4.8 Article

High-Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 4, Pages 1182-+

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja905170x

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Funding

  1. Office of Science, Office of Basic Energy Sciences
  2. Division of Chemical Sciences, Geo-sciences, and Biosciences of the U.S. Department of Energy [DE-AC02-05CH11231]
  3. NSF Predoctotal Fellowship

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The self-assembled supramolecular host [Ga4L6](12-) can bind cationic guest molecules to both the interior and exterior of the host assembly through noncovalent interactions. Very small equilibrium isotope effects (EIEs) have been precisely measured for the association of benzyltrimethylphosphonium isotopologues to the host exterior surface by adapting an NMR titration method originally developed by the Perrin group for measuring isotope effects on acidity constants. Deuteration of the phosphonium methyl groups was found to have a larger EIE than deuteration at the ring and benzyl positions, Suggesting subtle differences in the noncovalent interactions between the host exterior and different guest C-H/D bonds. The application of this method to the measurement of EIEs on noncovalent host-guest interactions demonstrates the generality of this NMR technique in precisely measuring relative equilibrium constants.

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