Solid-state NMR and short-range order in crystalline oxides and silicates: a new tool in paramagnetic resonances

Stebbins, Jonathan F., McCarty, Ryan J. and Palke, Aaron C. (2017) Solid-state NMR and short-range order in crystalline oxides and silicates: a new tool in paramagnetic resonances. Acta Crystallographica Section C: Structural Chemistry, 73 3: 128-136. doi:10.1107/S2053229616015606

Author Stebbins, Jonathan F.
McCarty, Ryan J.
Palke, Aaron C.
Title Solid-state NMR and short-range order in crystalline oxides and silicates: a new tool in paramagnetic resonances
Journal name Acta Crystallographica Section C: Structural Chemistry   Check publisher's open access policy
ISSN 2053-2296
Publication date 2017-03-01
Sub-type Article (original research)
DOI 10.1107/S2053229616015606
Open Access Status Not yet assessed
Volume 73
Issue 3
Start page 128
End page 136
Total pages 9
Place of publication Hoboken, NJ, United States
Publisher Wiley-Blackwell Publishing
Language eng
Abstract Most applications of high-resolution NMR to questions of short-range order/disorder in inorganic materials have been made in systems where ions with unpaired electron spins are of negligible concentration, with structural information extracted primarily from chemical shifts, quadrupolar coupling parameters, and nuclear dipolar couplings. In some cases, however, the often-large additional resonance shifts caused by interactions between unpaired electron and nuclear spins can provide unique new structural information in materials with contents of paramagnetic cations ranging from hundreds of ppm to several per cent and even higher. In this brief review we focus on recent work on silicate, phosphate, and oxide materials with relatively low concentrations of paramagnetic ions, where spectral resolution can remain high enough to distinguish interactions between NMR-observed nuclides and one or more magnetic neighbors in different bonding configurations in the first, second, and even farther cation shells. We illustrate the types of information available, some of the limitations of this approach, and the great prospects for future experimental and theoretical work in this field. We give examples for the effects of paramagnetic transition metal, lanthanide, and actinide cation substitutions in simple oxides, pyrochlore, zircon, monazite, olivine, garnet, pyrochlores, and olivine structures.In many oxide and silicate materials containing paramagnetic components at the hundreds of ppm to many percent level, high-resolution solid-state NMR spectra can provide important new types of information about short-range cation order/disorder, through often-large effects of unpaired electron spins on nuclear spins.
Keyword Contact shift
Crystal structure
Nuclear magnetic resonance
Paramagnetic shift
Rare earth cations
Solid-state NMR
Transition metals
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Earth Sciences Publications
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