Publication | Open Access
Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids
11
Citations
47
References
2020
Year
Bi<sub>2</sub> S<sub>3</sub> was dissolved in the presence of either AuCl/PtCl<sub>2</sub> or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl<sub>3</sub> (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<sub>4</sub> S<sub>4</sub> )[AlCl<sub>4</sub> ]<sub>5</sub> (1) or Ag(Bi<sub>7</sub> S<sub>8</sub> )[S(AlCl<sub>3</sub> )<sub>3</sub> ]<sub>2</sub> [AlCl<sub>4</sub> ]<sub>2</sub> (2) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl<sub>2</sub> , suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi<sub>4</sub> S<sub>4</sub> )<sup>4+</sup> heterocubanes and [AlCl<sub>4</sub> ]<sup>-</sup> tetrahedra as well as [BMIm]<sup>+</sup> 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<sub>7</sub> S<sub>8</sub> )<sup>5+</sup> spiro-dicubanes, [S(AlCl<sub>3</sub> )<sub>3</sub> ]<sup>2-</sup> tetrahedra triples, isolated [AlCl<sub>4</sub> ]<sup>-</sup> tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K.
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