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Mercaptothiacalixarenes Steer 24 Copper(I) Centers to form a Hollow‐Sphere Structure Featuring Cu 2 S 2 Motifs with Exceptionally Short Cu⋅⋅⋅Cu Distances
Author(s) -
Frank Nicolas,
Dallmann André,
BraunCula Beatrice,
Herwig Christian,
Limberg Christian
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201915882
Subject(s) - random hexamer , thioether , chemistry , copper , acetonitrile , monomer , crystallography , coordination sphere , calixarene , host–guest chemistry , ion , stereochemistry , inorganic chemistry , molecule , crystal structure , supramolecular chemistry , organic chemistry , polymer
Tetramercaptotetrathiacalix[4]arene ( LH 4 ) can be used as a coordination platform to bind four Cu I ions at the thiolate and thioether S atoms. Donor ligands such as phosphanes can stabilize the resulting [LCu 4 ] units, which then remain monomeric ( [(Ph 3 PCu) 4 L] ). In the absence of donor ligands, they aggregate, providing a hexamer ( [LCu 4 ] 6 ) in high yields, with a hollow‐sphere structure formed by an unprecedented Cu 24 S 48 cage that is surrounded by the organic framework of the calixarene chalices. Preliminary NMR experiments with regard to the host‐guest chemistry in solution showed that the compound represents a polytopic host for acetonitrile and methane.