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.

中文翻译：

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离子液体中阳离子硫化铋古巴烷的金属辅助合成

Bi ₂ S ₃在 AuCl/PtCl ₂或 AgCl 存在下通过退火溶解在离子液体 [BMIm]Cl ⋅  x AlCl ₃ (BMIm=1 - n-丁基-3-甲基咪唑；x =4-4.3)中混合物在 180 或 200 °C。冷却至室温后，[BMIm](Bi ₄ S ₄ )[AlCl ₄ ] ₅ ( 1 ) 或 Ag(Bi ₇ S ₈ )[S(AlCl ₃ ) ₃ ] ₂ [AlCl ₄ ] 的橙色、空气敏感晶体] ₂ ( 2) 分别沉淀。1在没有 AuCl/PtCl ₂的情况下不会形成，这表明金属阳离子的重要作用。单晶1的 X 射线衍射显示单斜晶体结构，包含 (Bi ₄ S ₄ ) ⁴⁺杂立方和 [AlCl ₄ ] ^-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嵌入，揭示了不寻常的耦合行为。2的晶体结构由 (Bi ₇ S ₈ ) ⁵⁺ 螺二立方烷组成，[S(AlCl₃ ) ₃ ] ^2-四面体三元组、孤立的 [AlCl ₄ ] ^-四面体和严重无序的银 (I) 阳离子。在缓慢冷却到 100 K 时， 2中没有发生阳离子排序。