Abstract
Bi(2) S(3) was dissolved in the presence of either AuCl/PtCl(2) or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl(3) (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](Bi(4) S(4) )[AlCl(4) ](5) (1) or Ag(Bi(7) S(8) )[S(AlCl(3) )(3) ](2) [AlCl(4) ](2) (2) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl(2) , suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi(4) S(4) )(4+) heterocubanes and [AlCl(4) ](-) 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 (Bi(7) S(8) )(5+) spiro-dicubanes, [S(AlCl(3) )(3) ](2-) tetrahedra triples, isolated [AlCl(4) ](-) tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K.