Open AccessMetal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids
Author(s) -
Knies Maximilian,
Groh Matthias F.,
Pietsch Tobias,
Lê Anh Mai,
Ruck Michael
Publication year - 2021
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.202000246
Subject(s) - ionic liquid , chemistry , monoclinic crystal system , crystallography , intercalation (chemistry) , cationic polymerization , ionic bonding , crystal structure , metal , tetrahedron , inorganic chemistry , ion , organic chemistry , catalysis
Bi 2 S 3 was dissolved in the presence of either AuCl/PtCl 2 or AgCl in the ionic liquids [BMIm]Cl ⋅ x AlCl 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.