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
This publication has 13 references indexed in Scilit:
- Synthesis and alkali cation extraction ability of 1,3-alt-thiacalix[4]mono(crown) ethersTetrahedron Letters, 2002
- Lariat Ether Receptor Systems Show Experimental Evidence for Alkali Metal Cation−π InteractionsAccounts of Chemical Research, 2002
- Synthesis and alkali cation extraction ability of 1,3-alt-thiacalix[4]bis(crown) ethersTetrahedron Letters, 2002
- Heterogeneous Binuclear Complexation of 1,3-Alternate Calix[4]-Bis-Crown Bearing Two Different Crown RingsThe Journal of Organic Chemistry, 2000
- High Complexation Ability of Thiacalixarene with Transition Metal Ions. The Effects of Replacing Methylene Bridges of Tetra(p-t-butyl)calix[4]arenetetrol by Epithio GroupsBulletin of the Chemical Society of Japan, 1998
- Cation binding properties of a novel 1,3-alternate calix[4]biscrown. Formation of 1:1 and 1:2 complexes and unique cation tunneling across a calix[4]arene cavityTetrahedron Letters, 1995
- Synthesis, Complexation, and Membrane Transport Studies of 1,3-Alternate Calix[4]arene-crown-6 Conformers: A New Class of Cesium Selective IonophoresJournal of the American Chemical Society, 1995
- X-ray crystallographic studies of a 1,3-alternate-calix[4]arene·Na+ complex. Is the cation-π interaction operative between the benzene rings and Na+?Tetrahedron Letters, 1994
- On the Origin of High Ionophoricity of 1,3-Alternate Calix[4]arenes: .pi.-donor Participation in Complexation of Cations and Evidence for Metal-Tunneling through the Calix[4]arene CavityJournal of the American Chemical Society, 1994
- Selective Transport of Alkali Metal Cations in Solvent Extraction by Proton-Ionizable Dibenzocrown EthersJournal of Coordination Chemistry, 1992