17O nuclear magnetic resonance:mutual effect between two β oxygen atoms and α,β double bond effect on 17O chemical shift

Kintzinger, J.-P.; Delseth, Claude; Nguyên, Thi Thanh-tâm

doi:10.1016/0040-4020(80)80196-7

Cited by 42 publications

(6 citation statements)

References 13 publications

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“…The signal at K21.6 ppm is assumed to be the terminal methoxy group of the polyethylene glycol side chain. This chemical shift is consistent with that one of ethyl methyl ether, where a chemical shift of K22.5 ppm was reported [21]. The relatively low linewidth of 130 Hz reflects the more steric freedom.…”

Section: Signal Assignmentsupporting

confidence: 87%

“…However, the oxygen atom of the sildiphenyl ether unit complicated signal assignment, as it could not be detected. The reference compounds diphenyl ether and a poly-mphenyl ether (OS-138) resonated at 117 and 119 ppm, which corresponds roughly to values from the literature ranging from 102 to 114 ppm [21][22][23]. However, the linewidth increased with molecular weight: diphenyl ether (molecular weight 170) exhibits a linewidth of 330 Hz, whereas the poly-m-phenyl ether (molecular weight 554) has a linewidth of above 870 Hz.…”

Section: Signal Assignmentmentioning

confidence: 56%

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Characterization of siloxane copolymers by solution 17O NMR spectroscopy

Kählig

Mayer-Helm

2005

Polymer

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Section: Signal Assignmentsupporting

confidence: 87%

Section: Signal Assignmentmentioning

confidence: 56%

Characterization of siloxane copolymers by solution 17O NMR spectroscopy

Kählig

Mayer-Helm

2005

Polymer

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“…In addition to greater amounts of aggregate sulfur, a higher Li:S ratio for the (Li 2 S 4 ) z clusters may play a role in the greater number of close Li-Li contacts in the large (Li 2 S 4 ) z clusters. As with the pure (Li 2 S 4 ) z in DOL/DME solvent classical MD trajectory, larger (Li 2 S 6 ) z>4 clusters are observed (as shown in Figure1e).DOL alone have been reported to be -23 to -23.9 ppm[65][66][67] and 33.5 to 34.8 ppm,65,[68][69][70] respectively. Li chemical shifts with increasing cluster size.…”

mentioning

confidence: 65%

“…However, the change in chemical shifts with temperature for the DOL case is much less dramatic compared to that for the DME case. (Figure S4) The chemical shifts for DME and DOL alone have been reported to be −23 to −23.9 ppm − and 33.5 to 34.8 ppm, ,− respectively.…”

Section: Resultsmentioning

confidence: 99%

Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane

et al. 2019

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Molecular clustering and associated dynamic processes of lithium polysulfide species were unraveled using classical molecular dynamics and ab initio metadynamics calculations. The spectroscopic signatures of polysulfide clusters were analyzed using a multimodal analysis including experimental and computational NMR and XAS spectroscopies. Lithium polysulfide solutes (Li 2 S 4 , Li 2 S 6 , and Li 2 S 8 ) and their mixtures in 1,3-dioxolane and 1,2-dimethoxyethane (DOL/DME) solvent undergo aggregation driven by intramolecular Li-S interactions, leading to distributions of cluster sizes which could critically influence the functioning of lithium-sulfur batteries. Representative polysulfide clusters with systematic increases in molecular size were extracted from the classical MD trajectories for subsequent structural and spectroscopic property calculations using DFT analysis. Structural analysis of these clusters reveal progressively decreasing solvent involvement in Li + coordination varying from Li 2 S 4 to Li 2 S 8 , with more pronounced variation and changes in DME compared with that of DOL. These observations are reflected in the analysis of the experimental and theoretical 7 Li and 17 O NMR chemical shifts and PFG-NMR diffusion measurements. A comparison of experimental and theoretical S K-edge XANES spectra show that relatively large lithium sulfide chain clusters are likely to occur in the DOL/DME-solvated lithium sulfide systems. Ab initio metadynamics simulations and NMR analysis indicates that Li + solvated by only the solvent can occur through Li + dissociation from sulfide chains. However, the occurrence of "sulfide-free" Li + is a minor mechanism compared with the dynamic aggregation and shuttling processes of polysulfide solvates in DOL/DME based electrolytes of Li-S battery. Overall, atomistic insights gained about clustering and lithium exchange dynamics will be critical for predictive understanding of polysulfide shuttling and nucleation process that dictates the Li-S battery performance.

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“…270 ppm). This deshielding is not an effect specific to mesoionic compounds nor to heterocycles at all: it reappears in the difference between isoxazole 8 (6,350 ppm [26]) and furan (6,228 ppm [27]) as well as in that between 0-methylhydroxylamine (6, f 3 5 ppm [7]) and dimethyl ether (6, -52 ppm [28]). In the furoxans 6 and 7,0(1) is deshielded by the influence of two N-atoms, and the shift difference Ad, is doubled yielding 6, 475 ppm [7] and 490 ppm, respectively [24], confirming the attribution of the lower-field resonance to O(1).…”

Section: Ementioning

confidence: 88%

¹⁷O‐NMR Spectra of Mesoionic Compounds: The polarized carbonyl group

Dahn

Ung‐Truong

1988

Helvetica Chimica Acta

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The I70-NMR spectra of 5 mesoionic compounds have been measured; in two cases, the peak attribution between endo-and exocyclic 0-atoms has been made unambiguous by synthesizing specifically 0-labelled samples. The signal of the exocyclic 0-atom appears at particularly high field, closer to the values of enolate than of carbonyl 0-atoms. The cyclic 0-atom resonates close to values of furans (or isoxazol, if bound to N). The exocyclic 0-atom is much more susceptible to structure and substituent variations than the endocyclic, an observation which is in favour of a chain-conjugated (non-aromatic) structure 1E.

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17O nuclear magnetic resonance:mutual effect between two β oxygen atoms and α,β double bond effect on 17O chemical shift

Cited by 42 publications

References 13 publications

Characterization of siloxane copolymers by solution 17O NMR spectroscopy

Characterization of siloxane copolymers by solution 17O NMR spectroscopy

Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane

¹⁷O‐NMR Spectra of Mesoionic Compounds: The polarized carbonyl group

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17O nuclear magnetic resonance:mutual effect between two β oxygen atoms and α,β double bond effect on 17O chemical shift

Cited by 42 publications

References 13 publications

Characterization of siloxane copolymers by solution 17O NMR spectroscopy

Characterization of siloxane copolymers by solution 17O NMR spectroscopy

Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane

17O‐NMR Spectra of Mesoionic Compounds: The polarized carbonyl group

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¹⁷O‐NMR Spectra of Mesoionic Compounds: The polarized carbonyl group