. In BaGe(6-x), 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-x) is associated with the establishment of free electron pairs around the defects. In accordance with the electron precise composition of BaGe(6-x) for x = 0.5, physical measurements evidence semiconducting electron transport properties which are combined with low thermal conductivity.

Dumbbells of five-connected silicon atoms and superconductivity in the binary silicides MSi3 (M = Ca, Y, Lu).

The new metastable binary silicides MSi(3) (M = Ca, Y, Lu) have been synthesized by high-pressure, high-temperature reactions at pressures between 12(2) and 15(2) GPa and temperatures from 900(100) to 1400(150) K. The atomic patterns comprise intricate silicon layers of condensed molecule-like Si(2) dimers. The alkaline-earth element adopts the oxidation state +2, while the rare-earth and transition metals realize +3. All of the compounds exhibit BCS-type superconductivity with weak electron-phonon coupling below critical temperatures of up to 7 K.

Dumbbells of five-connected Ge atoms and superconductivity in CaGe3.

CaGe(3) has been synthesized at high-pressure, high-temperature conditions. The atomic pattern comprises intricate germanium layers of condensed moleculelike dimers. Below T(c) = 6.8 K, type II superconductivity with moderately strong electron-phonon coupling is observed.

Synthesis, crystal structures, and hydrogen-storage properties of Eu(AlH4)2 and Sr(AlH4)2 and of their decomposition intermediates, EuAlH5 and SrAlH5.

Complex Eu(AlH(4))(2) and Sr(AlH(4))(2) hydrides have been prepared by a mechanochemical metathesis reaction from NaAlH(4) and europium or strontium chlorides. The crystal structures were solved from powder X-ray diffraction data in combination with solid-state (27)Al NMR spectroscopy. The thermolysis pathway was analyzed in detail, allowing identification of new intermediate EuAlH(5)/SrAlH(5) compounds. Rehydrogenation experiments indicate that the second decomposition step is reversible.

Cs(8-x)Si(46): a type-I clathrate with expanded silicon framework.

The synthesis of the new binary Cs(8-x)Si(46) (shown here) completes the series of binary alkali metal silicides with a clathrate-I structure M(8-x)Si(46) (M = Na, K, Rb, Cs). In contrast with the lighter homologues, Cs(8-x)Si(46) can be prepared only at elevated pressures. The compound was obtained at 1200 degrees C between 2-10 GPa and the Cs content rises with applied pressure.