Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: Effect of receptor structure on sulphate-nitrate exchange selectivity

Bruce A. Moyer; Frederick V. Sloop; Christopher J. Fowler; Tamara J. Haverlock; Hyun Ah Kang; Ltitia H. Delmau; Diadra M. Bau; Md Alamgir Hossain; Kristin Bowman-James; James A. Shriver; Nathan L. Bill; Dustin E. Gross; Manuel Marquez; Vincent M. Lynch; Jonathan L. Sessler

doi:10.1080/10610271003763263

Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: Effect of receptor structure on sulphate-nitrate exchange selectivity

Bruce A. Moyer, Frederick V. Sloop, Christopher J. Fowler, Tamara J. Haverlock, Hyun Ah Kang, Ltitia H. Delmau, Diadra M. Bau, Md Alamgir Hossain, Kristin Bowman-James, James A. Shriver, Nathan L. Bill, Dustin E. Gross, Manuel Marquez, Vincent M. Lynch, Jonathan L. Sessler

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31 Scopus citations

Abstract

When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C _8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and β-decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1 receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range log K_bind = 2:14:8. Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.

Original language	English
Pages (from-to)	653-671
Number of pages	19
Journal	Supramolecular Chemistry
Volume	22
Issue number	11-12
DOIs	https://doi.org/10.1080/10610271003763263
State	Published - Nov 2010

Funding

Research at Oak Ridge National Laboratory (ORNL) was sponsored by the Division of Chemical Sciences, Geosciences and Biosciences, Office Basic Energy Sciences, US Department of Energy. Research at the University of Texas at Austin was supported by the US Department of Energy (Grant Nos DE-FG02-04ER63741 and DE-FG02-01ER15186 to J.L.S.). Work at the University of Kansas was supported by US Department of Energy (Grant No. DE-FG02-04ER63745 to K.B.-J.) and the National Science Foundation (Grant No. CHE-0316623 to K.B.-J.). M.M. gratefully acknowledges partial funding for this work from University of Malaga (Junta de Andalucia), Project P09-TEP-5369 in collaboration with Prof. Ignacio Loscertales.

Funders	Funder number
Junta de Andalucia	P09-TEP-5369
Office Basic Energy Sciences
US Department of Energy	DE-FG02-04ER63745, DE-FG02-04ER63741, DE-FG02-01ER15186
National Science Foundation	CHE-0316623
Oak Ridge National Laboratory
Universidad de Málaga
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

anion binding
calixpyrrole
equilibrium model
extraction
liquid-liquid anion exchange
macrocycle

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Moyer, B. A., Sloop, F. V., Fowler, C. J., Haverlock, T. J., Kang, H. A., Delmau, L. H., Bau, D. M., Hossain, M. A., Bowman-James, K., Shriver, J. A., Bill, N. L., Gross, D. E., Marquez, M., Lynch, V. M., & Sessler, J. L. (2010). Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: Effect of receptor structure on sulphate-nitrate exchange selectivity. Supramolecular Chemistry, 22(11-12), 653-671. https://doi.org/10.1080/10610271003763263

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title = "Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: Effect of receptor structure on sulphate-nitrate exchange selectivity",

abstract = "When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C 8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and β-decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1 receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range log Kbind = 2:14:8. Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.",

keywords = "anion binding, calixpyrrole, equilibrium model, extraction, liquid-liquid anion exchange, macrocycle",

author = "Moyer, {Bruce A.} and Sloop, {Frederick V.} and Fowler, {Christopher J.} and Haverlock, {Tamara J.} and Kang, {Hyun Ah} and Delmau, {Ltitia H.} and Bau, {Diadra M.} and Hossain, {Md Alamgir} and Kristin Bowman-James and Shriver, {James A.} and Bill, {Nathan L.} and Gross, {Dustin E.} and Manuel Marquez and Lynch, {Vincent M.} and Sessler, {Jonathan L.}",

year = "2010",

month = nov,

doi = "10.1080/10610271003763263",

language = "English",

volume = "22",

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Moyer, BA, Sloop, FV, Fowler, CJ, Haverlock, TJ, Kang, HA, Delmau, LH, Bau, DM, Hossain, MA, Bowman-James, K, Shriver, JA, Bill, NL, Gross, DE, Marquez, M, Lynch, VM & Sessler, JL 2010, 'Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: Effect of receptor structure on sulphate-nitrate exchange selectivity', Supramolecular Chemistry, vol. 22, no. 11-12, pp. 653-671. https://doi.org/10.1080/10610271003763263

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T1 - Enhanced liquid-liquid anion exchange using macrocyclic anion receptors

T2 - Effect of receptor structure on sulphate-nitrate exchange selectivity

AU - Moyer, Bruce A.

AU - Sloop, Frederick V.

AU - Fowler, Christopher J.

AU - Haverlock, Tamara J.

AU - Kang, Hyun Ah

AU - Delmau, Ltitia H.

AU - Bau, Diadra M.

AU - Hossain, Md Alamgir

AU - Bowman-James, Kristin

AU - Shriver, James A.

AU - Bill, Nathan L.

AU - Gross, Dustin E.

AU - Marquez, Manuel

AU - Lynch, Vincent M.

AU - Sessler, Jonathan L.

PY - 2010/11

Y1 - 2010/11

N2 - When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C 8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and β-decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1 receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range log Kbind = 2:14:8. Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.

AB - When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C 8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and β-decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1 receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range log Kbind = 2:14:8. Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.

KW - anion binding

KW - calixpyrrole

KW - equilibrium model

KW - extraction

KW - liquid-liquid anion exchange

KW - macrocycle

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DO - 10.1080/10610271003763263

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AN - SCOPUS:78649461109

SN - 1061-0278

VL - 22

SP - 653

EP - 671

JO - Supramolecular Chemistry

JF - Supramolecular Chemistry

IS - 11-12

ER -

Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: Effect of receptor structure on sulphate-nitrate exchange selectivity

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