Erratum: “Temperature dependence of contact and dipolar NMR chemical shifts in paramagnetic molecules” [J. Chem. Phys. 142, 054108 (2015)]

Martin, Bob; Autschbach, Jochen

doi:10.1063/1.4959030

Cited by 26 publications

(71 citation statements)

References 1 publication

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“…16 for a discussion on the treatment of ZFS in paramagnetic NMR). Pseudocontact shifts were not included either, because the evaluation in spin‐delocalized systems should be approached differently from the conventional point‐dipole approximation,16c, 28 and several iron complexes have been successfully modeled by the contact term only 20. 25…”

Section: Computational Detailsmentioning

confidence: 79%

Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)–Oxo Complexes by DFT

Borgogno

Rastrelli

Bagno

2015

Chemistry A European J

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The relative energies of spin states of several iron(IV)-oxo complexes and related species have been calculated with DFT methods by employing the B3LYP* functional. We show that such calculations can predict the correct ground spin state of Fe(IV) complexes and can then be used to determine the (1) H NMR spectra of all spin states; the spectral features are remarkably different, hence calculated paramagnetic (1) H NMR spectra can be used to support the structure elucidation of numerous paramagnetic complexes. Applications to a number of stable and reactive iron(IV)-oxo species are described.

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Section: Computational Detailsmentioning

confidence: 79%

Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)–Oxo Complexes by DFT

Borgogno

Rastrelli

Bagno

2015

Chemistry A European J

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“…However, application of such computations to paramagnetic species is a considerable challenge. The first quantum‐chemical methods to calculate paramagnetic NMR (pNMR) properties that went beyond the pure contact shifts were only devised in the early 2000s and, even though refinements and further developments have been made since then, pNMR calculations remain far from routine . Extension of the present computational techniques to pNMR properties of infinite periodic solids is in its infancy and is probably one of the final frontiers of computational NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Paramagnetic NMR of Phenolic Oxime Copper Complexes: A Joint Experimental and Density Functional Study

Bühl

Ashbrook

Dawson

et al. 2016

Chemistry A European J

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H and C pNMR properties of bis(salicylaldoximato)copper(II) were studied in the solid state using magic-angle-spinning NMR spectroscopy and, for the isolated complex and selected oligomers, using density-functional theory at the PBE0-1/3 //PBE0-D3 level. Large paramagnetic shifts are observed, up to δ( H)=272 ppm and δ( C)=1006 ppm (at 298 K), which are rationalised through spin delocalisation from the metal onto the organic ligand and the resulting contact shifts arising from hyperfine coupling. The observed shift ranges are best reproduced computationally using exchange-correlation functionals with a high fraction of exact exchange (such as PBE0-1/3 ). Through a combination of experimental techniques and first-principles computation, a near-complete assignment of the observed signals is possible. Intermolecular effects on the pNMR shifts, modelled computationally in the dimers and trimers through effective decoupling between the local spins via A-tensor and total spin rescaling in the pNMR expression, are indicated to be small. Addition of electron-donating substituents and benzannelation of the organic ligand is predicted computationally to induce notable changes in the NMR signal pattern, which suggests that pNMR spectroscopy can be a sensitive probe for the spin distribution in paramagnetic phenolic oxime copper complexes.

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“…Thus, contact ( c c T −1 ) and pseudocontact ( c pc T −2 ) terms contribute to the change in chemical shifts. While the former is caused by a non‐zero spin densities on the nucleus of interest (the isotropic Fermi contact mechanism), the latter exclusively arises from the anisotropic dipole–dipole mechanism [18] . Figure 4 b represents a plot of paramagnetic shifts against reciprocal temperatures with the least squares regression.…”

Section: Figurementioning

confidence: 99%

Precise Fixation of an NO Molecule inside Carbon Nanopores: A Long‐Range Electron–Nuclear Interaction

2020

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[60]Fullerene‐based carbon nanopores were synthesized to enable the placement of two molecules of nitric oxide (NO) at an accurate distance from one another. A linear orientation of the two NO molecules inside the assembled nanopores was confirmed crystallographically. Theoretical studies suggested possible free rotation inside the carbon nanopore, while the two conformations of NO in which its long axis was oriented toward the orifice of the nanopore were predicted to be dominant. The paramagnetic shifts caused by NO showed a major contribution from the Fermi contact mechanism. The Solomon–Bloembergen theory was found to describe well the paramagnetic relaxation enhancement of a water molecule in a paired nanopore even under equilibrium as a result of fixing of the NO molecule with a distance of approximately 12 Å, thus demonstrating a long‐range bimolecular magnetic interaction.

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Erratum: “Temperature dependence of contact and dipolar NMR chemical shifts in paramagnetic molecules” [J. Chem. Phys. 142, 054108 (2015)]

Cited by 26 publications

References 1 publication

Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)–Oxo Complexes by DFT

Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)–Oxo Complexes by DFT

Paramagnetic NMR of Phenolic Oxime Copper Complexes: A Joint Experimental and Density Functional Study

Precise Fixation of an NO Molecule inside Carbon Nanopores: A Long‐Range Electron–Nuclear Interaction

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