Phonon-Driven Proton Transfer in 3,5-Pyridine Dicarboxylic Acid Studied by 2H, 14N, and 17O Nuclear Quadrupole Resonance

Seliger, J.; Žagar, V.

doi:10.1021/jp206897v

Cited by 5 publications

(7 citation statements)

References 31 publications

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“…At higher temperature the apparent dynamical rate saturates above 110 K whereas it could be expected to continue to increase given that diffraction [40], nuclear quadrupole resonance [50], and vibrational spectroscopy [51] report the crossover from donor to acceptor species at 200 K. Similarly, the temperature dependence of the spectral density amplitude [ Fig. 3(b)] shows a clear maximum at 105 K. In the usual model [21], in which …”

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confidence: 94%

Measurement of Proton Tunneling in Short Hydrogen Bonds in Single Crystals of 3,5 Pyridinedicarboxylic Acid Using Nuclear Magnetic Resonance Spectroscopy

et al. 2014

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. (2014) 'Measurement of proton tunneling in short hydrogen bonds in single crystals of 3,5 pyridinedicarboxylic acid using nuclear magnetic resonance spectroscopy.', Physical review letters., 113 (1). 018301.Further information on publisher's website:http://dx.doi.org/10.1103/PhysRevLett.113.018301Publisher's copyright statement:Reprinted with permission from the American Physical Society: Phys. Rev. Lett. 113, 018301 c (2014) by the American Physical Society. Readers may view, browse, and/or download material for temporary copying purposes only, provided these uses are for noncommercial personal purposes. Except as provided by law, this material may not be further reproduced, distributed, transmitted, modi ed, adapted, performed, displayed, published, or sold in whole or part, without prior written permission from the American Physical Society.Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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confidence: 94%

Measurement of Proton Tunneling in Short Hydrogen Bonds in Single Crystals of 3,5 Pyridinedicarboxylic Acid Using Nuclear Magnetic Resonance Spectroscopy

et al. 2014

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“…In pyridine-3,5-dicarboxylic acid, where a strong short NÁ Á ÁHÁ Á ÁO hydrogen bond is formed, proton continuously migrates from the N + -HÁ Á ÁO À position at low temperature to the NÁ Á ÁH-O position at high temperature. 25,26 The NQR measurements 24 show a continuous temperature variation of the 14 N quadrupole coupling constant e 2 qQ/h. The ratio DR(NÁ Á ÁH)/De 2 qQ/h is equal to 0.36 Å MHz À1 .…”

Section: Resultsmentioning

confidence: 98%

“…They are in the range of 14 N NQR frequencies observed in pyridine-3,5dicarboxylic acid, where short, strong NÁ Á ÁHÁ Á ÁO hydrogen bonds are formed. 24 In this system, by varying temperature, phonon driven proton transfer occurs. 25,26 At low temperature proton is closer to the hydrogen bond acceptor than to the hydrogen bond donor (N + -HÁ Á ÁO À ).…”

Section: Resultsmentioning

confidence: 99%

Hydrogen bonding and proton transfer in cocrystals of 4,4′-bipyridyl and organic acids studied using nuclear quadrupole resonance

Seliger

Žagar

2014

Phys. Chem. Chem. Phys.

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Cocrystals of 4,4'-bipyridyl and several carboxylic acids were grown from the methanol solution of the cocrystal formers. Complete (14)N NQR spectra of these cocrystals have been measured using (1)H-(14)N nuclear quadrupole double resonance. The principal values of the quadrupole coupling tensor are calculated from the (14)N NQR frequencies. A large variation in the (14)N quadrupole coupling constant between 1.3 MHz and 4.7 MHz is observed. A very low (14)N quadrupole coupling constant, characteristic for proton transfer O-H···N → O(-)···H-N(+), is observed in 4,4'-bipyridyl-oxalic acid (1 : 1). In 4,4'-bipyridyl-5-chlorosalycilic acid (1 : 1) the (14)N NQR data show the presence of a short, strong N···H···O hydrogen bond. A correlation of the principal values of the (14)N quadrupole coupling tensor is observed. The correlation is analyzed in the model, where the deformation of the lone pair electron orbital and the change of the population of the π-electron orbital produce the variation of the (14)N quadrupole coupling tensor in the hydrogen bonded 4,4'-bipyridyl. The temperature variation of the (14)N quadrupole coupling tensor in 4,4'-bipyridyl-5-chlorosalycilic acid (1 : 1) is analyzed. Proton displacement within the N···H···O hydrogen bond and the change of the population of the π-electron orbital at the two nitrogen positions in a 4,4'-bipyridyl molecule in the temperature interval between 157 K and 323 K are determined.

