Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids.

ABSTRACT: Bi₂ S₃ 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](Bi₄ S₄ )[AlCl₄ ]₅ (1) or Ag(Bi₇ S₈ )[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 (Bi₄ S₄ )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 (Bi₇ S₈ )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.

SUBMITTER: Knies M 

PROVIDER: S-EPMC7874255 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature