[PDF]    https://doi.org/10.3952/physics.v62i2.4744

Open access article / Atviros prieigos straipsnis
Lith. J. Phys. 62, 114–125 (2022)
 

17O NMR AND DFT STUDY OF HYDROGEN BONDING: PROTON SHARING AND INCIPIENT TRANSFER
Vytautas Balevičiusa, Kęstutis Aidasa, Arūnas Maršalkaa, Feliksas Kuliešiusa, Virginija Jakubkienėb, and Sigitas Tumkevičiusb
  a Institute of Chemical Physics, Vilnius University, Saulėtekio 3, 10257 Vilnius, Lithuania
b Department of Organic Chemistry, Vilnius University, Naugarduko 24, 03225 Vilnius, Lithuania
Email: vytautas.balevicius@ff.vu.lt

Received 16 June 2022; accepted 30 June 2022

17O NMR spectra of pyridine N-oxide (PyO) complexes with the acids – acetic (AA), cyanoacetic (CyA), propiolic (PA), trichloroacetic (TCA), trifluoroacetic (TFA), hydrochloric (HCl) and methanesulfonic (MSA) – as well as some related molecules with intramolecular H-bonds (4-substituted picolinic acid N-oxides) were studied in an acetonitrile (ACN) solution. In order to evaluate the effect of proton positioning along the O–H…O bond on the measured chemical shifts the full geometry optimization was carried out, and 17O magnetic shielding tensors were calculated using density functional theory (DFT). The modified hybrid functional PBE1PBE with the 6-311++G** basis set and the gauge-including atomic orbital (GIAO) approach were applied. The solvent effect was taken into account by a polarized continuum model using the integral equation formalism (IEFPCM). Two stable structures were deduced for the PyO complexes with TCA and TFA that correspond to the H-bonds with and without proton transfer (PT). Two minima on the potential surface were separated by ca 0.2 Å. The experimental 17O NMR spectra have shown that the PyO-TCA complex in ACN can be considered as H-bonding with incipient PT, whereas it is known from neutron diffraction that in its crystalline state PT occurs. The proton location in PyO-TFA due to the thermally induced proton sharing was found at the middle point. The 17O NMR data for the acids with an intramolecular H-bond (nitroPANO, PANO and methoxyPANO) deviate from the general trend. The factors that can cause it, such as the substitution effect, persistence of nano-crystallites in a solution due to a low solubility, etc., have been discussed.
Keywords: NMR spectra, hydrogen bond, proton transfer, pyridine N-oxide


VANDENILINIO RYŠIO TYRIMAS TAIKANT 17O BMR IR TANKIO FUNKCIONALO TEORIJĄ: PROTONO DALYBOS IR PRADINĖ PERNAŠA
Vytautas Balevičiusa, Kęstutis Aidasa, Arūnas Maršalkaa, Feliksas Kuliešiusa, Virginija Jakubkienėb, Sigitas Tumkevičiusb

a Vilniaus universiteto Cheminės fizikos institutas, Vilnius, Lietuva
b Vilniaus universiteto Organinės chemijos katedra, Vilnius, Lietuva
Šiame darbe buvo eksperimentiškai ištirti piridino N-oksido vandenilinio ryšio (H-ryšio) kompleksų su rūgštimis (acto (AA), cianacto (CyA), propiolo (PA), vandenilio chloridu (HCl), metansulfonrūgštimi (MSA)) bei kai kurių panašių molekulių su vidiniais H-ryšiais (4-pakeisti pikolino rūgšties N-oksidai) 17O BMR spektrai acetonitrilo (ACN) tirpaluose. Siekiant nustatyti protono lokalizaciją ir H-ryšių geometriją bei terpės reakcijos lauko įtaką išmatuotiesiems 17O cheminiams poslinkiams, pasitelkus kvantinės mechanikos tankio funkcionalo teoriją (DFT), buvo visiškai optimizuota H-ryšio kompleksų geometrija ir apskaičiuoti deguonies magnetinio ekranavimo tenzoriai. Skaičiavimai atlikti taikant modifikuotąjį hibridinį Perdew, Burke ir Ernzerhof funkcionalą (PBE1PBE) kartu su 6-311++G** bazinių funkcijų rinkiniu bei GIAO atominių orbitalių artinį. Dielektrinės terpės (ACN) reakcijos laukas buvo įskaitytas pritaikant poliarizuojamojo kontinuumo modelį ir naudojant integralinių lygčių formalizmą (IEFPCM). PyO kompleksams su TCA ir TFA buvo nustatyta po dvi energetiškai stabilias struktūras, kurios priklauso H-ryšiams su protono pernaša (PP) ir be jos. Atstumas, skiriantis šių struktūrų potencinės energijos duobes, yra apie 0,2 Å. Eksperimentiškai išmatuoti 17O BMR spektrai leidžia teigti, kad ACN tirpale PyO-TCA kompleksas gali būti apibūdintas kaip H-ryšys su pradine PP. Tai esmingai skiriasi nuo jų H-ryšio kristale, kur iš neutronų difrakcijos duomenų galima matyti, kad PP vyksta. PyO-TFA komplekse dėl termiškai sukeltų protono dalybų protonas yra lokalizuotas ties H-ryšio centru (O...H...O). 17O BMR duomenys, gautieji molekulėms su vidiniais H-ryšiais (4-pakeisti pikolino rūgšties N-oksidai), skiriasi nuo bendrosios schemos, nustatytos PyO-rūgšties kompleksams. Darbe aptartos galimos to priežastys, tarp kurių – cheminių pakaitų ir H-ryšio efektų persiklojimas, tirpinamųjų medžiagų nanokristalitai, kurie išlieka tirpale dėl blogo tirpumo ir kt.


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