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 × 1010 to 1 for perfluorooctanesulfonate over chloride, and of 2.5 × 107 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.
Original language | English (US) |
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Pages (from-to) | 961-967 |
Number of pages | 7 |
Journal | Journal of Fluorine Chemistry |
Volume | 129 |
Issue number | 10 |
DOIs | |
State | Published - Oct 2008 |
Bibliographical note
Funding Information:This project was supported by the National Science Foundation (Grant CTS-0428046) and the National Institutes of Health (Grant 1R01 EB005225-01). We also thank the University of Minnesota for sponsoring this work through a Doctoral Dissertation Fellowship to P.G.B. and a Heisig summer undergraduate research fellowship to A.A.C.
Keywords
- Fluorous
- Ion-selective electrode
- Perfluorinated acids
- Phase-transfer catalyst
- Phosphonium
- Potentiometry