Remarkably selective Ag+ extraction and transport by thiolariat ethers

Synthesis and metal binding properties of thiolariat ethers, where a sulfide side chain is introduced into a framework of a crown ether, have been performed. Remarkably high Ag+ selectivity among heavy metal ions was observed in solvent extraction and transport across a liquid membrane using thiolariat ethers with a 15-crown-5 ring as carriers. Thiolariat ethers with a 12-crown-4 or a 18-crown-6 do not exhibit such a high Agi selectivity. The former binds metal ions weakly, and the latter recognizes Pb2+ as well as Ag+. The corresponding oxygen analogs, i.e. lariat ethers, do not show Ag+ selectivity. The Ag+ binding strength of the sulfoxide and sulfone analogs is much lower than that of thiolariat ethers. Thiolariat ethers with a benzocrown framework containing a sulfide chain at the 4 position of the benzene nucleus showed very low affinity to Ag+. Extractability and transport ability using various thiolariat ether derivatives strongly suggested that this high Ag+ selectivity is a result of the synergistic coordination of the ring oxygen and the sulfur atom of the thiolariat ether. NMR chemical shifts of protons and carbons in the proximity of the sulfur atom of the thiolariat ether were changed significantly in accordance with the synergistic coordination described above. 1:1 Complexation between a thiolariat ether and Ag+ were supported by a Job plot using the chemical shift of the methylene protons adjacent to the sulfur atom.