Abstract
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.