Rapid Metal Ions Shuttling through 1,3-Alternate Thiacalix[4]crown Tubes
- 26 July 2003
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (17) , 6720-6725
- https://doi.org/10.1021/jo034666y
Abstract
Several new thiacalix[4]monocrown and thiacalix[4]biscrown compounds were synthesized. Their metal ion extractabilities are found to be lower than those of conventional calix[4]crowns. By use of X-ray crystal structures and 1H NMR spectroscopy, this result is explained by weaker electrostatic interactions of the polyether ring oxygen atoms with the metal ions and diminished π-metal ion interactions between the metal ions and the aromatic rings of the thiacalix[4]crowns. Temperature-dependent 1H NMR spectroscopic measurements reveal coalescence temperatures Tcintra and Tcinter for metal ion exchange. In one case, this exchange was rationalized as metal ion shuttling through a thiacalix[4]biscrown tube. Since the metal ions are less tightly complexed by the polyether units in thiacalix[4]biscrowns than in conventional calix[4]biscrowns, more facile metal ion exchange between the two polyether units takes place in the former.Keywords
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