title: Selective solid-liquid extraction of lithium halide salts using a ditopic macrobicyclic receptor.
abstract: A ditopic salt receptor that is known to bind and extract solid NaCl, KCl, NaBr, and KBr into organic solution as their contact ion pairs is now shown by NMR and X-ray crystallography to bind and extract solid LiCl and LiBr as water-separated ion pairs. The receptor can transport these salts from an aqueous phase through a liquid organic membrane with a cation selectivity of K+ > Na+ > Li+. However, the selectivity order is strongly reversed when the receptor extracts solid alkali metal chlorides and bromides into organic solution. For a three-component mixture of solid LiCl, NaCl, and KCl, the ratio of salts extracted and complexed to the receptor in CDCl3 was 94:4:2, respectively. The same strong lithium selectivity was also observed in the case of a three-component mixture of solid LiBr, NaBr, and KBr where the ratio of extracted salts was 92:5:3. This observation is attributed to the unusually high solubility of lithium salts in organic solvents. The study suggests that ditopic receptors with an ability to extract solid salts as associated ion pairs may have application in separation processes.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Mahoney
authors.forename: Alicia M
authors.initials: AM
authors.lastname: Beatty
authors.forename: Bradley D
authors.initials: BD
authors.lastname: Smith
mesh_terms: D001965:Bromides / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D018360:Crystallography, X-Ray; D007477:Ions; D008094:Lithium / Q000737:chemistry*; D046911:Macromolecular Substances; D009682:Magnetic Resonance Spectroscopy; D008567:Membranes, Artificial; D008956:Models, Chemical; D008968:Molecular Conformation; D015394:Molecular Structure; D011189:Potassium Chloride / Q000737:chemistry; D012492:Salts / Q000737:chemistry*; D012965:Sodium Chloride / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D001965:Bromides; D002712:Chlorides; D007477:Ions; D046911:Macromolecular Substances; D008567:Membranes, Artificial; D012492:Salts; D012965:Sodium Chloride; D011189:Potassium Chloride; D008094:Lithium