KF and CsF recognition and extraction by a calix[4]crown-5 strapped calix[4]pyrrole multitopic receptor

Sung Kuk Kim, Vincent M. Lynch, Neil J. Young, Benjamin P. Hay, Chang Hee Lee, Jong Seung Kim, Bruce A. Moyer, Jonathan L. Sessler

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

On the basis of 1H NMR spectroscopic analyses and single crystal X-ray crystal structural data, the ion-pair receptor 1, bearing a calix[4]pyrrole for anion binding and calix[4]arene crown-5 for cation recognition, was found to act as a receptor for both CsF and KF ion-pairs. Both substrates are bound strongly but via different binding modes and with different complexation dynamics. Specifically, exposure to KF in 10% CD3OD in CDCl3 leads first to complexation of the K+ cation by the calix[4]arene crown-5 moiety. As the relative concentration of KF increases, then the calix[4]pyrrole subunit binds the F- anion. Once bound, the K+ cation and the F- anion give rise to a stable 1:1 ion-pair complex that generally precipitates from solution. In contrast to what is seen with KF, the CsF ion-pair interacts with receptor 1 in two different modes in 10% CD3OD in CDCl3. In the first of these, the Cs+ cation interacts with the calix[4]arene crown-5 ring weakly. In the second interaction mode, which is thermodynamically more stable, the Cs + cation and the counteranion, F-, are simultaneously bound to the receptor framework. Further proof that system 1 acts as a viable ion-pair receptor came from the finding that receptor 1 could extract KF from an aqueous phase into nitrobenzene, overcoming the high hydration energies of the K+ and F- ions. It was more effective in this regard than a 1:1 mixture of the constituent cation and anion receptors (4 and 5).

Original languageEnglish
Pages (from-to)20837-20843
Number of pages7
JournalJournal of the American Chemical Society
Volume134
Issue number51
DOIs
Publication statusPublished - 2012 Dec 26

    Fingerprint

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Kim, S. K., Lynch, V. M., Young, N. J., Hay, B. P., Lee, C. H., Kim, J. S., Moyer, B. A., & Sessler, J. L. (2012). KF and CsF recognition and extraction by a calix[4]crown-5 strapped calix[4]pyrrole multitopic receptor. Journal of the American Chemical Society, 134(51), 20837-20843. https://doi.org/10.1021/ja310673p