| Abstract: | Extraction and transport behaviors of isomeric oxathia macrocycles (L2, ortho-; L3, meta- and L4, para-isomer) and their structure related open-chain compound (L1) towards Ag(I) picrate have been examined. From the plot of log (DAg(I)/[pic−]) vs. log [L]0 for all of the ionophores were linear with slope near unity, thereby confirming the 1:1:1 complex formations of Ag(I)/ligand/picrate ion to be extracted into the dichloromethane phase. The extractability of an acyclic ionophore was superior to those of the corresponding cyclic ones. In membrane transport experiments, the slow rate of release of Ag(I) from the membrane into the receiving phase seems to be responsible for lower transport efficiency. Upon addition of sodium thiosulfate as a stripping reagent in receiving phase, the efficiency of transport is significantly enhanced in the order of L1 (acyclic)>L2 (ortho-)>L3 (meta-)>L4 (para-) in accordance with those of log Kex values. It is hypothesized that the ion-pair complexation of L1 in extraction step would be more favorable in extraction and transport of Ag(I). Its structure have been confirmed by X-ray diffraction analysis of [Ag(L1)pic], where L1=1,10-bis(mercaptobenzylyl)-4,7-dioxadecane. |
