Low-temperature ordering in the cluster compound (Bi8)T1[AlCl4]3

Knies, Maximilian; Kaiser, Martin; Lê Anh, Mai; Efimova, Anastasia; Doert, Thomas; Ruck, Michael

doi:10.3390/inorganics7040045

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Low-temperature ordering in the cluster compound (Bi₈)T1[AlCl₄]₃

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Ruck, Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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引用

Knies, M., Kaiser, M., Lê Anh, M., Efimova, A., Doert, T., & Ruck, M. (2019). Low-temperature ordering in the cluster compound (Bi₈)T1[AlCl₄]₃. Inorganics, 7:, pp. 1-9. doi:10.3390/inorganics7040045.

引用: https://hdl.handle.net/21.11116/0000-0003-BCED-F

要旨

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 roomtemperature revealed a structure containing 1 ∞ [Tl(AlCl 4)3]2- 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. © 2019 by the authors.