Ca3Pt4+xGe13−y and Yb3Pt4Ge13: new derivatives of the Pr3Rh4Sn13 structure type

• Published in: Dalton transactions : an international journal of inorganic chemistry 2012-01, Vol.41 (2), p.6299-639
• Main Authors: Gumeniuk, Roman, Akselrud, Lev, Kvashnina, Kristina O, Schnelle, Walter, Tsirlin, Alexander A, Curfs, Caroline, Rosner, Helge, Schöneich, Michael, Burkhardt, Ulrich, Schwarz, Ulrich, Grin, Yuri, Leithe-Jasper, Andreas
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt30339f

The new phases Ca 3 Pt 4+ x Ge 13− y ( x = 0.1; y = 0.4; space group I 2 1 3; a = 18.0578(1) Å; R I = 0.063; R P = 0.083) and Yb 3 Pt 4 Ge 13 (space group P 4 2 cm ; a = 12.7479(1) Å; c = 9.0009(1) Å; R I = 0.061, R P = 0.117) are obtained by high-pressure, high-temperature synthesis and crystallize in new distortion variants of the Pr 3 Rh 4 Sn 13 type. Yb 3 Pt 4 Ge 13 features Yb in a temperature-independent non-magnetic 4f 14 (Yb 2+ ) configuration validated by X-ray absorption spectra and resonant inelastic X-ray scattering data. Ca 3 Pt 4+ x Ge 13− y is diamagnetic ( χ 0 = −5.05 × 10 −6 emu mol −1 ). The Sommerfeld coefficient γ = 4.4 mJ mol −1 K −2 for Ca 3 Pt 4+ x Ge 13− y , indicates metallic properties with a low density of states at the Fermi level in good agreement with electronic structure calculation ( N ( E F ) = 3.3 eV −1 /f.u.)); the Debye temperature ( D ) is 398 K. The new phases Ca 3 Pt 4+ x Ge 13− y ( x = 0.1; y = 0.4; space group I 2 1 3; a = 18.0578(1) Å) and Yb 3 Pt 4 Ge 13 (space group P 4 2 cm ; a = 12.7479(1) Å; c = 9.0009(1) Å) are obtained by high-pressure, high-temperature synthesis.