Anion Binding in Solution: Beyond the Electrostatic Regime

Liu, Yun; Sengupta, Arkajyoti; Raghavachari, Krishnan; Flood, Amar H.

doi:10.1016/j.chempr.2017.08.003

Title: Anion Binding in Solution: Beyond the Electrostatic Regime

Journal Article · Fri Sep 01 00:00:00 EDT 2017 · Chem

DOI:https://doi.org/10.1016/j.chempr.2017.08.003· OSTI ID:1470777

Liu, Yun; Sengupta, Arkajyoti; Raghavachari, Krishnan; Flood, Amar H.

A fundamental understanding of anion binding by receptors is essential for managing salts during energy, water, and food production. However, the limited understanding of solvent effects in ion recognition leads to a persistent blind spot that prevents effective receptor design. Here we experimentally discovered an underlying 1/ε_r dependence of anion affinity on solvent dielectric constant (ε_r). We found this relationship by measuring how chloride binds to macrocyclic triazolophane receptors across a wide range of solvents: ε_r = 4.7–56.2. Solvent weakens affinity by screening electrostatics; electrostatics dominates when ε_r < 4.7 (chloroform) and then transits a cross-over region (4.7 < ε_r < 20.5; acetone), after which it no longer governs affinity (acetonitrile and DMSO). Density functional theory helped us understand this dependence. Our theory-backed model accurately predicts Cl^– affinity in solvents used in liquid-liquid extractions in the nuclear fuel cycle. This model offers a general foundation for anion recognition and electrostatically driven complexation.

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Research Organization:: Indiana Univ., Bloomington, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Lilly Endowment Inc

Grant/Contract Number:: FG02-09ER16068; SC0002728; 2008 1639-000; 2004 2058-0000

OSTI ID:: 1470777

Alternate ID(s):: OSTI ID: 1533636

Journal Information:: Chem, Journal Name: Chem Vol. 3 Journal Issue: 3; ISSN 2451-9294

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 104 works

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References (57)

