Tautomerism of azo dyes in the solid state studied by 15N, 14N, 13C and 1H NMR spectroscopy, X-ray diffraction and quantum-chemical calculations

Bártová, Kateřina; Cı́sařová, Ivana; Lyčka, Antonı́n; Dračínský, Martin

doi:10.1016/j.dyepig.2020.108342

Cited by 18 publications

(7 citation statements)

References 59 publications

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“…In this way, hybrid density functionals or even post-Hartree-Fock wave function methods can be used in the molecular calculation to more accurately model the intramolecular effects on the CS tensor. A more detailed description of the GIPAW + MC method applied to CS tensor predictions can be found in the literature (Nakajima, 2017;Dračínský et al, 2019;Bártová et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

2021

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Modern approaches for calculating electric field gradient (EFF) tensors in molecular solids rely upon plane-wave calculations employing periodic boundary conditions (PBC). In practice, models employing PBCs are limited to generalized gradient approximation (GGA) density functionals. Hybrid density functionals applied in the context of gauge-including atomic orbital (GIAO) calculations have been shown to substantially improve the accuracy of predicted NMR parameters. Here we propose an efficient method that effectively combines the benefits of both periodic calculations and single-molecule techniques for predicting electric field gradient tensors in molecular solids. Periodic calculations using plane-wave basis sets were used to model the crystalline environment. We then introduce a molecular correction to the periodic result obtained from a single-molecule calculation performed with a hybrid density functional. Single-molecule calculations performed using hybrid density functionals were found to significantly improve the agreement of predicted 17O quadrupolar coupling constants (Cq) with experiment. We demonstrate a 31% reduction in the RMS error for the predicted 17O Cq values relative to standard plane-wave methods using a carefully constructed test set comprised of 22 oxygen-containing molecular crystals. We show comparable improvements in accuracy using five different hybrid density functionals and find predicted Cq values to be relatively insensitive to the choice of basis set used in the single molecule calculation. Finally, the utility of high-accuracy 17O Cq predictions is demonstrated by examining the disordered 4-Nitrobenzaldehyde crystal structure.

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Section: Introductionmentioning

confidence: 99%

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

2021

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“…[9][10][11][12][13][14] In particular, 1 H detection is advantageous for the identification of specific correlations to nuclei with low gyromagnetic ratio, , such as the two naturalabundant isotopes of nitrogen, 14 N and 15 N. Our focus here is on the spin I = 1/2 15 N, though it is to be noted that there is increasing application of 14 N-1 H experiments for the much higher natural abundance (99.6%) spin I = 1 nucleus. [15][16][17][18][19][20][21][22] The low sensitivity of 15 N, associated with its low natural abundance and gyromagnetic ratio, can be overcome by the use of 15 N-1 H correlation experiments with proton acquisition, thanks to the high natural abundance and  that characterise protons, provided that fast MAS can achieve sufficient 1 H line narrowing. [23][24][25][26] We note that an 15 N-detected MAS-J-HMQC 1 H- 15 N two-dimensional spectrum has also been recorded at natural abundance and 12.5 kHz MAS using Frequency Switched Lee-Goldburg (FSLG) 1 H homonuclear decoupling.…”

Section: Introductionmentioning

confidence: 99%

Optimisation of ¹H PMLG homonuclear decoupling at 60 kHz MAS to enable ¹⁵N–¹H through-bond heteronuclear correlation solid-state NMR spectroscopy

Tognetti

Franks

Lewandowski

et al. 2022

Phys. Chem. Chem. Phys.

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“…The tautomeric form can thus be determined. The authors find that “even when the crystal structure is not known, a comparison of gas-phase calculated 13 C chemical shifts of both possible tautomeric structures with those obtained experimentally by SS-NMR can be used for the determination of the tautomeric form” [ 61 ].…”

Section: Resultsmentioning

confidence: 99%

The Synergy between Nuclear Magnetic Resonance and Density Functional Theory Calculations

Hansen

2024

Molecules

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This paper deals with the synergy between Nuclear Magnetic Resonance (NMR) spectroscopic investigations and DFT calculations, mainly of NMR parameters. Both the liquid and the solid states are discussed here. This text is a mix of published results supplemented with new findings. This paper deals with examples in which useful results could not have been obtained without combining NMR measurements and DFT calculations. Examples of such cases are tautomeric systems in which NMR data are calculated for the tautomers; hydrogen-bonded systems in which better XH bond lengths can be determined; cage compounds for which assignment cannot be made based on NMR data alone; revison of already published structures; ionic compounds for which reference data are not available; assignment of solid-state spectra and crystal forms; and the creation of libraries for biological molecules. In addition to these literature cases, a revision of a cage structure and substituent effects on pyrroles is also discussed.

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Tautomerism of azo dyes in the solid state studied by 15N, 14N, 13C and 1H NMR spectroscopy, X-ray diffraction and quantum-chemical calculations

Cited by 18 publications

References 59 publications

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

Optimisation of ¹H PMLG homonuclear decoupling at 60 kHz MAS to enable ¹⁵N–¹H through-bond heteronuclear correlation solid-state NMR spectroscopy

The Synergy between Nuclear Magnetic Resonance and Density Functional Theory Calculations

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Tautomerism of azo dyes in the solid state studied by 15N, 14N, 13C and 1H NMR spectroscopy, X-ray diffraction and quantum-chemical calculations

Cited by 18 publications

References 59 publications

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

Optimisation of 1H PMLG homonuclear decoupling at 60 kHz MAS to enable 15N–1H through-bond heteronuclear correlation solid-state NMR spectroscopy

The Synergy between Nuclear Magnetic Resonance and Density Functional Theory Calculations

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Optimisation of ¹H PMLG homonuclear decoupling at 60 kHz MAS to enable ¹⁵N–¹H through-bond heteronuclear correlation solid-state NMR spectroscopy