Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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An NMR Study on Complexation of Cesium Ion by p-tert-Butylcalix[6]arene Ethyl Ester

  • Chung, Kee-Choo (School of Chemistry and Molecular Engineering, College of Natural Sciences, Seoul National University) ;
  • Namgoong, Hyun (E&A Center, Kolon Central Research Park) ;
  • Lee, Jo-Woong (School of Chemistry and Molecular Engineering, College of Natural Sciences, Seoul National University)
  • Published : 2004.05.20
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Abstract

Complexation of cesium ion by p-tert-butylcalix[6]arene ethyl ester was studied by NMR spectroscopy in nonpolar $CDCl_3$ and polar acetone-$d_6$ and the results were compared with each other. Analysis of temperature dependent $^1H$ spectra and titration curves reveals that both solvents result in a 1 : 1 cone-form complex with nonpolar $CDCl_3$yielding a more tightly bound one than acetone-$d_6$. Unexpectedly, at very low temperature, we have found that two phenyl ring proton peaks of equal intensity appear both in $CDCl_3$and in acetone-$d_6$ solution which gradually collapse and eventually coalesce into a single line as temperature is raised. This observation could be interpreted in terms of the chemical exchange through direct and/or indirect interconversion between two equivalent conformations possible the complex in both solvents over the temperature range observed. And broadening of $^{133}Cs$ (I = 7/2) nmr line with increasing temperature has also been observed, indicating the exchange of $^{133}Cs$ ion between the complex and the solvent. From numerical fitting of lineshape changes for one-dimensional $^1H$ and $^{133}Cs$ spectra, the exchange rate constants and other relevant parameters for this conformational interconversion and the complex-solvent exchange were deduced.

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