Unique self-assembly patterns based on thiacalix[4]arene–silver interactions

Novel self-assembled supramolecular networks were prepared by the interactions of thiacalix[4]arenes bearing simple alkyl groups on the lower rim (4×MeO–, 4×n-PrO–) with silver triflate. Contrary to the classical calix[4]arenes (with CH2 bridges between the aromatic moieties), the presence of four sulfur atoms enables the formation of S–Ag–S connections between the individual molecules leading to the coordination topology so far unknown in calixarene chemistry. These systems form infinite 1-D coordination polymeric structures in the solid state, where the thiacalixarene moieties are preorganized in a side-by-side arrangement. Interestingly, the linear coordination polymers were obtained using both the conformational immobilised (4×n-PrO, cone, 1,3-alternate conformers) and the conformational mobile (4×MeO) thiacalix[4]arenes, which indicates the generality of this behaviour in thiacalixarene series.