Flexible Thioether−Ag(I) Interactions for Assembling Large Organic Ligands into Crystalline Networks

From searching the Cambridge Structural Database (CSD), we noticed an exceptionally widespread distribution of the interatomic distances (from 2.39 to 3.52 Å) between thioether S atoms and Ag(I) ions, in comparison with the cases in other common ligands such as nitriles and pyridyls. The variable bonding distances point to a highly flexible and reversible nature of thioether−Ag(I) interaction, which might help crystallize large and complex organic molecules into ordered coordination networks under mild conditions. We provide a number of new structures for illustration. In 1, two Ag(I) ions are coordinated by three 1,2,3-tris(methylthio)phenyl groups (i.e., 9 S atoms) to form a three-bladed paddlewheel block as a node for an enlarged honeycomb sheet. In 2, a porphyrin molecule with four 1,2,3-tris(phenylthio)phenyl groups coordinates to Ag(I) atoms to form a parallelogram net, featuring free-standing phenylthio groups in the channel. In 3, a starburst molecule with six 4-methylthiophenyl groups attached to the triphenylene core is crystallized with AgOTf (triflate) to form a complex three-dimensional net, with a supramolecular topology featuring a combination of edge-sharing octahedra (the rutile chain) and vertex-sharing octahedra (the ReO3 chain).