Chercher de l'eau: The switching mechanism of the rotary switch ethyl-2-(2-(quinolin-8-yl)hydrazono)-2-(pyridin-2-yl)acetate

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creativework.keywordsDFT, NMR, Proton transfer, Rotary switch, Solvent effect, Tautomerism, Ultrafast spectroscopy
creativework.publisherElsevier B.V.en
dc.contributor.authorDeneva V.
dc.contributor.authorVassilev N.
dc.contributor.authorHristova S.
dc.contributor.authorYordanov D.
dc.contributor.authorHayashi Y.
dc.contributor.authorKawauchi S.
dc.contributor.authorFennel F.
dc.contributor.authorVölzer T.
dc.contributor.authorLochbrunner S.
dc.contributor.authorAntonov L.
dc.date.accessioned2024-07-10T14:27:04Z
dc.date.accessioned2024-07-10T14:49:31Z
dc.date.available2024-07-10T14:27:04Z
dc.date.available2024-07-10T14:49:31Z
dc.date.issued2020-05-01
dc.description.abstractThe E/Z switching mechanism of the rotary switch ethyl-2-(2-(quinolin-8-yl)hydrazono)-2-(pyridin-2-yl)acetate was studied by NMR, UV–Vis, and ultrafast spectroscopy and modeled by advanced quantum-chemical calculations. Three possible mechanisms were considered theoretically: out-of-plane rotation, in-plane inversion and proton transfer. Neither of them correctly describes the experimental data by using implicit solvation. Taking into account the existence of water in the used solvents, which influence the measured rate constants, an explicit solvation was attempted in the quantum-chemical calculations. According to a simplified model, the water molecules form a wire, being able to transfer the proton from Z to E form of the switch. This leads to substantially lower transition states and corresponds to the experimentally observed rate constants. This information shines new light on the mechanism of isomerization in the rotary switches and on the understanding of the mechanism of hydrazone tautomerism as a whole.
dc.identifier.doi10.1016/j.commatsci.2020.109570
dc.identifier.issn0927-0256
dc.identifier.scopusSCOPUS_ID:85078932903en
dc.identifier.urihttps://rlib.uctm.edu/handle/123456789/570
dc.language.isoen
dc.source.urihttps://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85078932903&origin=inward
dc.titleChercher de l'eau: The switching mechanism of the rotary switch ethyl-2-(2-(quinolin-8-yl)hydrazono)-2-(pyridin-2-yl)acetate
dc.typeArticle
oaire.citation.volume177
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