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Title: α, α', α", α'"- meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

Abstract

α, α', α", α'"- meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA +(1 or 2)Cl in both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. In addition, the free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.

Authors:
 [1];  [2];  [2];  [3];  [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Texas, Austin, TX (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1236597
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Supramolecular Chemistry
Additional Journal Information:
Journal Volume: 28; Journal Issue: 1-2; Journal ID: ISSN 1061-0278
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; pyrrole; solubility; anion binding; chloride; extraction

Citation Formats

Williams, Neil J., Bryantsev, Vyacheslav S., Custelcean, Radu, Seipp, Charles A., and Moyer, Bruce A. α, α', α", α'"-meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents. United States: N. p., 2016. Web. doi:10.1080/10610278.2015.1120873.
Williams, Neil J., Bryantsev, Vyacheslav S., Custelcean, Radu, Seipp, Charles A., & Moyer, Bruce A. α, α', α", α'"-meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents. United States. doi:10.1080/10610278.2015.1120873.
Williams, Neil J., Bryantsev, Vyacheslav S., Custelcean, Radu, Seipp, Charles A., and Moyer, Bruce A. Fri . "α, α', α", α'"-meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents". United States. doi:10.1080/10610278.2015.1120873. https://www.osti.gov/servlets/purl/1236597.
@article{osti_1236597,
title = {α, α', α", α'"-meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents},
author = {Williams, Neil J. and Bryantsev, Vyacheslav S. and Custelcean, Radu and Seipp, Charles A. and Moyer, Bruce A.},
abstractNote = {α, α', α", α'"-meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA+(1 or 2)Cl– in both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. In addition, the free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.},
doi = {10.1080/10610278.2015.1120873},
journal = {Supramolecular Chemistry},
number = 1-2,
volume = 28,
place = {United States},
year = {2016},
month = {1}
}

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    Works referencing / citing this record:

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    • Williams, Neil J.; Bryanstev, Vyacheslav S.; Custelcean, Radu
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    Hydration of the halide ions in certain organic solvents
    journal, January 1974


    Selectivity Control in Synergistic Liquid–Liquid Anion Exchange of Univalent Anions via Structure-Specific Cooperativity between Quaternary Ammonium Cations and Anion Receptors
    journal, September 2012

    • Borman, Christopher J.; Bonnesen, Peter V.; Moyer, Bruce A.
    • Analytical Chemistry, Vol. 84, Issue 19
    • DOI: 10.1021/ac301315c

    Applications of Supramolecular Anion Recognition
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    Design of complexes between synthetic hosts and organic guests
    journal, January 1978

    • Cram, Donald J.; Cram, Jane M.
    • Accounts of Chemical Research, Vol. 11, Issue 1
    • DOI: 10.1021/ar50121a002

    Thermodynamic and kinetic data for macrocycle interactions with cations and anions
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    • Chemical Reviews, Vol. 91, Issue 8
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    Stabilization and Structure Calculations for Noncovalent Interactions in Extended Molecular Systems Based on Wave Function and Density Functional Theories
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    Partition coefficients and their uses
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    • Journal of the American Chemical Society, Vol. 132, Issue 16
    • DOI: 10.1021/ja100715e

    Thermodynamic Characterization of Halide−π Interactions in Solution Using “Two-Wall” Aryl Extended Calix[4]pyrroles as Model System
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    Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion
    journal, October 2014

    • Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J.
    • Journal of the American Chemical Society, Vol. 136, Issue 42
    • DOI: 10.1021/ja5086996

    Calix[4]pyrrole:  A New Ion-Pair Receptor As Demonstrated by Liquid−Liquid Extraction
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    • Wintergerst, Matthieu P.; Levitskaia, Tatiana G.; Moyer, Bruce A.
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    • DOI: 10.1021/ja7102179

    Calix[4]pyrroles:  Old Yet New Anion-Binding Agents
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    • Gale, Philip A.; Sessler, Jonathan L.; Král, Vladimír
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    • DOI: 10.1021/ja960307r

    Calix[4]pyrroles Containing Deep Cavities and Fixed Walls. Synthesis, Structural Studies, and Anion Binding Properties of the Isomeric Products Derived from the Condensation of p -Hydroxyacetophenone and Pyrrole
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    • DOI: 10.1021/ja993195n

    Infinite Dilution Activity Coefficients in Tributyl Phosphate and Triacetin
    journal, November 2000

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    • DOI: 10.1021/je000094s

    Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
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    • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
    • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
    • DOI: 10.1021/jp810292n

    Supramolecular organization of calix[4]pyrrole with a methyl-trialkylammonium anion exchanger leads to remarkable reversal of selectivity for sulfate extraction vs. nitrate
    journal, January 2011

    • Borman, Christopher J.; Custelcean, Radu; Hay, Ben P.
    • Chemical Communications, Vol. 47, Issue 27
    • DOI: 10.1039/c1cc12060c

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    Crown Ethers as Solvent Extraction Reagents: Where do We Stand?
    journal, October 1988


    Enhanced liquid–liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate–nitrate exchange selectivity
    journal, August 2010

    • Moyer, Bruce A.; Sloop, Frederick V.; Fowler, Christopher J.
    • Supramolecular Chemistry, Vol. 22, Issue 11-12, p. 653-671
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    Isomer Effects in the Extraction of Metal Ionsfrom Acidic Nitrate Media by Dicyclohexano-18-crown-6†
    journal, January 1999