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Through-space contributions to two-dimensional double-quantum J correlation NMR spectra of magic-angle-spinning solids

Through-space contributions to two-dimensional double-quantum J correlation NMR spectra of magic-angle-spinning solids
Through-space contributions to two-dimensional double-quantum J correlation NMR spectra of magic-angle-spinning solids
A routinely used assumption when interpreting two-dimensional NMR spectra obtained with a commonly used double-quantum (DQ) magic-angle-spining (MAS) pulse sequence referred to as the refocused incredible natural abundance double-quantum transfer experiment (INADEQUATE) [A. Lesage, M. Bardet, and L. Emsley, J. Am. Chem. Soc. 121, 10987 (1999)] has been that correlation peaks are only observed for pairs of nuclei with a through-bond connectivity. The validity of this assumption is addressed here by theory, experiment, and computer simulations. If the isotropic chemical shifts of the two nuclei are different and the MAS frequency is far from rotational resonance, the theoretical description demonstrates that DQ correlation peaks are indeed indicative of a J coupling. However, if the isotropic chemical shifts are the same, it is shown that DQ peaks can appear for pairs of nuclei even in the absence of a through-bond J coupling. These peaks appear in the specific case of a pair of nuclei with a nonzero through-space dipole-dipole coupling and chemical shift anisotropy tensors having different principal magnitudes or orientations, provided that the MAS frequency is comparable to or smaller than, the chemical shift anisotropies. Experimental P-31 Spectra recorded on a sample of TiP2O7 and computer simulations show that the magnitude of these anomalous peaks increases with increasing B-0 magnetic field and that they decrease with increasing MAS frequency. This behavior is explained theoretically.
bond carbon-carbon, state nmr, mas nmr, correlation spectroscopy, magnetic-resonance, cross-polarization, disordered solids, rotatingsolids, direct dipolar, j-couplings
0021-9606
Fayon, Franck
366b7294-0b7c-480f-8f20-b6b688c70c67
Massiot, Dominique
8ad65440-c369-4c18-a7b3-be59b8e67e09
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Titman, Jeremy J.
696945e8-848a-4527-89a2-0da50520ecbe
Gregory, Duncan H.
3bd441f7-725f-4b8d-83e1-63d26f574339
Duma, Luminita
a1547c7d-c031-4a5a-ba78-8428fab15f79
Emsley, Lyndon
3234816a-24e9-44a0-b134-70c09de78257
Brown, Steven P.
ecbc78d6-023f-41d3-8e84-bd8c7fbfcbfa
Fayon, Franck
366b7294-0b7c-480f-8f20-b6b688c70c67
Massiot, Dominique
8ad65440-c369-4c18-a7b3-be59b8e67e09
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Titman, Jeremy J.
696945e8-848a-4527-89a2-0da50520ecbe
Gregory, Duncan H.
3bd441f7-725f-4b8d-83e1-63d26f574339
Duma, Luminita
a1547c7d-c031-4a5a-ba78-8428fab15f79
Emsley, Lyndon
3234816a-24e9-44a0-b134-70c09de78257
Brown, Steven P.
ecbc78d6-023f-41d3-8e84-bd8c7fbfcbfa

Fayon, Franck, Massiot, Dominique, Levitt, Malcolm H., Titman, Jeremy J., Gregory, Duncan H., Duma, Luminita, Emsley, Lyndon and Brown, Steven P. (2005) Through-space contributions to two-dimensional double-quantum J correlation NMR spectra of magic-angle-spinning solids. The Journal of Chemical Physics, 122 (19).

Record type: Article

Abstract

A routinely used assumption when interpreting two-dimensional NMR spectra obtained with a commonly used double-quantum (DQ) magic-angle-spining (MAS) pulse sequence referred to as the refocused incredible natural abundance double-quantum transfer experiment (INADEQUATE) [A. Lesage, M. Bardet, and L. Emsley, J. Am. Chem. Soc. 121, 10987 (1999)] has been that correlation peaks are only observed for pairs of nuclei with a through-bond connectivity. The validity of this assumption is addressed here by theory, experiment, and computer simulations. If the isotropic chemical shifts of the two nuclei are different and the MAS frequency is far from rotational resonance, the theoretical description demonstrates that DQ correlation peaks are indeed indicative of a J coupling. However, if the isotropic chemical shifts are the same, it is shown that DQ peaks can appear for pairs of nuclei even in the absence of a through-bond J coupling. These peaks appear in the specific case of a pair of nuclei with a nonzero through-space dipole-dipole coupling and chemical shift anisotropy tensors having different principal magnitudes or orientations, provided that the MAS frequency is comparable to or smaller than, the chemical shift anisotropies. Experimental P-31 Spectra recorded on a sample of TiP2O7 and computer simulations show that the magnitude of these anomalous peaks increases with increasing B-0 magnetic field and that they decrease with increasing MAS frequency. This behavior is explained theoretically.

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More information

Published date: 15 May 2005
Keywords: bond carbon-carbon, state nmr, mas nmr, correlation spectroscopy, magnetic-resonance, cross-polarization, disordered solids, rotatingsolids, direct dipolar, j-couplings

Identifiers

Local EPrints ID: 20793
URI: http://eprints.soton.ac.uk/id/eprint/20793
ISSN: 0021-9606
PURE UUID: 5b4ac7c4-05a0-4a3d-a71e-6b2de8ae2bc3
ORCID for Malcolm H. Levitt: ORCID iD orcid.org/0000-0001-9878-1180

Catalogue record

Date deposited: 03 Mar 2006
Last modified: 07 Oct 2020 07:07

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Contributors

Author: Franck Fayon
Author: Dominique Massiot
Author: Jeremy J. Titman
Author: Duncan H. Gregory
Author: Luminita Duma
Author: Lyndon Emsley
Author: Steven P. Brown

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