Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy

Beerwerth, Joachim; Storek, M.; Greim, Dominik; Lueg, J.; Siegel, Renée; Cetinkaya, Burak; Hiller, Wolf; Zimmermann, Herbert; Senker, Jürgen; Böhmer, Roland

doi:10.1016/j.jmr.2018.01.016

Cited by 18 publications

(10 citation statements)

References 48 publications

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“…Merely, a finite final-state correlation Z ( t p ) remains which, in general, has to be computed numerically, whereas for the cos–cos variant Z ( t p → 0) trivially equals 1. In this limit, for the sin–sin variant, here designated as Z 0 ( t p ), analytical expressions have been found for simple motional models . This is also possible for the quasitetrahedral tensor arrangement sketched in the Supporting Information.…”

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confidence: 92%

“…Conversely, in the present study, the second-order quadrupolar interactions dominate the exchange-driven modulation of the NMR frequencies. On the basis of the recent development of the central-transition stimulated-echo technique, an efficient exploitation of the second-order quadrupolar interaction allowed us to obtain detailed insights concerning the dynamics in a number of crystalline , and amorphous , materials. Applying this approach to KMnO 4 , we will find an energy barrier of about 0.35 eV for the reorientational dynamics of the manganate group in this substance.…”

Section: Introductionmentioning

confidence: 99%

“…This is also possible for the quasitetrahedral tensor arrangement sketched in the Supporting Information. Using the procedures outlined in refs and for first-order anisotropies, this yields This quantity varies from 0 to 1/12 for η from 0 to 1, respectively. The result for η = 0 is compatible with previous numerical simulations .…”

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confidence: 99%

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confidence: 99%

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Time Scales of the Quasitetrahedral Motion in KMnO₄ Observed by ¹⁷O Central-Transition NMR Spectroscopy

et al. 2020

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Oxygen-17 spin relaxation and stimulated-echo experiments are carried out to study temperature-dependent reorientational time scales in potassium permanganate. From an analysis of the present data, an energy barrier of 0.35 eV is found. This activation energy is much larger than the one reported previously (Jakobsen et al. Quantitative Dynamics and Structure for Crystalline Cs2WO4 and KMnO4 Determined from High-Field 17O Variable-Temperature MAS NMR Experiments, J. Phys. Chem. C 2014, 118, 20639–20646), but it is on the order of magnitude expected from observations for the dynamics of other tetraoxoanions in ionic crystals. The various contributions to the measured spin relaxation times and details regarding the two-time correlation functions for KMnO4 are discussed.

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confidence: 92%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Time Scales of the Quasitetrahedral Motion in KMnO₄ Observed by ¹⁷O Central-Transition NMR Spectroscopy

et al. 2020

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“…Thus, any information about the rotational dynamics of an oxygen-containing functional group may provide insights into hydrogen bonding interactions. To date, the majority 17 O NMR applications for studying molecular motion has been focused on inorganic solids where the oxygen sites usually display relatively narrow 17 O NMR signals. − In the past several years, an increasing number of 17 O NMR studies have emerged concerning molecular motions in ionic, organic, and biological solids. − …”

Section: Introductionmentioning

confidence: 99%

Solid-State ¹⁷O NMR Studies of Sulfonate Jump Dynamics in Crystalline Sulfonic Acids: Insights into the Hydrogen Bonding Effect

Dai

2020

J. Phys. Chem. A

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We report variable-temperature (VT) 17O solid-state nuclear magnetic resonance (NMR) spectra for three crystalline sulfonic acids: l-cysteic acid monohydrate (CA), 3-pyridinesulfonic acid (PSA), and p-toluenesulfonic acid monohydrate (TSA). We were able to analyze the experimental VT 17O NMR spectra to obtain the activation barriers for SO3 – jumps in these systems. Using the density functional-based tight-binding (DFTB) method, we performed potential energy surface scans for SO3 – jumps in the crystal lattice of CA, PSA, and TSA, as well as for three related crystalline sulfonic acids (taurine, homotaurine, and 4-aminobutane-1-sulfonic acid) for which relevant 17O solid-state NMR data are available in the literature. The calculated activation barriers are in reasonable agreement with the experimental values. On the basis of the DFTB results, we hypothesized that activation barriers for SO3 – jumps in the crystal lattice depend largely on the hydrogen bonding energy difference between the ground state and the transition state.

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¹⁷O NMR Spectroscopy Reveals CO₂ Speciation and Dynamics in Hydroxide‐based Carbon Capture Materials

Rhodes,

Schaaf,

Zick

et al. 2024

ChemPhysChem

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Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid‐state 17O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide‐based CO2 capture systems by 17O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO2 capture products, finding that 17O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO2 binding in two test case hydroxide‐functionalised metal‐organic frameworks (MOFs): MFU‐4l and KHCO3‐cyclodextrin‐MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine‐learning forcefields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU‐4l, we parameterise a two‐component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO3‐CD‐MOF, we combined experimental and modelling approaches to propose a new mixed carbonate‐bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide‐based CO2 capture materials by 17O NMR.

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Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy

Cited by 18 publications

References 48 publications

Time Scales of the Quasitetrahedral Motion in KMnO₄ Observed by ¹⁷O Central-Transition NMR Spectroscopy

Time Scales of the Quasitetrahedral Motion in KMnO₄ Observed by ¹⁷O Central-Transition NMR Spectroscopy

Solid-State ¹⁷O NMR Studies of Sulfonate Jump Dynamics in Crystalline Sulfonic Acids: Insights into the Hydrogen Bonding Effect

¹⁷O NMR Spectroscopy Reveals CO₂ Speciation and Dynamics in Hydroxide‐based Carbon Capture Materials

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Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy

Cited by 18 publications

References 48 publications

Time Scales of the Quasitetrahedral Motion in KMnO4 Observed by 17O Central-Transition NMR Spectroscopy

Time Scales of the Quasitetrahedral Motion in KMnO4 Observed by 17O Central-Transition NMR Spectroscopy

Solid-State 17O NMR Studies of Sulfonate Jump Dynamics in Crystalline Sulfonic Acids: Insights into the Hydrogen Bonding Effect

17O NMR Spectroscopy Reveals CO2 Speciation and Dynamics in Hydroxide‐based Carbon Capture Materials

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Time Scales of the Quasitetrahedral Motion in KMnO₄ Observed by ¹⁷O Central-Transition NMR Spectroscopy

Time Scales of the Quasitetrahedral Motion in KMnO₄ Observed by ¹⁷O Central-Transition NMR Spectroscopy

Solid-State ¹⁷O NMR Studies of Sulfonate Jump Dynamics in Crystalline Sulfonic Acids: Insights into the Hydrogen Bonding Effect

¹⁷O NMR Spectroscopy Reveals CO₂ Speciation and Dynamics in Hydroxide‐based Carbon Capture Materials