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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Knies, Maximilian
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (4/4 displayed)
- 2021Speciation of Copper(II)‐Betaine Complexes as Starting Point for Electrochemical Copper Deposition from Ionic Liquidscitations
- 2021Pb[PtBi6I12] – Infinite Chains of Heavy Atom Clusterscitations
- 2018The Intermetalloid Cluster Cation (CuBi8)3+citations
- 2015Bi2S3 bipyramids in layered sulfides M2Bi2S3(AlCl4)2 (M = AG, CU)citations
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article
Bi2S3 bipyramids in layered sulfides M2Bi2S3(AlCl4)2 (M = AG, CU)
Abstract
<p>Black Cu<sub>2</sub>Bi<sub>2</sub>S<sub>3</sub>(AlCl<sub>4</sub>)<sub>2</sub> and orange Ag<sub>2</sub>Bi<sub>2</sub>S<sub>3</sub>(AlCl<sub>4</sub>)<sub>2</sub> were synthesized by solvent-free reaction (polycrystalline powders) as well as in Lewis-acidic ionic liquids (crystals) at temperatures of 200 ° C or lower. X-ray diffraction on single-crystals of Cu<sub>2</sub>Bi<sub>2</sub>S<sub>3</sub>(AlCl<sub>4</sub>)<sub>2</sub> revealed two centrosymmetric polytypes: a rhombohedral one, space group R3¯c [a = 658.02(3) pm, c = 6794.3(3) pm], with six formula units in the unit cell (6R polytype), and a hexagonal one, space group P6<sub>3</sub>/m [a = 658.71(6) pm, c = 2265.5(3) pm], with two formula units (2H polytype). Ag<sub>2</sub>Bi<sub>2</sub>S<sub>3</sub>(AlCl<sub>4</sub>)<sub>2</sub> is homeotypic and crystallizes in the acentric hexagonal space group P6 2c with [a = 691.65(3) pm, c = 2207.86(9) pm, and two formula units per unit cell (2H′ polytype). All structures consist of <sup>2</sup><sub>∞</sub>[(M<sup>+</sup>)<sub>2</sub>Bi<sub>2</sub>S<sub>3</sub>] layers (M = Cu, Ag) separated bydouble layers of AlCl<sub>4</sub><sup>-</sup> tetrahedra and differ mainly in their stacking sequences and the orientation of the AlCl<sub>4</sub><sup>-</sup> groups. The sulfidometalate layer is a honeycomb-like network with M<sup>+</sup> and S<sup>2-</sup> ions in plane, whereas pairs of Bi<sup>3+</sup> cations occupy positions above and below the plane. The analysis of chemical bonding reveals strong covalent twocenter two-electron bonds in the five-atomic bipyramidal Bi<sub>2</sub>S<sub>3</sub> unit (D<sub>3h</sub> symmetry) and covalent bonding with much higher ionic component to the coin metal cations. The DFT-optimized shape of an isolated hypothetical Bi<sub>2</sub>S<sub>3</sub> molecule differs only marginally from that in the layer. Hence, the compounds might be interpreted as Bi<sub>2</sub>S<sub>3</sub> molecules embedded in MAlCl<sub>4</sub> salts. Optical bandgaps of 1.6 eV (M = Cu) and 2.2 eV (M = Ag) were deduced from diffuse reflectance measurements. DFT-based quantum chemical calculations indicate direct bandgaps of the same magnitude.</p>