Cesium Complex of an Unsymmetrical Calix[4]crown-dibenzocrown-6

An unsymmetrical calix4]-bis-crown ether having both conventional crown-6 and dibenzocrown-6 rings in a fixed 1,3-alternate conformation was synthesized with good yield by the reaction of a monocyclic calix4]crown-6 with dibenzodimesylate in the presence of cesium carbonate. The cesium ion selectivity among alkali metal ions increased compared to symmetrical calix4]-bis-crown-6. The solid state structureof the ligand-cesium complex illustrates a 1:2 complex ratio. On the contrary, insolution, e.g., extraction equilibrium and ¹H NMR experiment gave a 1:1 complex ratio. From the result of the chemical shift change upon metal ion complex, the cesium ion seems to prefer the dibenzocrown loop to the conventional crown-6 ring.