Optical rotation of noncovalent aggregates.

Journal Article (Journal Article)

Dilute solutions of (R)-(-)-pantolactone in CCl4 were studied by polarimetry in conjunction with theoretical calculations of [alpha]D. Our data demonstrate that the self-association of a chiral solute results in a change in [alpha]D that can be accounted for by the presence of hydrogen-bonded dimeric species. The theoretical analysis predicts a concentration-dependent specific rotation in good agreement with experiment. Further exploration of monomer and dimer [alpha]D differences, through atomic map analysis, reveals large contributions to [alpha]D from the hydrogen-bonded hydroxyl groups in the tightly-coupled dimer. This study extends the computation of chiroptical properties to the accurate concentration-dependent prediction of [alpha]D for noncovalently interacting self-associating species.

Full Text

Duke Authors

Cited Authors

  • Goldsmith, M-R; Jayasuriya, N; Beratan, DN; Wipf, P

Published Date

  • December 2003

Published In

Volume / Issue

  • 125 / 51

Start / End Page

  • 15696 - 15697

PubMed ID

  • 14677931

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja0376893


  • eng