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

Williams, Neil J.; Bryantsev, Vyacheslav S.; Custelcean, Radu; Seipp, Charles A.; Moyer, Bruce A.

doi:10.1080/10610278.2015.1120873

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

Journal Article · Fri Jan 29 00:00:00 EST 2016 · Supramolecular Chemistry

DOI:https://doi.org/10.1080/10610278.2015.1120873· OSTI ID:1236597

Williams, Neil J. ^[1]; Bryantsev, Vyacheslav S. ^[2]; Custelcean, Radu ^[2]; Seipp, Charles A. ^[3]; Moyer, Bruce A. ^[2]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Texas, Austin, TX (United States)

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1236597

Journal Information:: Supramolecular Chemistry, Vol. 28, Issue 1-2; ISSN 1061-0278

Publisher:: Taylor & FrancisCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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Unexpected halide anion binding modes in meso -bis-ethynyl picket-calix[4]pyrroles: effects of meso -π (ethynyl) extension Dutta, Ranjan; Firmansyah, Dikhi; Kim, Jihoon Chemical Communications, Vol. 54, Issue 57 https://doi.org/10.1039/c8cc04393k	journal	January 2018
Enhancing selectivity of cation exchange with anion receptors Williams, Neil J.; Roy, Santanu; Reynolds, Campbell O. Chemical Communications, Vol. 55, Issue 25 https://doi.org/10.1039/c9cc00287a	journal	January 2019
Simple guanidinium motif for the selective binding and extraction of sulfate Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S. Separation Science and Technology, Vol. 53, Issue 12 https://doi.org/10.1080/01496395.2017.1318922	journal	March 2017
Determination of Extractant Solubility in Ionic Liquids by Thermogravimetric Analysis Smith, Charles D.; Downs, Ryan P.; Carrick, Jesse D. Solvent Extraction and Ion Exchange, Vol. 36, Issue 3 https://doi.org/10.1080/07366299.2018.1495683	journal	April 2018
Simple guanidinium motif for the selective binding and extraction of sulfate [Supplementary Data] Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S. Figshare-Supplementary information for journal article at DOI: 10.1080/01496395.2017.1318922, 1 docx (35.58 kB) https://doi.org/10.6084/m9.figshare.5162083.v2	preprint	October 2017
Simple guanidinium motif for the selective binding and extraction of sulfate Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S. Figshare, 35.58 kB https://doi.org/10.6084/m9.figshare.5162083	dataset	October 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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