Line-Shape Analyses of Solid-state 17O NMR Spectra for Hexagonal Ice

We present the results of experimental and theoretical investigations of line shapes in solid-state 17O NMR spectra of hexagonal ice, Ih. Stationary 17O NMR spectra of Ih at temperatures from 143 to 280 K were obtained at 11.7 and 16.4 T. Line shapes changed drastically as the temperature was increased from 143 to 243 K; at 253 K and above, pseudo-isotropic line shapes appear, indicating the presence of reorientational motions. We find that Ratcliffe’s model, which involves twelve orientations and four-step jumps for water reorientational motions, is effective for analyzing the NMR spectra at temperatures below 243 K. The present analysis demonstrates that the isotropic line shapes arise from proton disorder with respect to the solid-state 17O NMR time scale, producing pseudoicosahedral motional averaging that can completely average out second-order quadrupole interactions.

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14N Quadrupole Interactions in Nitrogen-Containing Ceramics. Effects on 29Si NMR Line Shapes and Structural Implications

Zeitschrift für Naturforschung A ◽

10.1515/zna-1992-1-209 ◽

1992 ◽

Vol 47 (1-2) ◽

pp. 39-44 ◽

Cited By ~ 3

Author(s):

Alejandro Olivieri

Keyword(s):

Solid State ◽

Nmr Spectra ◽

Dipolar Coupling ◽

Coupling Constants ◽

Simple Equation ◽

29Si Nmr ◽

Experimental Conditions ◽

Line Shapes ◽

Quadrupole Interactions ◽

Quadrupole Coupling

AbstractSimulations of solid-state 29Si NMR spectra in nitrogen-containing silicon ceramics and glasses are described. The range of SiNxO4-x tetrahedra is covered, with emphasis on the experimental conditions needed to observe the effect of the incompletely averaged 29Si, 14N dipolar coupling. A simple equation is discussed concerning its use in the interpretation of these 29Si spectra, including the computation of 14N quadrupole coupling constants with its absolute sign.

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High Resolution and Solid State NMR Investigations of Subvalent Gallium Compounds

Zeitschrift für Naturforschung A ◽

10.1515/zna-1986-1-258 ◽

1986 ◽

Vol 41 (1-2) ◽

pp. 315-318 ◽

Cited By ~ 11

Author(s):

Hubert Schmidbaur ◽

Theodore Zafiropoulos ◽

Wolfgang Bublak ◽

Paul Burkert ◽

Frank H. Köhler

Keyword(s):

Solid State ◽

Nmr Spectra ◽

Quadrupole Coupling Constant ◽

Coupling Constant ◽

Gallium Atom ◽

Line Shapes ◽

Quadrupole Coupling ◽

Structure Determinations ◽

Constant E ◽

Gallium Compounds

The 71Ga NMR spectra of Ga[GaX4] melts and of solutions in benzene and other hydrocarbons show discrete sharp GaI and broad GaIII resonances. In the light of recent structure determinations, the solution GaI signals must be attributed to bis(arene)Ga+ complexes in which the gallium atom is η6-bonded to the hydrocarbons. The low line widths and strong high field shifts are attributed to an almost spherical shielding of the metal nucleus by the 4 s2 electrons. Solid state 69Ga and 71Ga NMR spectra of Ga[GaCl4] crystalline powder show only Ga1 resonances. While the 71GaI line is rather narrow, the 69GaI line has a complex fine structure. Consistent with the crystal structure of Ga[GaCl4], the Ga1 ion is calculated to have a very low quadrupole coupling constant e2q Q/h = 1.7 ± 0.1 MHz and an asymmetry parameter η = 0.44. Experimental and simulated line shapes (using literature models) are in satisfactory agreement, implying that the 69Ga signal splitting is due to second order quadrupolar effects for the central m = + 1/2 ⇋ - 1/2 transition. The analogous splitting of the 71Ga NMR line is too small to be detected.

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Cobalt-59 chemical shift and quadrupolar tensors of simple octahedral cobalt(III) complexes

Canadian Journal of Chemistry ◽

10.1139/v01-025 ◽

2001 ◽

Vol 79 (3) ◽

pp. 296-303

Author(s):

Christopher W Kirby ◽

William P Power

Keyword(s):

Solid State ◽

Chemical Shift ◽

Principal Components ◽

Solid State Nmr ◽

Nmr Spectra ◽

Line Shapes ◽

Quadrupolar Coupling ◽

Molecular Frame ◽

Specific Ligand

Analysis of the solid-state powder 59Co NMR spectra of ten simple inorganic cobalt(III) complexes at 11.75, and in most cases, 4.7 T have permitted the assignment of specific ligand planes to ranges of values of the observed chemical shift principal components. The relevant chemical shift components were determined from the simulations of the powder line shapes. These simulations also provided the relative orientations of the chemical shift (CS) and electric field gradient (efg) tensors, as well as magnitude and asymmetry of the 59Co quadrupolar coupling. Using symmetry arguments and ab initio calculations, as appropriate or necessary, the orientations of the efg tensors in the molecular frame were deduced. This allowed the determination of the CS tensors in the molecular frame and thus assignment of the ligand planes responsible for the observed values of chemical shifts.Key words: cobalt, chemical shift, quadrupolar coupling, solid state NMR.

