Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids |
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| Authors: | Maximilian Knies Dr. Matthias F. Groh Tobias Pietsch Mai Lê Anh Prof. Dr. Michael Ruck |
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| Affiliation: | 1. Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01069 Dresden, Germany;2. Institut für Anorganische Chemie, RWTH Aachen, Landoltweg 1, 52074 Aachen, Germany |
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| Abstract: | Bi2S3 was dissolved in the presence of either AuCl/PtCl2 or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl3 (BMIm=1-n-butyl-3-methylimidazolium; x=4–4.3) through annealing the mixtures at 180 or 200 °C. Upon cooling to room temperature, orange, air-sensitive crystals of [BMIm](Bi4S4)[AlCl4]5 ( 1 ) or Ag(Bi7S8)[S(AlCl3)3]2[AlCl4]2 ( 2 ) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl2, suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi4S4)4+ heterocubanes and [AlCl4]− tetrahedra as well as [BMIm]+ cations. The intercalation of the ionic liquid was confirmed via solid state NMR spectroscopy, revealing unusual coupling behavior. The crystal structure of 2 consists of (Bi7S8)5+ spiro-dicubanes, [S(AlCl3)3]2− tetrahedra triples, isolated [AlCl4]− tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K. |
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| Keywords: | bismuth heterocubanes ionic liquids ionothermal synthesis spirocubanes |
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