Sb₂S₃ and CuCl were reacted in the ionic liquid [BMIm]Cl · 4.4AlCl₃ (BMIm=1-n-butyl-3-methylimidazolium) at 200°C. Upon cooling to room temperature, orange-red colored, air-sensitive crystals of Cu(Sb₂S₃)[AlCl₄] precipitated. X-ray diffraction on a single-crystal revealed an orthorhombic crystal structure, in which cationic [Cu(Sb₂S₃)]⁺ layers are separated by tetrahedral [AlCl₄]⁻ anions. The uncharged Sb₂S₃ partial structure consists of one-dimensional strands with covalent Sb-S single bonds. The copper(I) cation is coordinated by three sulfur atoms and by one of chlorine atoms of the [AlCl₄]⁻ anion. An optical band gap of 2.14 eV was deduced from UV/Vis spectra. In very good agreement, a band gap of 2.07 eV results from DFT-based calculations involving a new implementation of the bifunctional formalism for the exchange energy. By treatment with 0.1 molar hydrochloric acid, AlCl₃ was leached from Cu(Sb₂S₃)[AlCl₄] yielding a compound with the presumed composition Cu(Sb₂S₃)Cl. Hydrolysis at higher pH resulted in Cu₂₋ₓS and Sb₄O₅Cl₂.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:90569 |
| Date | 04 April 2024 |
| Creators | Grasser, Matthias A., Finzel, Kati, Ruck, Michael |
| Publisher | Wiley-VCH |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, doc-type:article, info:eu-repo/semantics/article, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 1521-3749, e202200021, 10.1002/zaac.202200021, info:eu-repo/grantAgreement/Deutsche Forschungsgemeinschaft/SPP 1708: Materialsynthese nahe Raumtemperatur/237028221/ |
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