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 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 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 spectra recorded on a sample of and computer simulations show that the magnitude of these anomalous peaks increases with increasing magnetic field and that they decrease with increasing MAS frequency. This behavior is explained theoretically.
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15 May 2005
Research Article|
May 18 2005
Through-space contributions to two-dimensional double-quantum correlation NMR spectra of magic-angle-spinning solids
Franck Fayon;
Franck Fayon
Centre de Recherches sur les Matériaux à Haute Température,
Centre National de la Recherche Scientifique (CNRS)
, 45071 Orléans Cedex 2, France
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Dominique Massiot;
Dominique Massiot
Centre de Recherches sur les Matériaux à Haute Température,
Centre National de la Recherche Scientifique (CNRS)
, 45071 Orléans Cedex 2, France
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Malcolm H. Levitt;
Malcolm H. Levitt
Chemistry Department,
Southampton University
, SO17 1BJ, United Kingdom
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Jeremy J. Titman;
Jeremy J. Titman
School of Chemistry,
University of Nottingham
, University Park, Nottingham NG7 2RD, United Kingdom
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Duncan H. Gregory;
Duncan H. Gregory
School of Chemistry,
University of Nottingham
, University Park, Nottingham NG7 2RD, United Kingdom
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Luminita Duma;
Luminita Duma
Laboratoire de Chimie [Unite Mixte de Recherche (UMR) 5182 Centre National de la Recherche Scientifique (CNRS)/Ecole Normale Supérieure (ENS)] Ecole Normale Supérieure de Lyon
, 69364 Lyon Cedex 07, France and Division of Structural Biology, Biozentrum, University of Basel
, Klingelbergstrasse 70, CH-4056 Basel, Switzerland
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Lyndon Emsley;
Lyndon Emsley
Laboratoire de Chimie [Unite Mixte de Recherche (UMR) 5182 Centre National de la Recherche Scientifique (CNRS)/Ecole Normale Supérieure (ENS)] Ecole Normale Supérieure de Lyon
, 69364 Lyon Cedex 07, France
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Steven P. Brown
Steven P. Brown
a)
Department of Physics,
University of Warwick
, Coventry CV4 7AL, United Kingdom
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 122, 194313 (2005)
Article history
Received:
December 22 2004
Accepted:
March 07 2005
Citation
Franck Fayon, Dominique Massiot, Malcolm H. Levitt, Jeremy J. Titman, Duncan H. Gregory, Luminita Duma, Lyndon Emsley, Steven P. Brown; Through-space contributions to two-dimensional double-quantum correlation NMR spectra of magic-angle-spinning solids. J. Chem. Phys. 15 May 2005; 122 (19): 194313. https://doi.org/10.1063/1.1898219
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