Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

Journal Article · Mon Dec 31 23:00:00 EST 2012 · Journal of Molecular Structure

DOI:https://doi.org/10.1016/j.molstruc.2012.07.049· OSTI ID:1055545

Makrlik, Emanuel ^[1]; Toman, Petr ^[2]; Vanura, Petr ^[3]; Moyer, Bruce A ^[4]

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1. Czech University of Life Sciences, Prague, Kamy´cká
2. Institute of Macromolecular Chemistry, Prague
3. Institute of Chemical Technology, Prague, Czech Republic
4. ORNL

From extraction experiments and c-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I (aq) + 1 (org),1Cs+ (org) + I (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logKex (1Cs+, I) = 2.1 0.1. Further, the stability constant of the 1Cs+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log borg (1Cs+) = 9.9 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1Cs+ was derived. In the resulting 1Cs+ complex, the central cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation p interaction.

• Research Organization: Oak Ridge National Laboratory (ORNL)
• Sponsoring Organization: SC USDOE - Office of Science (SC)
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 1055545
• Journal Information: Journal of Molecular Structure, Journal Name: Journal of Molecular Structure Vol. 1033; ISSN 0022-2860
• Country of Publication: United States
• Language: English

Related Subjects

cesium cation