Tunable Push-Pull Interactions in 5-Nitrosopyrimidines

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F16%3A00460816" target="_blank" >RIV/61388963:_____/16:00460816 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.joc.6b00446" target="_blank" >http://dx.doi.org/10.1021/acs.joc.6b00446</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.joc.6b00446" target="_blank" >10.1021/acs.joc.6b00446</a>

Result language
angličtina
Original language name
Tunable Push-Pull Interactions in 5-Nitrosopyrimidines
Original language description
The effect of push-pull interactions in a series of variously substituted 5-nitrosopyrimidines on the strength of intramolecular hydrogen bonds, the height of rotational barriers around formally single bonds, UV-vis spectra and electrochemical behavior is explored. Intramolecular charge transfer (ICT) leads to a shift of electron density from electron-donating substituents, which is readily observable by NMR spectroscopy. The 5-nitroso group is able to form strong intramolecular hydrogen bonds with neighboring amino substituents. As a result, two rotamers with reversed orientation of the 5-nitroso group are observed for compounds with two different hydrogen-bond donors in neighboring positions. The barriers of interconversion between the two rotamers are strongly influenced by ICT, whereas the ratio of such rotamers depends primarily on the character of the hydrogen-bond donors. The ICT also significantly affects the position of UV-vis absorption maxima, which can be tuned in a broad range of 100 nm by the selection of appropriate substituents. Finally, ICT influences oxidation potential of the 5-nitrosopyrimidines and the stability of the resulting nitroso radical cations, the structures of which are determined by EPR spectroscopy.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CC - Organic chemistry
OECD FORD branch
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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
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2016
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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