title: Preparation of a Highly Fluorophilic Phosphonium Salt and its Use in a Fluorous Anion-Exchanger Membrane with High Selectivity for Perfluorinated Acids.
abstract: Fluorous solvents are the most nonpolar, nonpolarizable phases known, whereas ions are inherently polar. This makes it difficult to create salts that are soluble in a fluorous solvent. Here we present the synthesis and characterization of a new fluorophilic phosphonium salt, tris{3,5-bis[(perfluorooctyl)propyl]phenyl}methylphosphonium methyl sulfate. The salt has a solubility of at least 14 mM in perfluoro(perhydrophenanthrene), perfluoro(methylcyclohexane), and perfluorohexanes. It also shows immediate potential for use as a phase-transfer catalyst in fluorous biphasic catalysis, but in this work it is used as an anion exchanger site in the first potentiometric fluorous-membrane anion-selective electrode. The membrane sensor exhibited the exceptional selectivity of 3.9 × 10(10) to 1 for perfluorooctanesulfonate over chloride, and of 2.5 × 10(7) to 1 for perfluorooctanoate over chloride. With improvements to the sensor's detection limit and lifetime, it has the potential to be an attractive alternative to the expensive, time-consuming methods currently employed for measurement of perfluorinated acids.
authors.affiliation: University of Minnesota, Department of Chemistry 207 Pleasant St. SE, Minneapolis, Minnesota 55455.
authors.forename: Paul G
authors.initials: PG
authors.lastname: Boswell
authors.forename: Alyce C
authors.initials: AC
authors.lastname: Anfang
authors.forename: Philippe
authors.initials: P
authors.lastname: Bühlmann
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