title: Selectivity control in synergistic liquid-liquid anion exchange of univalent anions via structure-specific cooperativity between quaternary ammonium cations and anion receptors.
abstract: Two anion receptors enhance liquid-liquid anion exchange when added to quaternary alkylammonium chloride anion exchangers, but with a striking dependence on the structure of the alkylammonium cation that suggests a supramolecular cooperative effect. Two anion receptors were investigated, meso-octamethylcalix[4]pyrrole (C4P) and the bisthiourea tweezer 1,1'-(propane-1,3-diyl)bis(3-(4-sec-butylphenyl)thiourea (BTU). Whereas synergism is comparatively weak when either methyltri(C(8,10))alkylammonium chloride (Aliquat 336) or tetraheptylammonium chloride is used with the BTU receptor, synergism between C4P and Aliquat 336 is so pronounced that anion exchange prefers chloride over more extractable nitrate and trifluoroacetate, effectively overcoming the ubiquitous Hofmeister bias. A thermochemical analysis of synergistic anion exchange has been provided for the first time, resulting in the estimation of binding constants for C4P with the ion pairs of A336(+) with Cl(-), Br(-), OAc(F3)(-), NO(3)(-), and I(-).
authors.affiliation: Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37831-6119, USA.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Borman
authors.forename: Peter V
authors.initials: PV
authors.lastname: Bonnesen
authors.forename: Bruce A
authors.initials: BA
authors.lastname: Moyer
mesh_terms: D000838:Anions / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D002852:Chromatography, Ion Exchange; D015394:Molecular Structure; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*
chemical_list: D000838:Anions; D002412:Cations; D000644:Quaternary Ammonium Compounds