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 (4xMeO-, 4xn-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 (4xn-PrO, cone, 1,3-alternate conformers) and the conformational mobile (4xMeO) thiacalix[4]arenes, which indicates the generality of this behaviour in thiacalixarene series. (c) 2007 Elsevier Ltd. All rights reserved.