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Low-Temperature Ordering in the Cluster Compound (Bi₈)Tl[AlCl₄]₃

  • The reaction of Bi, BiCl₃, and TlCl in the ionic liquid [BMIm]Cl·4AlCl₃ (BMIm = 1-n-butyl-3-methylimidazolium) at 180 °C yielded air-sensitive black crystals of (Bi₈)Tl[AlCl₄]₃. X-ray diffraction on single crystals at room temperature revealed a structure containing [Tl(AlCl₄)₃]∞12− strands separated by isolated Bi₈²⁺ square antiprisms. The thallium(I) ion is coordinated by twelve Cl⁻ ions of six [AlCl₄]⁻ groups, resulting in a chain of face-sharing [TlCl₁₂]¹¹⁻ icosahedra. The Bi₈²⁺ polycation is disordered, simulating a threefold axis through its center and overall hexagonal symmetry (space group P6₃/m). Slowly cooling the crystals to 170 K resulted in increased order in the Bi₈ cluster orientations. An ordered structure model in a supercell with a’ = 2a, b’ = 2b, c’ = 3c and the space group P6₅ was refined. The structure resembles a hexagonal perovskite, with complex groups in place of simple ions.

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Metadaten
Author: Maximilian Knies, Martin Kaiser, Mai Lê Anh, Anastasia EfimovaORCiD, Thomas DoertORCiD, Michael RuckORCiD
DOI:https://doi.org/10.3390/inorganics7040045
Title of the source (English):Inorganics
Document Type:Scientific journal article peer-reviewed
Language:English
Year of publication:2019
Tag:bismuth; cluster compounds; hexagonal perovskite; ionic liquids; low-valen; low-valent compounds; order–disorder transition; orientational disorder; polycations; pseudosymmetry
Volume/Year:7
Issue number:4
First Page:1
Last Page:9
Faculty/Chair:Fakultät 2 Umwelt und Naturwissenschaften / FG Anorganische Chemie
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