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High-resolution F-19 MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate

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High-resolution F-19 MAS NMR spectroscopy : structural disorder and unusual J couplings in a fluorinated hydroxy-silicate. / Griffin, John M.; Yates, Jonathan R.; Berry, Andrew J. et al.

In: Journal of the American Chemical Society, Vol. 132, No. 44, 10.11.2010, p. 15651-15660.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Harvard

Griffin, JM, Yates, JR, Berry, AJ, Wimperis, S & Ashbrook, SE 2010, 'High-resolution F-19 MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate', Journal of the American Chemical Society, vol. 132, no. 44, pp. 15651-15660. https://doi.org/10.1021/ja105347q

APA

Griffin, J. M., Yates, J. R., Berry, A. J., Wimperis, S., & Ashbrook, S. E. (2010). High-resolution F-19 MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate. Journal of the American Chemical Society, 132(44), 15651-15660. https://doi.org/10.1021/ja105347q

Vancouver

Griffin JM, Yates JR, Berry AJ, Wimperis S, Ashbrook SE. High-resolution F-19 MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate. Journal of the American Chemical Society. 2010 Nov 10;132(44):15651-15660. Epub 2010 Oct 19. doi: 10.1021/ja105347q

Author

Griffin, John M. ; Yates, Jonathan R. ; Berry, Andrew J. et al. / High-resolution F-19 MAS NMR spectroscopy : structural disorder and unusual J couplings in a fluorinated hydroxy-silicate. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 44. pp. 15651-15660.

Bibtex

@article{7badc1e009fb4723a2b6b7c9b10fb4e7,
title = "High-resolution F-19 MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate",
abstract = "High-resolution F-19 magic angle spinning (MAS) NMR spectroscopy is used to study disorder and bonding in a crystalline solid. F-19 MAS NMR reveals four distinct F sites in a 50% fluorine-substituted deuterated hydrous magnesium silicate (clinohumite, 4Mg(2)SiO(4)center dot Mg(OD1-xFx)(2) with x = 0.5), indicating extensive structural disorder. The four F-19 peaks can be assigned using density functional theory (DFT) calculations of NMR parameters for a number of structural models with a range of possible local F environments generated by F-/OH- substitution. These assignments are supported by two-dimensional F-19 double-quantum MAS NMR experiments that correlate F sites based on either spatial proximity (via dipolar couplings) or through-bond connectivity (via scalar, or J, couplings). The observation of F-19-F-19 J couplings is unexpected as the fluorines coordinate Mg atoms and the Mg-F interaction is normally considered to be ionic in character (i.e., there is no formal F-Mg-F covalent bonding arrangement). However, DFT calculations predict significant F-19-F-19 J couplings, and these are in good agreement with the splittings observed in a F-19 J-resolved MAS NMR experiment. The existence of these J couplings is discussed in relation to both the nature of bonding in the solid state and the occurrence of so-called {"}through-space{"} F-19-F-19 J couplings in solution. Finally, we note that we have found similar structural disorder and spin spin interactions in both synthetic and naturally occurring clinohumite samples.",
keywords = "SOLID-STATE NMR, MAGNETIC-RESONANCE-SPECTROSCOPY, 1ST-PRINCIPLES CALCULATIONS, MULTIPLE-QUANTUM, MAGNESIUM SILICATES, NEUTRON-DIFFRACTION, SCALAR COUPLINGS, CHEMICAL-SHIFT, POWDER NEUTRON, O-17",
author = "Griffin, {John M.} and Yates, {Jonathan R.} and Berry, {Andrew J.} and Stephen Wimperis and Ashbrook, {Sharon E.}",
year = "2010",
month = nov,
day = "10",
doi = "10.1021/ja105347q",
language = "English",
volume = "132",
pages = "15651--15660",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "AMER CHEMICAL SOC",
number = "44",

}

RIS

TY - JOUR

T1 - High-resolution F-19 MAS NMR spectroscopy

T2 - structural disorder and unusual J couplings in a fluorinated hydroxy-silicate

AU - Griffin, John M.

AU - Yates, Jonathan R.

AU - Berry, Andrew J.

AU - Wimperis, Stephen

AU - Ashbrook, Sharon E.

PY - 2010/11/10

Y1 - 2010/11/10

N2 - High-resolution F-19 magic angle spinning (MAS) NMR spectroscopy is used to study disorder and bonding in a crystalline solid. F-19 MAS NMR reveals four distinct F sites in a 50% fluorine-substituted deuterated hydrous magnesium silicate (clinohumite, 4Mg(2)SiO(4)center dot Mg(OD1-xFx)(2) with x = 0.5), indicating extensive structural disorder. The four F-19 peaks can be assigned using density functional theory (DFT) calculations of NMR parameters for a number of structural models with a range of possible local F environments generated by F-/OH- substitution. These assignments are supported by two-dimensional F-19 double-quantum MAS NMR experiments that correlate F sites based on either spatial proximity (via dipolar couplings) or through-bond connectivity (via scalar, or J, couplings). The observation of F-19-F-19 J couplings is unexpected as the fluorines coordinate Mg atoms and the Mg-F interaction is normally considered to be ionic in character (i.e., there is no formal F-Mg-F covalent bonding arrangement). However, DFT calculations predict significant F-19-F-19 J couplings, and these are in good agreement with the splittings observed in a F-19 J-resolved MAS NMR experiment. The existence of these J couplings is discussed in relation to both the nature of bonding in the solid state and the occurrence of so-called "through-space" F-19-F-19 J couplings in solution. Finally, we note that we have found similar structural disorder and spin spin interactions in both synthetic and naturally occurring clinohumite samples.

AB - High-resolution F-19 magic angle spinning (MAS) NMR spectroscopy is used to study disorder and bonding in a crystalline solid. F-19 MAS NMR reveals four distinct F sites in a 50% fluorine-substituted deuterated hydrous magnesium silicate (clinohumite, 4Mg(2)SiO(4)center dot Mg(OD1-xFx)(2) with x = 0.5), indicating extensive structural disorder. The four F-19 peaks can be assigned using density functional theory (DFT) calculations of NMR parameters for a number of structural models with a range of possible local F environments generated by F-/OH- substitution. These assignments are supported by two-dimensional F-19 double-quantum MAS NMR experiments that correlate F sites based on either spatial proximity (via dipolar couplings) or through-bond connectivity (via scalar, or J, couplings). The observation of F-19-F-19 J couplings is unexpected as the fluorines coordinate Mg atoms and the Mg-F interaction is normally considered to be ionic in character (i.e., there is no formal F-Mg-F covalent bonding arrangement). However, DFT calculations predict significant F-19-F-19 J couplings, and these are in good agreement with the splittings observed in a F-19 J-resolved MAS NMR experiment. The existence of these J couplings is discussed in relation to both the nature of bonding in the solid state and the occurrence of so-called "through-space" F-19-F-19 J couplings in solution. Finally, we note that we have found similar structural disorder and spin spin interactions in both synthetic and naturally occurring clinohumite samples.

KW - SOLID-STATE NMR

KW - MAGNETIC-RESONANCE-SPECTROSCOPY

KW - 1ST-PRINCIPLES CALCULATIONS

KW - MULTIPLE-QUANTUM

KW - MAGNESIUM SILICATES

KW - NEUTRON-DIFFRACTION

KW - SCALAR COUPLINGS

KW - CHEMICAL-SHIFT

KW - POWDER NEUTRON

KW - O-17

U2 - 10.1021/ja105347q

DO - 10.1021/ja105347q

M3 - Journal article

VL - 132

SP - 15651

EP - 15660

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 44

ER -