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Influence of Intramolecular Charge Transfer and Nuclear Quantum Effects on Intramolecular Hydrogen Bonds in Azopyrimidines

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00480814" target="_blank" >RIV/61388963:_____/17:00480814 - isvavai.cz</a>

  • Alternative codes found

    RIV/00216208:11310/17:10371080

  • Result on the web

    <a href="http://dx.doi.org/10.1021/acs.joc.7b01810" target="_blank" >http://dx.doi.org/10.1021/acs.joc.7b01810</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1021/acs.joc.7b01810" target="_blank" >10.1021/acs.joc.7b01810</a>

Alternative languages

  • Result language

    angličtina

  • Original language name

    Influence of Intramolecular Charge Transfer and Nuclear Quantum Effects on Intramolecular Hydrogen Bonds in Azopyrimidines

  • Original language description

    Intramolecular hydrogen bonds (IMHBs) in 5-azopyrimidines are investigated by NMR spectroscopy and DFT computations that involve nuclear quantum effects. A series of substituted 5-phenylazopyrimidines with one or two hydrogen bond donors able to form IMHBs with the azo group is prepared by azo coupling. The barrier of interconversion between two rotamers of the compounds with two possible IMHBs is determined by variable temperature NMR spectroscopy and it is demonstrated that the barrier is significantly affected by intramolecular charge transfer. Through-hydrogen-bond scalar coupling is investigated in N-15 labeled compounds and the stability of the IMHBs is correlated with experimental NMR parameters and rationalized by path integral molecular dynamics simulations that involve nuclear quantum effects. Detailed information on the hydrogen bond geometry upon hydrogen-to-deuterium isotope exchange is obtained from a comparison of experimental and calculated NMR data.

  • Czech name

  • Czech description

Classification

  • Type

    J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • OECD FORD branch

    10403 - Physical chemistry

Result continuities

  • Project

    <a href="/en/project/GA15-11223S" target="_blank" >GA15-11223S: Hydrogen bonds and nuclear quantum delocalisation studied by NMR spectroscopy and theoretical calculations</a><br>

  • Continuities

    P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Others

  • Publication year

    2017

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Journal of Organic Chemistry

  • ISSN

    0022-3263

  • e-ISSN

  • Volume of the periodical

    82

  • Issue of the periodical within the volume

    19

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    10

  • Pages from-to

    10350-10359

  • UT code for WoS article

    000412789000041

  • EID of the result in the Scopus database

    2-s2.0-85040289731