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  NMR discrimination in nonrigid prochiral solutes dissolved in chiral liquid crystals: symmetry considerations

Lesot, P., Luz, Z., Aroulanda, C., & Zimmermann, H. (2014). NMR discrimination in nonrigid prochiral solutes dissolved in chiral liquid crystals: symmetry considerations. Magnetic Resonance in Chemistry, 52(10), 581-594. doi:10.1002/mrc.4110.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0023-E091-3 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0023-E092-1
Genre: Journal Article

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Lesot, Philippe, Author
Luz, Zeev, Author
Aroulanda, Christie, Author
Zimmermann, Herbert1, Author              
Affiliations:
1Department of Biomolecular Mechanisms, Max Planck Institute for Medical Research, Max Planck Society, ou_1497700              

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Free keywords: enantiotopy; chiral liquid crystals; 2H NMR; average symmetry; spectral discrimination; Saupe matrix
 Abstract: Enantiodiscrimination in the NMR spectra of flexible prochiral solutes dissolved in chiral liquid crystals (CLCs) is reviewed and compared with the analog phenomenon in such rigid solutes. In rigid prochiral solutes, the discrimination is brought about by the cancellation of improper symmetry elements upon dissolving in CLC within the frame of solute-solvent ordering mechanisms. If this reduction in symmetry renders the ordering of enantiotopic sites dissimilar, spectral discrimination may be observed. Symmetry considerations indicate that this is only possible for improper nonaxial groups lacking inversion symmetry. Nonrigid prochiral solutes consist of rapidly (on the NMR timescale) interconverting enantiomers, in which the racemization is accompanied by exchange of nonequivalent sites. These sites become, on the average, enantiotopically related, and in CLC, they exhibit spectral discrimination. The mechanism of the effect and the symmetry selection rules are different for the two cases. Specifically, the discrimination in flexible prochiral compounds results from the different ordering of the interchanging enantiomers in CLC. Using Altman's definition of average symmetry (Proc. R. Soc. A, 1967, 298, 184), selection rules for the phenomenon are derived. It follows that chiral discrimination in nonrigid prochiral solutes is much more abundant and can occur in all symmetry types except those possessing inversion. In particular, contrary to earlier thoughts, the effect can occur in compounds with axial symmetry. Illustrative examples of such studies with particular emphasis on compounds with average axial symmetry of the type D3h, C3v and C3h are reviewed in this contribution.

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Language(s): eng - English
 Dates: 2014-06-202014-05-162014-06-232014-08-222014-10-01
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1002/mrc.4110
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Title: Magnetic Resonance in Chemistry
  Abbreviation : Magn. Reson. Chem.
Source Genre: Journal
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Publ. Info: Hoboken, N.Y., USA : John Wiley & Sons
Pages: 14 Volume / Issue: 52 (10) Sequence Number: - Start / End Page: 581 - 594 Identifier: ISSN: 0749-1581
CoNE: https://pure.mpg.de/cone/journals/resource/954928503544