Guest inclusion properties of calix[6]arene-based unimolecular cage compounds. On their high Cs+ and Ag+ selectivity and very slow metal exchange rates

Article abstract of DOI:10.1016/S0040-4020(97)10261-7

The reaction of 1.3.5-tri-O-alkylated calix[6]arenes with 1,3,5- tris(bromomethyl)benzene yielded capped calix[6]arenes (2 with ten-butyl groups on the upper tim and 3 without tert-butyl groups) in unexpectedly high yields (80 - 91%). Combined studies of 2 and 3 by MM3 computation, X-ray analysis, and ¹H NMR spectroscopy established that these calix[6]arenes feature a unique structure consisting of alternately-arranged three flattened mesitylene-linked phenyl units and three stand-up anisole units. Particularly, compound 2 possesses a closed ionophoric cavity: the upper hemisphere is closed by three ten-butyl groups of anisole units and the lower hemisphere is closed by a mesitylene cap and three anisole methoxy groups. The ¹H NMR spectrum was scarcely changed at wide temperature range (30 ~ 130 °C), indicating that the structure is extremely rigidified. Both solvent extraction and spectroscopic studies established that this cavity shows the high selectivity toward Cs⁺ among alkali metal cations, the high affinity with Ag⁺, and the moderate affinity with RNH₃⁺. Very surprisingly, the association-dissociation processes for 2 and cesium picrate was so slow that the rate could be followed by a conventional spectroscopic method. The thermodynamic parameters determined by kinetic studies disclosed that the major driving-force for Cs⁺ inclusion is the entropy term based on the desolvation.