Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

Journal Article · Mon Dec 31 23:00:00 EST 2007 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja7102179· OSTI ID:972007

Wintergerst, Mr. Matthieu ^[1]; Levitskaia, Tatiana G. ^[2]; Moyer, Bruce A ^[3]; Sessler, Jonathan L. ^[4]; Delmau, Laetitia Helene ^[3]

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1. Ecole Nationale Superieure de Chimie de Paris
2. Pacific Northwest National Laboratory (PNNL)
3. ORNL
4. University of Texas

Solvent extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs. cesium salt and receptor concentration, indicating the formation of an ion-paired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent extraction system, either with chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride than for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a very polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion-pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.

• Research Organization: Oak Ridge National Laboratory (ORNL)
• Sponsoring Organization: SC USDOE - Office of Science (SC)
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 972007
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 130; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
BINDING ENERGY
CATIONS
CESIUM
CESIUM BROMIDES
CESIUM CHLORIDES
CHLORIDES
DISTRIBUTION
HALIDES
NITRATES
NITROBENZENE
SOLVENT EXTRACTION
SOLVENTS
STOICHIOMETRY
STRUCTURAL MODELS
WATER
anion binding
anion receptor
bromide
calixpyrrole
cesium
chloride
halide
ion-pair extraction
macrocycle
nitrate