High-Resolution Carbon-13 NMR of Retinal Derivatives in the Solid State

G. S. Harbison, P. P.J. Mulder, H. Pardoen, J. Lugtenburg, J. Herzfeld, R. G. Griffin

Research output: Contribution to journalArticle

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Abstract

13C NMR spectra of a large number of crystalline retinal derivatives have been obtained by using cross-polarization and magic-angle sample spinning. Most derivatives yield spectra with narrow lines (width around 20 Hz) which can be assigned via their 13C-1H dipolar coupling, their chemical shift tensors, comparison with solution spectra, or specific labeling. Measurement of the rotational sideband intensities in the spectra permit calculation of the chemical shielding tensors, and these data have allowed us to analyze variations in isotropic shifts of these compounds in more detail. We show that the tensors exhibit an odd/even effect which results from the steric crowding on one side of the polyene chain, that 7r-electron perturbations affect primarily the in-plane elements of the tensor, and, conversely, that strong steric interactions due to cis-trans isomerization affect the out-of-plane element. Finally, we observe a downfield shift at the C-5 position on isomerization about the 6–7 bond, and thus deduce from the observed shifts that retinal derivatives are 25-30% 6-s-trans in solution.

Original languageEnglish (US)
Pages (from-to)4809-4816
Number of pages8
JournalJournal of the American Chemical Society
Volume107
Issue number17
DOIs
StatePublished - Aug 1985

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Tensors
Carbon
Nuclear magnetic resonance
Derivatives
Polyenes
Isomerization
Electrons
Chemical shift
Linewidth
Shielding
Labeling
Polarization
Crystalline materials
Carbon-13 Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Harbison, G. S., Mulder, P. P. J., Pardoen, H., Lugtenburg, J., Herzfeld, J., & Griffin, R. G. (1985). High-Resolution Carbon-13 NMR of Retinal Derivatives in the Solid State. Journal of the American Chemical Society, 107(17), 4809-4816. https://doi.org/10.1021/ja00303a001

High-Resolution Carbon-13 NMR of Retinal Derivatives in the Solid State. / Harbison, G. S.; Mulder, P. P.J.; Pardoen, H.; Lugtenburg, J.; Herzfeld, J.; Griffin, R. G.

In: Journal of the American Chemical Society, Vol. 107, No. 17, 08.1985, p. 4809-4816.

Research output: Contribution to journalArticle

Harbison, GS, Mulder, PPJ, Pardoen, H, Lugtenburg, J, Herzfeld, J & Griffin, RG 1985, 'High-Resolution Carbon-13 NMR of Retinal Derivatives in the Solid State', Journal of the American Chemical Society, vol. 107, no. 17, pp. 4809-4816. https://doi.org/10.1021/ja00303a001
Harbison, G. S. ; Mulder, P. P.J. ; Pardoen, H. ; Lugtenburg, J. ; Herzfeld, J. ; Griffin, R. G. / High-Resolution Carbon-13 NMR of Retinal Derivatives in the Solid State. In: Journal of the American Chemical Society. 1985 ; Vol. 107, No. 17. pp. 4809-4816.
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N2 - 13C NMR spectra of a large number of crystalline retinal derivatives have been obtained by using cross-polarization and magic-angle sample spinning. Most derivatives yield spectra with narrow lines (width around 20 Hz) which can be assigned via their 13C-1H dipolar coupling, their chemical shift tensors, comparison with solution spectra, or specific labeling. Measurement of the rotational sideband intensities in the spectra permit calculation of the chemical shielding tensors, and these data have allowed us to analyze variations in isotropic shifts of these compounds in more detail. We show that the tensors exhibit an odd/even effect which results from the steric crowding on one side of the polyene chain, that 7r-electron perturbations affect primarily the in-plane elements of the tensor, and, conversely, that strong steric interactions due to cis-trans isomerization affect the out-of-plane element. Finally, we observe a downfield shift at the C-5 position on isomerization about the 6–7 bond, and thus deduce from the observed shifts that retinal derivatives are 25-30% 6-s-trans in solution.

AB - 13C NMR spectra of a large number of crystalline retinal derivatives have been obtained by using cross-polarization and magic-angle sample spinning. Most derivatives yield spectra with narrow lines (width around 20 Hz) which can be assigned via their 13C-1H dipolar coupling, their chemical shift tensors, comparison with solution spectra, or specific labeling. Measurement of the rotational sideband intensities in the spectra permit calculation of the chemical shielding tensors, and these data have allowed us to analyze variations in isotropic shifts of these compounds in more detail. We show that the tensors exhibit an odd/even effect which results from the steric crowding on one side of the polyene chain, that 7r-electron perturbations affect primarily the in-plane elements of the tensor, and, conversely, that strong steric interactions due to cis-trans isomerization affect the out-of-plane element. Finally, we observe a downfield shift at the C-5 position on isomerization about the 6–7 bond, and thus deduce from the observed shifts that retinal derivatives are 25-30% 6-s-trans in solution.

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