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NMR spectroscopy of the solid-state isomerization of nitrito- and nitro-pentamminecobalt(III) chloride

Canadian Journal of Chemistry ◽

10.1139/v06-001 ◽

2006 ◽

Vol 84 (2) ◽

pp. 300-308 ◽

Cited By ~ 8

Author(s):

Kristopher J Ooms ◽

Roderick E Wasylishen

Keyword(s):

Solid State ◽

Chemical Shift ◽

Nmr Spectra ◽

Spin Coupling ◽

Chemical Shift Tensor ◽

Coupling Constant ◽

Line Shapes ◽

Quadrupolar Coupling ◽

Shielding Tensor ◽

Spin Spin Coupling

Cobalt-59 and nitrogen-15 NMR spectra of the nitritopentamminecobalt(III) chloride, [(NH3)5Co-ONO]Cl2, and nitropentamminecobalt(III) chloride, [(NH3)5Co-NO2]Cl2, isomers in the solid state have been obtained at several applied magnetic field strengths. The 59Co NMR line shapes indicate that both the cobalt nuclear quadrupolar coupling constant (CQ) and the span of the chemical shift tensor (Ω) decrease when the complex isomerizes from [(NH3)5Co-ONO]2+ to [(NH3)5Co-NO2]2+; CQ decreases from 23 to 10.3 MHz and Ω changes from 1650 to 260 ppm. The 15N NMR line shapes also show a significant change in the nitrogen magnetic shielding tensor upon isomerization, with Ω decreasing from 710 to 547 ppm; also, an indirect spin-spin coupling, 1J(59Co,15N) = 63 Hz, is observed in the 15N NMR spectra of the nitro isomer. The NMR parameters are rationalized based on differences in the molecular structure of the two isomers. NMR spectra have also been recorded as the isomerization progresses with time and demonstrate the practicality of the technique for the study of solid-state isomerizations.Key words: 15N, 59Co, solid-state NMR, linkage isomerization, chemical shift tensor, electric field gradient tensor.

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Influence of low-barrier hydrogen bonds on solid state 17O NMR spectra of labelled phthalate species

Chemical Communications ◽

10.1039/b104308k ◽

2001 ◽

pp. 1448-1449 ◽

Cited By ~ 10

Author(s):

A. P. Howes ◽

M. E. Smith ◽

R. Dupree ◽

R. Jenkins ◽

D. H. G. Crout

Keyword(s):

Solid State ◽

Hydrogen Bonds ◽

Nmr Spectra ◽

17O Nmr ◽

Low Barrier Hydrogen Bonds

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Both experimental and theoretical investigations of solid-state 17O NMR for l-valine and l-isoleucine

Solid State Nuclear Magnetic Resonance ◽

10.1016/j.ssnmr.2006.09.003 ◽

2006 ◽

Vol 30 (3-4) ◽

pp. 182-191 ◽

Cited By ~ 10

Author(s):

Kazuhiko Yamada ◽

Takahiro Nemoto ◽

Miwako Asanuma ◽

Hisashi Honda ◽

Toshio Yamazaki ◽

...

Keyword(s):

Solid State ◽

17O Nmr ◽

Theoretical Investigations

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Solid-State 17O NMR Study of α-D-Glucose: Exploring New Frontiers in Isotopic Labeling, Sensitivity Enhancement, and NMR Crystallography

Chemical Science ◽

10.1039/d1sc06060k ◽

2022 ◽

Author(s):

Jiahui Shen ◽

Victor Terskikh ◽

Jochem Struppe ◽

Alia Hassan ◽

Martine Monette ◽

...

Keyword(s):

Solid State ◽

Nmr Spectra ◽

Isotopic Labeling ◽

Sensitivity Enhancement ◽

17O Nmr ◽

Nmr Study ◽

Nmr Characterization ◽

Nmr Crystallography ◽

Oxygen Atoms

We report synthesis and solid-state 17O NMR characterization of α-D-glucose for which all six oxygen atoms are site-specifically 17O-labeled. Solid-state 17O NMR spectra were recorded for α-D-glucose/NaCl/H2O (2/1/1) cocrystals under...

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