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Issue 48, 2009
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Mg-25 ultra-high field solid state NMR spectroscopy and first principles calculations of magnesium compounds

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Abstract

Due to sensitivity problems, 25Mg remains a largely under-explored nucleus in solid state NMR spectroscopy. In this work at an ultrahigh magnetic field of 21.1 T, we have studied at natural abundance the 25Mg solid state (SS) NMR spectra for a number of previously unreported magnesium compounds with known crystal structures. Some previously reported compounds have been revisited to clarify the spectra that were obtained at lower fields and were either not sufficiently resolved, or misinterpreted. First principles calculations of the 25Mg SS NMR parameters have been carried out using plane wave basis sets and periodic boundary conditions (CASTEP) and the results are compared with experimental data. The calculations produce the 25Mg absolute shielding scale and give us insight into the relationship between the NMR and structural parameters. At 21.1 T the effects of the quadrupolar interactions are reduced significantly and the sensitivity and accuracy in determining chemicals shifts and quadrupole coupling parameters improve dramatically. Although T1 measurements were not performed explicitly, these proved to be longer than assumed in much of the previously reported work. We demonstrate that the chemical shift range of magnesium in diamagnetic compounds may approach 200 ppm. Most commonly, however, the observed shifts are between −15 and +25 ppm. Quadrupolar effects dominate the 25Mg spectra of magnesium cations in non-cubic environments. The chemical shift anisotropy appears to be rather small and only in a few cases could the contribution of the CSA be detected reliably. A good correspondence between the calculated shielding constants and experimental chemical shifts was obtained, demonstrating the good potential of computational methods in spectroscopic assignments of solid state 25Mg NMR spectroscopy.

Graphical abstract: Mg-25 ultra-high field solid state NMR spectroscopy and first principles calculations of magnesium compounds

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Publication details

The article was received on 06 Aug 2009, accepted on 23 Sep 2009 and first published on 20 Oct 2009


Article type: Paper
DOI: 10.1039/B916076K
Citation: Phys. Chem. Chem. Phys., 2009,11, 11487-11500
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    Mg-25 ultra-high field solid state NMR spectroscopy and first principles calculations of magnesium compounds

    P. J. Pallister, I. L. Moudrakovski and J. A. Ripmeester, Phys. Chem. Chem. Phys., 2009, 11, 11487
    DOI: 10.1039/B916076K

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