Preorganization?From Solvents to Spherands Cram, Donald J. Angewandte Chemie International Edition in English, Vol. 25, Issue 12 https://doi.org/10.1002/anie.198610393	journal	December 1986
A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[ n ]uril⋅Guest Binding Interactions Hostaš, Jiří; Sigwalt, David; Šekutor, Marina Chemistry - A European Journal, Vol. 22, Issue 48 https://doi.org/10.1002/chem.201601833	journal	October 2016
Pure CH Hydrogen Bonding to Chloride Ions: A Preorganized and Rigid Macrocyclic Receptor Li, Yongjun; Flood, Amar H. Angewandte Chemie International Edition, Vol. 47, Issue 14 https://doi.org/10.1002/anie.200704717	journal	March 2008
Seeing through solvent effects using molecular balances Mati, Ioulia K.; Adam, Catherine; Cockroft, Scott L. Chemical Science, Vol. 4, Issue 10 https://doi.org/10.1039/c3sc51764k	journal	January 2013
Dielectric Relaxation in Dimethyl Sulfoxide/Water Mixtures Studied by Microwave Dielectric Relaxation Spectroscopy Lu, Zijie; Manias, Evangelos; Macdonald, Digby D. The Journal of Physical Chemistry A, Vol. 113, Issue 44 https://doi.org/10.1021/jp9059246	journal	November 2009
Density fitting and Cholesky decomposition approximations in symmetry-adapted perturbation theory: Implementation and application to probe the nature of π-π interactions in linear acenes Hohenstein, Edward G.; Sherrill, C. David The Journal of Chemical Physics, Vol. 132, Issue 18 https://doi.org/10.1063/1.3426316	journal	May 2010
Solvent Effects on Crown Ether Complexations ¹ Solov'ev, Vitally P.; Strakhova, Nadezhda N.; Raevsky, Oleg A. The Journal of Organic Chemistry, Vol. 61, Issue 16 https://doi.org/10.1021/jo952250h	journal	January 1996
Quantifying Intermolecular Interactions: Guidelines for the Molecular Recognition Toolbox Hunter, Christopher A. Angewandte Chemie International Edition, Vol. 43, Issue 40 https://doi.org/10.1002/anie.200301739	journal	October 2004
Precedent and Theory Unite in the Hypothesis of a Highly Selective Fluoride Receptor Mascal, Mark Angewandte Chemie International Edition, Vol. 45, Issue 18 https://doi.org/10.1002/anie.200504417	journal	April 2006
H-Bond Acceptor Parameters for Anions Pike, Sarah J.; Hutchinson, Jordan J.; Hunter, Christopher A. Journal of the American Chemical Society, Vol. 139, Issue 19 https://doi.org/10.1021/jacs.7b02008	journal	May 2017
Anion Binding of Short, Flexible Aryl Triazole Oligomers Juwarker, Hemraj; Lenhardt, Jeremy M.; Castillo, José C. The Journal of Organic Chemistry, Vol. 74, Issue 23 https://doi.org/10.1021/jo901966f	journal	December 2009
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Cooperativity and Complexity in the Binding of Anions and Cations to a Tetratopic Ion-Pair Host Howe, Ethan N. W.; Bhadbhade, Mohan; Thordarson, Pall Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja503383e	journal	May 2014
Flexibility Coexists with Shape-Persistence in Cyanostar Macrocycles Liu, Yun; Singharoy, Abhishek; Mayne, Christopher G. Journal of the American Chemical Society, Vol. 138, Issue 14 https://doi.org/10.1021/jacs.6b00712	journal	March 2016
Hydrophobic Collapse of Foldamer Capsules Drives Picomolar-Level Chloride Binding in Aqueous Acetonitrile Solutions Hua, Yuran; Liu, Yun; Chen, Chun-Hsing Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja4074744	journal	September 2013
Solvent Effects on Hydrogen Bonding Cook, Joanne L.; Hunter, Christopher A.; Low, Caroline M. R. Angewandte Chemie International Edition, Vol. 46, Issue 20 https://doi.org/10.1002/anie.200604966	journal	May 2007
The statistical-thermodynamic basis for computation of binding affinities: a critical review Gilson, M. K.; Given, J. A.; Bush, B. L. Biophysical Journal, Vol. 72, Issue 3 https://doi.org/10.1016/S0006-3495(97)78756-3	journal	March 1997
Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4 https://doi.org/10.1002/wcms.93	journal	October 2011
A synthetic host-guest system achieves avidin-biotin affinity by overcoming enthalpy-entropy compensation Rekharsky, M. V.; Mori, T.; Yang, C. Proceedings of the National Academy of Sciences, Vol. 104, Issue 52 https://doi.org/10.1073/pnas.0706407105	journal	December 2007
Quantum Mechanical Continuum Solvation Models Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto Chemical Reviews, Vol. 105, Issue 8 https://doi.org/10.1021/cr9904009	journal	August 2005
Solvent effects in molecular recognition Smithrud, D. B.; Sanford, E. M.; Chao, I. Pure and Applied Chemistry, Vol. 62, Issue 12 https://doi.org/10.1351/pac199062122227	journal	January 1990
Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes Jeziorski, Bogumil; Moszynski, Robert; Szalewicz, Krzysztof Chemical Reviews, Vol. 94, Issue 7 https://doi.org/10.1021/cr00031a008	journal	November 1994
A universal approach for continuum solvent pK a calculations: are we there yet? Ho, Junming; Coote, Michelle L. Theoretical Chemistry Accounts, Vol. 125, Issue 1-2 https://doi.org/10.1007/s00214-009-0667-0	journal	November 2009
Substituent Effects in CH Hydrogen Bond Interactions: Linear Free Energy Relationships and Influence of Anions Tresca, Blakely W.; Hansen, Ryan J.; Chau, Calvin V. Journal of the American Chemical Society, Vol. 137, Issue 47 https://doi.org/10.1021/jacs.5b08767	journal	November 2015
Anion Binding to Hydrophobic Concavity Is Central to the Salting-in Effects of Hofmeister Chaotropes Gibb, Corinne L. D.; Gibb, Bruce C. Journal of the American Chemical Society, Vol. 133, Issue 19 https://doi.org/10.1021/ja202308n	journal	May 2011
Nonprotonophoric Electrogenic Cl − Transport Mediated by Valinomycin-like Carriers Wu, Xin; Judd, Luke W.; Howe, Ethan N. W. Chem, Vol. 1, Issue 1 https://doi.org/10.1016/j.chempr.2016.04.002	journal	July 2016
Aromatic and Aliphatic CH Hydrogen Bonds Fight for Chloride while Competing Alongside Ion Pairing within Triazolophanes Hua, Yuran; Ramabhadran, Raghunath O.; Uduehi, Esther O. Chemistry - A European Journal, Vol. 17, Issue 1 https://doi.org/10.1002/chem.201002340	journal	November 2010
Structural Design Criteria for Anion Hosts: Strategies for Achieving Anion Shape Recognition through the Complementary Placement of Urea Donor Groups Hay, Benjamin P.; Firman, Timothy K.; Moyer, Bruce A. Journal of the American Chemical Society, Vol. 127, Issue 6 https://doi.org/10.1021/ja043995k	journal	February 2005
Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory Grimme, Stefan Chemistry - A European Journal, Vol. 18, Issue 32 https://doi.org/10.1002/chem.201200497	journal	July 2012
How nitrate leaching from agricultural lands provokes phosphate eutrophication in groundwater fed wetlands: the sulphur bridge Smolders, Alfons J. P.; Lucassen, Esther C. H. E. T.; Bobbink, Roland Biogeochemistry, Vol. 98, Issue 1-3 https://doi.org/10.1007/s10533-009-9387-8	journal	November 2009
Conformational Features and Anion-Binding Properties of Calix[4]pyrrole: A Theoretical Study Wu, Yun-Dong; Wang, Di-Fei; Sessler, Jonathan L. The Journal of Organic Chemistry, Vol. 66, Issue 11 https://doi.org/10.1021/jo0016273	journal	June 2001
Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes Sure, Rebecca; Grimme, Stefan Journal of Chemical Theory and Computation, Vol. 11, Issue 8 https://doi.org/10.1021/acs.jctc.5b00296	journal	July 2015
Health effects assessment for environmental perchlorate contamination: the dose response for inhibition of thyroidal radioiodine uptake in humans. Greer, Monte A.; Goodman, Gay; Pleus, Richard C. Environmental Health Perspectives, Vol. 110, Issue 9 https://doi.org/10.1289/ehp.02110927	journal	September 2002
Calix[4]pyrrole as a Chloride Anion Receptor: Solvent and Countercation Effects Sessler, Jonathan L.; Gross, Dustin E.; Cho, Won-Seob Journal of the American Chemical Society, Vol. 128, Issue 37 https://doi.org/10.1021/ja064012h	journal	September 2006
Cooperative Binding at Lipid Bilayer Membrane Surfaces Doyle, Emma L.; Hunter, Christopher A.; Phillips, Helen C. Journal of the American Chemical Society, Vol. 125, Issue 15 https://doi.org/10.1021/ja021048a	journal	April 2003
Nuclear Magnetic Resonance as a Tool for Determining Protonation Constants of Natural Polyprotic Bases in Solution Frassineti, Chiara; Ghelli, Stefano; Gans, Peter Analytical Biochemistry, Vol. 231, Issue 2 https://doi.org/10.1006/abio.1995.9984	journal	November 1995
Phosphate Bound to Histidine in a Protein as an Intermediate in a Novel Phospho-Transferase System Kundig, W.; Ghosh, S.; Roseman, S. Proceedings of the National Academy of Sciences, Vol. 52, Issue 4 https://doi.org/10.1073/pnas.52.4.1067	journal	October 1964
Self-consistent description of a metal–water interface by the Kohn–Sham density functional theory and the three-dimensional reference interaction site model Kovalenko, Andriy; Hirata, Fumio The Journal of Chemical Physics, Vol. 110, Issue 20 https://doi.org/10.1063/1.478883	journal	May 1999
Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin Assaf, Khaleel I.; Ural, Merve S.; Pan, Fangfang Angewandte Chemie International Edition, Vol. 54, Issue 23 https://doi.org/10.1002/anie.201412485	journal	May 2015
Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, .pi.*, .alpha., and .beta., and some methods for simplifying the generalized solvatochromic equation Kamlet, Mortimer J.; Abboud, Jose Luis M.; Abraham, Michael H. The Journal of Organic Chemistry, Vol. 48, Issue 17 https://doi.org/10.1021/jo00165a018	journal	August 1983
NMR Method for Simultaneous Host–Guest Binding Constant Measurement Kadam, Sandip A.; Haav, Kristjan; Toom, Lauri The Journal of Organic Chemistry, Vol. 79, Issue 6 https://doi.org/10.1021/jo4027963	journal	February 2014
PUBLIC HEALTH: Enhanced: Worldwide Occurrences of Arsenic in Ground Water Nordstrom, D. K. Science, Vol. 296, Issue 5576 https://doi.org/10.1126/science.1072375	journal	June 2002
Preferential Solvation and Hydrogen Bonding in Mixed Solvents Cook, Joanne L.; Hunter, Christopher A.; Low, Caroline M. R. Angewandte Chemie International Edition, Vol. 47, Issue 33 https://doi.org/10.1002/anie.200801349	journal	August 2008
Evidence for Halogen Bond Covalency in Acyclic and Interlocked Halogen-Bonding Receptor Anion Recognition Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G. Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja511648d	journal	December 2014
pH-Regulated Nonelectrogenic Anion Transport by Phenylthiosemicarbazones Howe, Ethan N. W.; Busschaert, Nathalie; Wu, Xin Journal of the American Chemical Society, Vol. 138, Issue 26 https://doi.org/10.1021/jacs.6b04656	journal	June 2016
Noncovalent Interactions within a Synthetic Receptor Can Reinforce Guest Binding Rodriguez-Docampo, Zaida; Pascu, Sofia I.; Kubik, Stefan Journal of the American Chemical Society, Vol. 128, Issue 34 https://doi.org/10.1021/ja062389h	journal	August 2006
Anion Complexation and The Hofmeister Effect Carnegie, Ryan S.; Gibb, Corinne L. D.; Gibb, Bruce C. Angewandte Chemie International Edition, Vol. 53, Issue 43 https://doi.org/10.1002/anie.201405796	journal	September 2014
Anion Receptor Chemistry Gale, Philip A.; Howe, Ethan N. W.; Wu, Xin Chem, Vol. 1, Issue 3 https://doi.org/10.1016/j.chempr.2016.08.004	journal	September 2016
Determining association constants from titration experiments in supramolecular chemistry Thordarson, Pall Chem. Soc. Rev., Vol. 40, Issue 3 https://doi.org/10.1039/C0CS00062K	journal	January 2011
Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts Langton, Matthew J.; Robinson, Sean W.; Marques, Igor Nature Chemistry, Vol. 6, Issue 12 https://doi.org/10.1038/nchem.2111	journal	November 2014
An Overlooked yet Ubiquitous Fluoride Congenitor: Binding Bifluoride in Triazolophanes Using Computer-Aided Design Ramabhadran, Raghunath O.; Liu, Yun; Hua, Yuran Journal of the American Chemical Society, Vol. 136, Issue 13 https://doi.org/10.1021/ja500125r	journal	March 2014
A data-intensive approach to mechanistic elucidation applied to chiral anion catalysis Milo, A.; Neel, A. J.; Toste, F. D. Science, Vol. 347, Issue 6223 https://doi.org/10.1126/science.1261043	journal	February 2015
Allosteric and Chelate Cooperativity in Divalent Crown Ether/Ammonium Complexes with Strong Binding Enhancement von Krbek, Larissa K. S.; Achazi, Andreas J.; Solleder, Marthe Chemistry - A European Journal, Vol. 22, Issue 43 https://doi.org/10.1002/chem.201603098	journal	September 2016
Solvent dependent anion selectivity exhibited by neutral ferrocenoyl receptors Beer, Paul D. Chemical Communications, Issue 24 https://doi.org/10.1039/a707181g	journal	January 1997
Detailed Spectroscopic, Thermodynamic, and Kinetic Characterization of Nickel(II) Complexes with 2,2‘-Bipyridine and 1,10-Phenanthroline Attained via Equilibrium-Restricted Factor Analysis Vander Griend, Douglas A.; Bediako, Daniel Kwabena; DeVries, Michael J. Inorganic Chemistry, Vol. 47, Issue 2 https://doi.org/10.1021/ic700553d	journal	January 2008
Cyclic polyethers and their complexes with metal salts Pedersen, Charles J. Journal of the American Chemical Society, Vol. 89, Issue 26 https://doi.org/10.1021/ja01002a035	journal	December 1967
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni Journal of Computational Chemistry, Vol. 24, Issue 6 https://doi.org/10.1002/jcc.10189	journal	April 2003

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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chloride
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Title: Anion Binding in Solution: Beyond the Electrostatic Regime

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