TY - GEN A1 - Poddig, Hagen A1 - Donath, Tom A1 - Gebauer, Paul A1 - Finzel, Kati A1 - Kohout, Miroslav A1 - Wu, Yuandong A1 - Schmidt, Peer A1 - Doert, Thomas T1 - Rare Earth Metal Polytellurides RETe1.8 (RE = Gd, Tb, Dy) – Directed Synthesis, Crystal and Electronic Structures, and Bonding Features T2 - Zeitschrift für Anorganische und Allgemeine Chemie N2 - Single crystals of the polytellurides RETe1.8 of gadolinium, terbium, and dysprosium were prepared by chemical vapor transport and alkali metal halide flux reactions. To determine proper synthesis conditions for the desired target composition, the binary phase diagram Gd-Te was evaluated by CalPhaD methods. The compounds are isostructural to SmTe1.8 and crystallize in space group P4/n (no. 85) with lattice parameters of a = 966.10(4), 960.00(3), and 957.33(2) pm and c = 1794.15(10), 1785.77(6), and 1779.38(5) pm for GdTe1.8, TbTe1.8 and DyTe1.8, respectively. The structures consist of puckered [RETe] double slabs and planar telluride layers composed of Te2 dumbbells and linear Te3 units in accordance with ELI-D based bonding analyses. The latter can be understood as a Te3(4–) anion. GdTe1.8 is a semiconductor with a bandgap of 0.19 eV/0.17 eV (experimental / calculated). Magnetization data confirm trivalent RE ions and indicate antiferromagnetic order at T(N) = 12 K for TbTe1.8 and T(N) = 9.8 K for DyTe1.8, whereas GdTe1.8 remains paramagnetic down to 2 K. KW - Phase diagrams KW - Crystal structure KW - Crystal growth KW - Chemical vapor transport KW - Thermodynamc modelling KW - Chalcogenides KW - Polytellurides KW - Bonding analysis Y1 - 2018 UR - https://onlinelibrary.wiley.com/doi/10.1002/zaac.201800382 U6 - https://doi.org/10.1002/zaac.201800382 SN - 1521-3749 SN - 0044-2313 VL - 644 IS - 24 SP - 1886 EP - 1896 ER - TY - GEN A1 - Pabst, Falk A1 - Chang, Jen‐Hui A1 - Finzel, Kati A1 - Kohout, Miroslav A1 - Schmidt, Peer A1 - Ruck, Michael T1 - The Subbromide Bi5Br4 – On the Existence of a Hidden Phase T2 - Zeitschrift für Anorganische und Allgemeine Chemie N2 - Black and irregularly shaped crystals of the bismuth‐rich bromide Bi5Br4 were obtained as a by‐product of the reaction of CsBr, Bi, and BiBr3. X‐ray diffraction on a single‐crystal revealed its orthorhombic structure with the space group Pmmn (no. 59) and lattice parameters a = 1800.0(2) pm, b = 1476.1(1) pm, and c = 924.5(2) pm at 296 K. The structure is composed of Bi82+ and Bi95+ polycations and bromidobismuthate(III) anions according to the structured formula Bi5Br4 = Bi20Br16 = Bi82+Bi95+[BiBr5]2–[Bi2Br11]5–. Bi5Br4 is the bismuth‐richest among the bismuth subhalides containing isolated polycations. Extensive differential scanning calorimetry studies indicate that Bi5Br4 decomposes at 262 °C, i.e. one degree below the bismuth‐rich eutectic at 263 °C. All attempts towards a rational synthesis yielded predominantly the neighboring phases BiBr and Bi6Br7. KW - Bromine KW - Bismuth KW - Cluster KW - Phase Diagrams KW - Polycations KW - Crystal structure Y1 - 2020 UR - https://onlinelibrary.wiley.com/doi/10.1002/zaac.201800149 U6 - https://doi.org/10.1002/zaac.201800149 VL - 646 IS - 3 SP - 149 EP - 155 ER -