Knies Maximilian, Groh Matthias F, Pietsch Tobias, Lê Anh Mai, Ruck Michael
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01069, Dresden, Germany.
Institut für Anorganische Chemie, RWTH Aachen, Landoltweg 1, 52074, Aachen, Germany.
ChemistryOpen. 2021 Feb;10(2):110-116. doi: 10.1002/open.202000246. Epub 2020 Oct 19.
Bi S was dissolved in the presence of either AuCl/PtCl or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl (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 S )[AlCl ] (1) or Ag(Bi S )[S(AlCl ) ] [AlCl ] (2) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl , suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi S ) heterocubanes and [AlCl ] 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 S ) spiro-dicubanes, [S(AlCl ) ] tetrahedra triples, isolated [AlCl ] tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K.
在离子液体[BMIm]Cl⋅xAlCl（BMIm = 1 - 正丁基 - 3 - 甲基咪唑鎓；x = 4 - 4.3）中，通过在180或200°C对混合物进行退火处理，将Bi₂S₃溶解于AuCl/PtCl或AgCl存在的体系中。冷却至室温后，分别析出橙色、对空气敏感的BMIm[AlCl₄]（1）或Ag(Bi₂S₃)[S(AlCl₄)] [AlCl₄]（2）晶体。在没有AuCl/PtCl的情况下不会形成1，这表明金属阳离子起着至关重要的作用。对1的单晶进行X射线衍射分析，揭示了一种单斜晶体结构，其中包含（Bi₂S₃）异立方烷和[AlCl₄]四面体以及[BMIm]阳离子。通过固态核磁共振光谱证实了离子液体的插入，揭示了不寻常的耦合行为。2的晶体结构由（Bi₂S₃）螺双立方烷、[S(AlCl₄)]四面体三聚体、孤立的[AlCl₄]四面体和严重无序的银（I）阳离子组成。在缓慢冷却至100 K时，2中未发生阳离子有序化。
