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

Emanuel Makrlík; Petr Toman; Petr Vaňura; Bruce A. Moyer

doi:10.1016/j.molstruc.2012.07.049

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

Emanuel Makrlík, Petr Toman, Petr Vaňura, Bruce A. Moyer

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

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Abstract

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs⁺ (aq) + I^- (aq) + 1 (org) ⇔ 1sCs⁺ (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 log K_ex (1sCs⁺, I ^-) = 2.1 ± 0.1. Further, the stability constant of the 1sCs⁺ complex in FS 13 saturated with water was calculated for a temperature of 25 °C: log β_org (1sCs⁺) = 9.9 ± 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1sCs⁺ was derived. In the resulting 1sCs⁺ 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-π interaction.

Original language	English
Pages (from-to)	14-18
Number of pages	5
Journal	Journal of Molecular Structure
Volume	1033
DOIs	https://doi.org/10.1016/j.molstruc.2012.07.049
State	Published - Feb 6 2013

Funding

This work was supported by the Grant Agency of Faculty of Environmental Sciences, Czech University of Life Sciences, Prague, Project No.: 42900/1312/3114 “Environmental Aspects of Sustainable Development of Society,” by the Czech Ministry of Education, Youth, and Sports (Project MSM 6046137307), and by the Czech Science Foundation (Project P 205/10/2280). The computer time at the MetaCentrum (Project LM 2010005), as well as at the Institute of Physics (computer Luna/Apollo), Academy of Sciences of the Czech Republic, is gratefully acknowledged. Finally, the participation of BAM was sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy.

Funders	Funder number
Czech Ministry of Education, Youth, and Sports	MSM 6046137307
Czech University of Life Sciences	42900/1312/3114
Grant Agency of Faculty of Environmental Sciences
U.S. Department of Energy
Basic Energy Sciences
Seventh Framework Programme	261323
Chemical Sciences, Geosciences, and Biosciences Division
Grantová Agentura České Republiky	P 205/10/2280

Keywords

Calix[4]arene-bis(t-octylbenzo-18-crown-6)
Cesium cation
Complex structure
Complexation
DFT calculations
Extraction and stability constants

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10.1016/j.molstruc.2012.07.049

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

abstract = "From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I- (aq) + 1 (org) ⇔ 1sCs+ (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 log Kex (1sCs+, I -) = 2.1 ± 0.1. Further, the stability constant of the 1sCs+ complex in FS 13 saturated with water was calculated for a temperature of 25 °C: log βorg (1sCs+) = 9.9 ± 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1sCs+ was derived. In the resulting 1sCs+ 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-π interaction.",

keywords = "Calix[4]arene-bis(t-octylbenzo-18-crown-6), Cesium cation, Complex structure, Complexation, DFT calculations, Extraction and stability constants",

author = "Emanuel Makrl{\'i}k and Petr Toman and Petr Va{\v n}ura and Moyer, {Bruce A.}",

year = "2013",

month = feb,

day = "6",

doi = "10.1016/j.molstruc.2012.07.049",

language = "English",

volume = "1033",

pages = "14--18",

journal = "Journal of Molecular Structure",

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T1 - Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18- crown-6)

T2 - Extraction and DFT study

AU - Makrlík, Emanuel

AU - Toman, Petr

AU - Vaňura, Petr

AU - Moyer, Bruce A.

PY - 2013/2/6

Y1 - 2013/2/6

N2 - From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I- (aq) + 1 (org) ⇔ 1sCs+ (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 log Kex (1sCs+, I -) = 2.1 ± 0.1. Further, the stability constant of the 1sCs+ complex in FS 13 saturated with water was calculated for a temperature of 25 °C: log βorg (1sCs+) = 9.9 ± 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1sCs+ was derived. In the resulting 1sCs+ 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-π interaction.

AB - From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I- (aq) + 1 (org) ⇔ 1sCs+ (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 log Kex (1sCs+, I -) = 2.1 ± 0.1. Further, the stability constant of the 1sCs+ complex in FS 13 saturated with water was calculated for a temperature of 25 °C: log βorg (1sCs+) = 9.9 ± 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1sCs+ was derived. In the resulting 1sCs+ 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-π interaction.

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KW - Complexation

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KW - Extraction and stability constants

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

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Keywords

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