A phosphonic acid anion and acid dimer dianion stabilized by proton transfer in OHN hydrogen bonds – models of structural motifs in blend polymer membranes

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A phosphonic acid anion and acid dimer dianion stabilized by proton transfer in OHN hydrogen bonds – models of structural motifs in blend polymer membranes. / Giba, I. S.; Tolstoy, P. M.; Mulloyarova, V. V.

In: Physical Chemistry Chemical Physics, Vol. 24, No. 18, 24, 03.05.2022, p. 11362-11369.

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

BibTeX

@article{7926f00868944e5e921f07ca498284ad,

title = "A phosphonic acid anion and acid dimer dianion stabilized by proton transfer in OHN hydrogen bonds – models of structural motifs in blend polymer membranes",

abstract = "The structure of intermolecular hydrogen-bonded complexes formed between tert-butylphosphonic acid and trimethylpyridine molecules has been experimentally studied as the simplest model system of the structural motifs in blend proton-conducting polymer membranes based on phosphonic acid residues. The stoichiometry of the formed complexes and proton positions in OHO and OHN hydrogen bonds were established by the H/D isotope effects and temperature dependences of the signals in 1H and 31P NMR spectra. Two structural motifs, namely, 1 : 2 and 2 : 2 acid-base complexes, were identified at the low temperature in a polar aprotic environment. In the 1 : 2 complex, one proton has passed through the hydrogen bond center creating a chain of two cooperatively coupled OHN bonds, while in the 2 : 2 complex both OHN bonds are zwitterionic and anti-cooperatively coupled to each other via a dianionic cyclic dimer of phosphonic acid in the middle. The dianionic cyclic dimer is metastable by itself, but under the used experimental conditions it is stabilized by complexation with two trimethylpyridinium cations. Additionally, quantum chemical calculations using the DFT method were carried out to support the experimental data. ",

keywords = "phosphonic acid, proton transfer, hydrogen bonds, polymer membranes, NMR spectroscopy",

author = "Giba, {I. S.} and Tolstoy, {P. M.} and Mulloyarova, {V. V.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = may,

day = "3",

doi = "10.1039/d2cp00551d",

language = "English",

volume = "24",

pages = "11362--11369",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "18",

}

RIS

TY - JOUR

T1 - A phosphonic acid anion and acid dimer dianion stabilized by proton transfer in OHN hydrogen bonds – models of structural motifs in blend polymer membranes

AU - Giba, I. S.

AU - Tolstoy, P. M.

AU - Mulloyarova, V. V.

PY - 2022/5/3

Y1 - 2022/5/3

N2 - The structure of intermolecular hydrogen-bonded complexes formed between tert-butylphosphonic acid and trimethylpyridine molecules has been experimentally studied as the simplest model system of the structural motifs in blend proton-conducting polymer membranes based on phosphonic acid residues. The stoichiometry of the formed complexes and proton positions in OHO and OHN hydrogen bonds were established by the H/D isotope effects and temperature dependences of the signals in 1H and 31P NMR spectra. Two structural motifs, namely, 1 : 2 and 2 : 2 acid-base complexes, were identified at the low temperature in a polar aprotic environment. In the 1 : 2 complex, one proton has passed through the hydrogen bond center creating a chain of two cooperatively coupled OHN bonds, while in the 2 : 2 complex both OHN bonds are zwitterionic and anti-cooperatively coupled to each other via a dianionic cyclic dimer of phosphonic acid in the middle. The dianionic cyclic dimer is metastable by itself, but under the used experimental conditions it is stabilized by complexation with two trimethylpyridinium cations. Additionally, quantum chemical calculations using the DFT method were carried out to support the experimental data.

AB - The structure of intermolecular hydrogen-bonded complexes formed between tert-butylphosphonic acid and trimethylpyridine molecules has been experimentally studied as the simplest model system of the structural motifs in blend proton-conducting polymer membranes based on phosphonic acid residues. The stoichiometry of the formed complexes and proton positions in OHO and OHN hydrogen bonds were established by the H/D isotope effects and temperature dependences of the signals in 1H and 31P NMR spectra. Two structural motifs, namely, 1 : 2 and 2 : 2 acid-base complexes, were identified at the low temperature in a polar aprotic environment. In the 1 : 2 complex, one proton has passed through the hydrogen bond center creating a chain of two cooperatively coupled OHN bonds, while in the 2 : 2 complex both OHN bonds are zwitterionic and anti-cooperatively coupled to each other via a dianionic cyclic dimer of phosphonic acid in the middle. The dianionic cyclic dimer is metastable by itself, but under the used experimental conditions it is stabilized by complexation with two trimethylpyridinium cations. Additionally, quantum chemical calculations using the DFT method were carried out to support the experimental data.

KW - phosphonic acid

KW - proton transfer

KW - hydrogen bonds

KW - polymer membranes

KW - NMR spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=85129919393&partnerID=8YFLogxK

U2 - 10.1039/d2cp00551d

DO - 10.1039/d2cp00551d

M3 - Article

VL - 24

SP - 11362

EP - 11369

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 18

M1 - 24

ER -

ID: 94913042