Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids

摘要

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.