Controlling cesium cation recognition via cation metathesis within an ion pair receptor

Sung Kuk Kim, Gabriela I. Vargas-Zúñiga, Benjamin P. Hay, Neil J. Young, Lætitia H. Delmau, Charles Masselin, Chang Hee Lee, Jong Seung Kim, Vincent M. Lynch, Bruce A. Moyer, Jonathan L. Sessler

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO 3, in solution (10% methanol-d 4 in chloroform-d) as inferred from 1H NMR spectroscopic analyses. The addition of KClO 4 to these cesium salt complexes leads to a novel type of cation metathesis in which the "exchanged" cations occupy different binding sites. Specifically, K + becomes bound at the expense of the Cs + cation initially present in the complex. Under liquid-liquid conditions, receptor 3 is able to extract CsNO 3 and CsCl from an aqueous D 2O layer into nitrobenzene-d 5 as inferred from 1H NMR spectroscopic analyses and radiotracer measurements. The Cs + cation of the CsNO 3 extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO 4 solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.

Original languageEnglish
Pages (from-to)1782-1792
Number of pages11
JournalJournal of the American Chemical Society
Volume134
Issue number3
DOIs
Publication statusPublished - 2012 Jan 25

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Cesium
Nitrobenzene
Cations
Positive ions
Ions
Binding sites
Binding Sites
Chloroform
Chlorine compounds
Bearings (structural)
Salts
Nuclear magnetic resonance
Liquids
Complexation
X-Ray Diffraction
Anions
Methanol
Negative ions
Gases
Single crystals

ASJC Scopus subject areas

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

Cite this

Kim, S. K., Vargas-Zúñiga, G. I., Hay, B. P., Young, N. J., Delmau, L. H., Masselin, C., ... Sessler, J. L. (2012). Controlling cesium cation recognition via cation metathesis within an ion pair receptor. Journal of the American Chemical Society, 134(3), 1782-1792. https://doi.org/10.1021/ja209706x

Controlling cesium cation recognition via cation metathesis within an ion pair receptor. / Kim, Sung Kuk; Vargas-Zúñiga, Gabriela I.; Hay, Benjamin P.; Young, Neil J.; Delmau, Lætitia H.; Masselin, Charles; Lee, Chang Hee; Kim, Jong Seung; Lynch, Vincent M.; Moyer, Bruce A.; Sessler, Jonathan L.

In: Journal of the American Chemical Society, Vol. 134, No. 3, 25.01.2012, p. 1782-1792.

Research output: Contribution to journalArticle

Kim, SK, Vargas-Zúñiga, GI, Hay, BP, Young, NJ, Delmau, LH, Masselin, C, Lee, CH, Kim, JS, Lynch, VM, Moyer, BA & Sessler, JL 2012, 'Controlling cesium cation recognition via cation metathesis within an ion pair receptor', Journal of the American Chemical Society, vol. 134, no. 3, pp. 1782-1792. https://doi.org/10.1021/ja209706x
Kim SK, Vargas-Zúñiga GI, Hay BP, Young NJ, Delmau LH, Masselin C et al. Controlling cesium cation recognition via cation metathesis within an ion pair receptor. Journal of the American Chemical Society. 2012 Jan 25;134(3):1782-1792. https://doi.org/10.1021/ja209706x
Kim, Sung Kuk ; Vargas-Zúñiga, Gabriela I. ; Hay, Benjamin P. ; Young, Neil J. ; Delmau, Lætitia H. ; Masselin, Charles ; Lee, Chang Hee ; Kim, Jong Seung ; Lynch, Vincent M. ; Moyer, Bruce A. ; Sessler, Jonathan L. / Controlling cesium cation recognition via cation metathesis within an ion pair receptor. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 3. pp. 1782-1792.
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