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“…The temperature dependence of the contributions P(1) and P(2) seem to be well described by the expression We may in the model of a resonance hybrid of two extreme electron configurations analyze also the 14 N NQR data in PDA. 16 A fit of these data to Expression 2 is presented as the solid line in Figure 11.…”

Section: ■ Discussionmentioning

confidence: 99%

“…We may in the model of a resonance hybrid of two extreme electron configurations analyze also the 14 N NQR data in PDA . A fit of these data to Expression 2 is presented as the solid line in Figure .…”

Section: Discussionmentioning

confidence: 99%

Nuclear Quadrupole Resonance Study of Proton and Deuteron Migration in Short Strong Hydrogen Bonds Formed in Molecular Complex 3,5-Dinitrobenzoic Acid–Nicotinic Acid and in Deuterated 3,5-Pyridinedicarboxylic Acid

et al. 2016

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Temperature dependences of the 14 N nuclear quadrupole resonance (NQR) frequencies have been measured in molecular complex 3,5-dinitrobenzoic acid−nicotinic acid (35DBNA) and in deuterated 3,5-pyridinedicarboxylic acid (DPDA). In deuterated DPDA, the temperature dependences of the deuterium quadrupole coupling constants and asymmetry parameters η have also been measured. In 35DBNA, the magnitude of the quadrupole coupling constant of the pyridine nitrogen agrees with the experimentally observed proton transfer. No proton exchange (O−H···N ↔ O − ···H−N + ) is observed. The temperature dependence of the 14 N quadrupole coupling constant is analyzed in a model of a resonance hybrid of two extreme electron configurations of the molecules. The energy difference of the two extreme electron configurations is determined. In the same model, we analyzed previously published 14 N NQR data of the NHO hydrogen bond in nondeuterated 3,5-pyridinedicarboxylic acid. The 14 N NQR data in DPDA show the presence of a quasi-continuous isosymmetric phase transition at around 210 K. No mixture of the high-temperature phase and the low-temperature phase has been observed below this temperature. We analyzed the temperature dependence of the 14 N quadrupole coupling constant in DPDA in the model of a resonance hybrid of two extreme electron configurations and determined the temperature dependences of their contributions to the electronic state of the molecule. ■ INTRODUCTIONHydrogen bonding is an important chemical interaction that occurs in a variety of organic and inorganic materials. These bonds, which are largely electrostatic in nature, are weaker than covalent and ionic bonds but stronger than ordinary dipole− dipole and dispersion forces. Hydrogen bonding plays a crucial role in many biological processes. It is further connected to some interesting physical properties including ferroelectricity, pyroelectricity, nonlinear optical properties, among others.Short strong hydrogen bonds (SSHB) possess a strongly covalent character. An interesting phenomena occurring in SSHB is temperature-dependent proton migration that has been observed by inelastic neutron scattering in 3,5-pyridinedicarboxylic acid (PDA), 1,2 urea phosphoric acid, 3,4 a 1:2 cocrystal of benzene-1,2,4,5-tetracarboxylic acid and 4,4-bipyridyl, 5 a 1:1 crystal of 2-methylpyridine and pentachlorophenol, 6 pyridinium 2,4-dinitrobenzoate, 7 3,5-dinitrobenzoic acid−3,5-dimethylpyridine complex, 8 dimethylurea−oxalic acid complex, 9 and in molecular complex 3,5-dinitrobenzoic acid− nicotinic acid (35DBNA). 10 The variable-temperature X-ray and neutron diffraction study of 35DBNA indicates a significant degree of proton transfer in the short NHO hydrogen bond. Complementary ab initio MD simulations at 400 K show the key proton hopping across the NHO short strong hydrogen bond, spending short periods along the trajectory (8% of the simulation time) bonded to the O atom. 10 Deuteration of a strong hydrogen bond is known to strongly change its properties. 11 Well-known effects a...

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Phonon-Driven Proton Transfer in 3,5-Pyridine Dicarboxylic Acid Studied by ²H, ¹⁴N, and ¹⁷O Nuclear Quadrupole Resonance

Cited by 5 publications

References 31 publications

Measurement of Proton Tunneling in Short Hydrogen Bonds in Single Crystals of 3,5 Pyridinedicarboxylic Acid Using Nuclear Magnetic Resonance Spectroscopy

Measurement of Proton Tunneling in Short Hydrogen Bonds in Single Crystals of 3,5 Pyridinedicarboxylic Acid Using Nuclear Magnetic Resonance Spectroscopy

Hydrogen bonding and proton transfer in cocrystals of 4,4′-bipyridyl and organic acids studied using nuclear quadrupole resonance

Nuclear Quadrupole Resonance Study of Proton and Deuteron Migration in Short Strong Hydrogen Bonds Formed in Molecular Complex 3,5-Dinitrobenzoic Acid–Nicotinic Acid and in Deuterated 3,5-Pyridinedicarboxylic Acid

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