Yb(3)AuGe(2)In(3) was obtained as large single crystals in high yield from reactions run in liquid indium. Single crystal X-ray diffraction data show that Yb(3)AuGe(2)In(3) is an ordered variant of YbAuIn with lattice constants, a = b = 7.3153(8) Å and c = 4.4210(5) Å, and space group P(6)2m. The parent compound YbAuIn was also studied for comparison. YbAuIn crystallizes in the ZrNiAl structure type, hexagonal, P(6)2m space group with lattice parameters a = b = 7.7127(11) Å and c = 4.0294(8) Å. In Yb(3)AuGe(2)In(3), Ge substitutes for one of the two Au positions in the ternary compound Yb(3)Au(3)In(3). The structure can be described as alternating [Ge(2)In(3)] and [Yb(3)Au] slabs that stack along the c-axis. The magnetic susceptibility data follow a modified Curie-Weiss law. The effective magnetic moment μ(eff) of 0.52 μ(B)/Yb atom was deduced from the Curie constant and Curie-Weiss constant of θ(p) = -1.5 K indicating antiferromagnetic interactions in Yb(3)AuGe(2)In(3). X-ray absorption near edge spectroscopy (XANES) measurements indicate intermediate valency for Yb in both compounds. The metallic nature of both compounds was confirmed by the resistivity measurements. Specific heat data for Yb(3)AuGe(2)In(3) and YbAuIn give an electronic γ term of 31 and 84 mJ/mol·K(2), respectively, suggesting that the ternary analog is a "light" heavy fermion compound.
The family of materials RE(4)TGe(8) (RE = Yb, Gd; T = transition metal) exhibits directional zero thermal expansion (ZTE) via a process that is associated with the linking of planar square nets in the third dimension. The Ge square nets in these compounds exhibit commensurate long-range modulations similar to those observed in charge-density-wave compounds. The ZTE is manifested in the plane of the square nets from 10 to 300 K with negligible volume expansion below ∼160 K. The specific atomic arrangement in RE(4)TGe(8) enables a Poisson-like mechanism that allows the structure to contract along one direction as it expands only slightly in the perpendicular direction.
The quaternary compounds RE7Co4InGe12 (RE = Dy, Ho, Yb) were obtained from In flux reactions
as thin silver needles. RE7Co4InGe12 crystallizes in the tetragonal P4/m space group under a new structure
type which is characterized by columnar units forming three different types of channels with the RE
atoms situated within these channels. Investigation of the Yb analog with magnetic susceptibility
measurements, X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy
(XANES) revealed that Yb7Co4InGe12 is a mixed-valence compound and that the relative Yb3+/Yb2+
ratio is slightly temperature-dependent. Additionally, resistivity measurements for Yb7Co4InGe12 exhibited
negative magnetoresistance at low temperatures.
The germanide Eu(2)AuGe(3) was obtained as large single crystals in high yield from a reaction of the elements in liquid indium. At room temperature Eu(2)AuGe(3) crystallizes with the Ca(2)AgSi(3) type, space group Fmmm, an ordered variant of the AlB(2) type: a = 857.7(4), b = 1485.5(10), c = 900.2(4) pm. The gold and germanium atoms build up slightly distorted graphite-like layers which consist of Ge(6) and Au(2)Ge(4) hexagons, leading to two different hexagonal-prismatic coordination environments for the europium atoms. Magnetic susceptibility data showed Curie-Weiss law behavior above 50 K and antiferromagnetic ordering at 11 K. The experimentally measured magnetic moment indicates divalent europium. The compound exhibits a distinct magnetic anisotropy based on single crystal measurements and at 5 K it shows a metamagnetic transition at ∼10 kOe. Electrical conductivity measurements show metallic behavior. The structural transition at 130 K observed in the single crystal data was very well supported by the conductivity measurements. (151)Eu Mössbauer spectroscopic data show an isomer shift of -11.24 mm/s at 77 K, supporting the divalent character of europium. In the magnetically ordered regime one observes superposition of two signals with hyperfine fields of 26.0 (89%) and 3.5 (11%) T, respectively, indicating differently ordered domains.
The Zintl phase, Yb8Ge3Sb5 exhibits a complex lattice response and an abrupt negative thermal expansion below 15 K - subtle structural changes before and after the transition are consistent with temperature-induced electron transfer from (to) Yb 4f bands to (from) Sb 5p and Ge 4p bands.
Yb4Ag0.56Ge8 (I), Yb4Co1.17Ge8 (II), Yb4Cr1.07Ge8 (III), Yb4Cr1.04Ge8 (IV), Yb4Fe1.10Ge8 (V), Yb4Mn1.00Ge8 (VI), Yb4Ni1.12Ge8 (VII), and Gd4Cr1.33Ge8 (VIII) are synthesized from the elements (850 °C, 144 h) and characterized by XRD, XANES, and DFT band structure calculations.
The new intermetallic compound Yb7Ni4InGe12 was obtained as large silver needle shaped single crystals from reactive indium flux. Single crystal X-ray diffraction suggests that Yb7Ni4InGe12 crystallizes in the Yb7Co4InGe12 structure type, and tetragonal space group P4/m and lattice constants are a = b = 10.291(2) Å and c = 4.1460(8) Å. The crystal structure of Yb7Ni4InGe12 consists of columnar units of three different types of channels filled with the Yb atoms. The crystal structure of Yb7Ni4InGe12 is closely related to Yb5Ni4Ge10. The effective magnetic moment obtained from the magnetic susceptibility measurements in the temperature range 200-300 K is 3.66μB/Yb suggests mixed/intermediate valence behavior of ytterbium atoms. X-ray absorption near edge spectroscopy (XANES) confirms that Yb7Ni4InGe12 exhibits mixed valence.
Thermal properties D 3000Temperature-Induced Abrupt Volume Inflation in the Mixed-Valence Ternary Zintl Phase Yb8Ge3Sb5. -As revealed by powder XRD the title compound exhibits a complex structural and electronic response to changes in temperature. Yb8Ge3Sb5 shows an abrupt negative thermal expansion below 15 K. Subtle structural changes before and after the transition are consistent with temperature-induced electron transfer from (to) Yb 4f bands to (from) Sb 5p and Ge 4p bands. -(MARGADONNA*, S.; PRASSIDES, K.; CHONDROUDI, M.; SALVADOR, J. R.; KANATZIDIS, M. G.; Chem. Commun. (Cambridge) 2005, 46, 5754-5756; Sch. Chem., Univ. Edinburgh, Edinburgh EH9 3JJ, UK; Eng.) -W. Pewestorf 11-008
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