Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines

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Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines : NMR, IR and ab initio MD study. / Koeppe, B.; Pylaeva, S. A.; Allolio, C.; Sebastiani, D.; Nibbering, E. T.J.; Denisov, G. S.; Limbach, H. H.; Tolstoy, P. M.

In: Physical Chemistry Chemical Physics, Vol. 19, No. 2, 2017, p. 1010-1028.

Research output: Contribution to journal › Article › peer-review

Author

Koeppe, B. ; Pylaeva, S. A. ; Allolio, C. ; Sebastiani, D. ; Nibbering, E. T.J. ; Denisov, G. S. ; Limbach, H. H. ; Tolstoy, P. M. / Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines : NMR, IR and ab initio MD study. In: Physical Chemistry Chemical Physics. 2017 ; Vol. 19, No. 2. pp. 1010-1028.

BibTeX

@article{c1d3adcfcac0434aae9529ef29b7811a,

title = "Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines: NMR, IR and ab initio MD study",

abstract = "We study a series of intermolecular hydrogen-bonded 1:1 complexes formed by chloroacetic acid with 19 substituted pyridines and one aliphatic amine dissolved in CD2Cl2 at low temperature by 1H and 13C NMR and FTIR spectroscopy. The hydrogen bond geometries in these complexes vary from molecular (O-H⋯N) to zwitterionic (O-⋯H-N+) ones, while NMR spectra show the formation of short strong hydrogen bonds in intermediate cases. Analysis of CO stretching and asymmetric CO2- stretching bands in FTIR spectra reveal the presence of proton tautomerism. On the basis of these data, we construct the overall proton transfer pathway. In addition to that, we also study by use of ab initio molecular dynamics the complex formed by chloroacetic acid with 2-methylpyridine, surrounded by 71 CD2Cl2 molecules, revealing a dual-maximum distribution of hydrogen bond geometries in solution. The analysis of the calculated trajectory shows that the proton jumps between molecular and zwitterionic forms are indeed driven by dipole-dipole solvent-solute interactions, but the primary cause of the jumps is the formation/breaking of weak CH⋯O bonds from solvent molecules to oxygen atoms of the carboxylate group.",

author = "B. Koeppe and Pylaeva, {S. A.} and C. Allolio and D. Sebastiani and Nibbering, {E. T.J.} and Denisov, {G. S.} and Limbach, {H. H.} and Tolstoy, {P. M.}",

note = "Publisher Copyright: {\textcopyright} 2017 the Owner Societies.",

year = "2017",

doi = "10.1039/c6cp06677a",

language = "English",

volume = "19",

pages = "1010--1028",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "2",

}

RIS

TY - JOUR

T1 - Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines

T2 - NMR, IR and ab initio MD study

AU - Koeppe, B.

AU - Pylaeva, S. A.

AU - Allolio, C.

AU - Sebastiani, D.

AU - Nibbering, E. T.J.

AU - Denisov, G. S.

AU - Limbach, H. H.

AU - Tolstoy, P. M.

PY - 2017

Y1 - 2017

N2 - We study a series of intermolecular hydrogen-bonded 1:1 complexes formed by chloroacetic acid with 19 substituted pyridines and one aliphatic amine dissolved in CD2Cl2 at low temperature by 1H and 13C NMR and FTIR spectroscopy. The hydrogen bond geometries in these complexes vary from molecular (O-H⋯N) to zwitterionic (O-⋯H-N+) ones, while NMR spectra show the formation of short strong hydrogen bonds in intermediate cases. Analysis of CO stretching and asymmetric CO2- stretching bands in FTIR spectra reveal the presence of proton tautomerism. On the basis of these data, we construct the overall proton transfer pathway. In addition to that, we also study by use of ab initio molecular dynamics the complex formed by chloroacetic acid with 2-methylpyridine, surrounded by 71 CD2Cl2 molecules, revealing a dual-maximum distribution of hydrogen bond geometries in solution. The analysis of the calculated trajectory shows that the proton jumps between molecular and zwitterionic forms are indeed driven by dipole-dipole solvent-solute interactions, but the primary cause of the jumps is the formation/breaking of weak CH⋯O bonds from solvent molecules to oxygen atoms of the carboxylate group.

AB - We study a series of intermolecular hydrogen-bonded 1:1 complexes formed by chloroacetic acid with 19 substituted pyridines and one aliphatic amine dissolved in CD2Cl2 at low temperature by 1H and 13C NMR and FTIR spectroscopy. The hydrogen bond geometries in these complexes vary from molecular (O-H⋯N) to zwitterionic (O-⋯H-N+) ones, while NMR spectra show the formation of short strong hydrogen bonds in intermediate cases. Analysis of CO stretching and asymmetric CO2- stretching bands in FTIR spectra reveal the presence of proton tautomerism. On the basis of these data, we construct the overall proton transfer pathway. In addition to that, we also study by use of ab initio molecular dynamics the complex formed by chloroacetic acid with 2-methylpyridine, surrounded by 71 CD2Cl2 molecules, revealing a dual-maximum distribution of hydrogen bond geometries in solution. The analysis of the calculated trajectory shows that the proton jumps between molecular and zwitterionic forms are indeed driven by dipole-dipole solvent-solute interactions, but the primary cause of the jumps is the formation/breaking of weak CH⋯O bonds from solvent molecules to oxygen atoms of the carboxylate group.

UR - http://www.scopus.com/inward/record.url?scp=85027264753&partnerID=8YFLogxK

U2 - 10.1039/c6cp06677a

DO - 10.1039/c6cp06677a

M3 - Article

C2 - 27942642

AN - SCOPUS:85027264753

VL - 19

SP - 1010

EP - 1028

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 2

ER -

ID: 100698374