Toward Fractioning of Isomers through Binding-Induced Acceleration of Azobenzene Switching

Rosaria Vulcano, Paolo Pengo, Simone Velari, Johan Wouters, Alessandro De Vita, Paolo Tecilla, Davide Bonifazi

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

The E/Z isomerization process of a uracil-azobenzene derivative in which the nucleobase is conjugated to a phenyldiazene tail is studied in view of its ability to form triply H-bonded complexes with a suitably complementary 2,6-diacetylamino-4-pyridine ligand. UV-vis and 1H NMR investigations of the photochemical and thermal isomerization kinetics show that the thermal Z E interconversion is 4-fold accelerated upon formation of the H-bonded complex. DFT calculations show that the formation of triple H-bonds triggers a significant elongation of the NN double bond, caused by an increase of its g∗ antibonding character. This results in a reduction of the NN torsional barrier and thus in accelerated thermal Z E isomerization. Combined with light-controlled E Z isomerization, this enables controllable fractional tuning of the two configurational isomers.

langue originaleAnglais
Pages (de - à)18271-18280
Nombre de pages10
journalJournal of the American Chemical Society
Volume139
Numéro de publication50
Les DOIs
étatPublié - 20 déc. 2017

Empreinte digitale

Azobenzene
Isomerization
Isomers
Hot Temperature
Uracil
Discrete Fourier transforms
Pyridine
Ligands
Light
Elongation
Tuning
Nuclear magnetic resonance
Derivatives
Kinetics
azobenzene

Citer ceci

Vulcano, Rosaria ; Pengo, Paolo ; Velari, Simone ; Wouters, Johan ; De Vita, Alessandro ; Tecilla, Paolo ; Bonifazi, Davide. / Toward Fractioning of Isomers through Binding-Induced Acceleration of Azobenzene Switching. Dans: Journal of the American Chemical Society. 2017 ; Vol 139, Numéro 50. p. 18271-18280.
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abstract = "The E/Z isomerization process of a uracil-azobenzene derivative in which the nucleobase is conjugated to a phenyldiazene tail is studied in view of its ability to form triply H-bonded complexes with a suitably complementary 2,6-diacetylamino-4-pyridine ligand. UV-vis and 1H NMR investigations of the photochemical and thermal isomerization kinetics show that the thermal Z E interconversion is 4-fold accelerated upon formation of the H-bonded complex. DFT calculations show that the formation of triple H-bonds triggers a significant elongation of the NN double bond, caused by an increase of its g∗ antibonding character. This results in a reduction of the NN torsional barrier and thus in accelerated thermal Z E isomerization. Combined with light-controlled E Z isomerization, this enables controllable fractional tuning of the two configurational isomers.",
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Toward Fractioning of Isomers through Binding-Induced Acceleration of Azobenzene Switching. / Vulcano, Rosaria; Pengo, Paolo; Velari, Simone; Wouters, Johan; De Vita, Alessandro; Tecilla, Paolo; Bonifazi, Davide.

Dans: Journal of the American Chemical Society, Vol 139, Numéro 50, 20.12.2017, p. 18271-18280.

Résultats de recherche: Contribution à un journal/une revueArticle

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AU - Vulcano, Rosaria

AU - Pengo, Paolo

AU - Velari, Simone

AU - Wouters, Johan

AU - De Vita, Alessandro

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AB - The E/Z isomerization process of a uracil-azobenzene derivative in which the nucleobase is conjugated to a phenyldiazene tail is studied in view of its ability to form triply H-bonded complexes with a suitably complementary 2,6-diacetylamino-4-pyridine ligand. UV-vis and 1H NMR investigations of the photochemical and thermal isomerization kinetics show that the thermal Z E interconversion is 4-fold accelerated upon formation of the H-bonded complex. DFT calculations show that the formation of triple H-bonds triggers a significant elongation of the NN double bond, caused by an increase of its g∗ antibonding character. This results in a reduction of the NN torsional barrier and thus in accelerated thermal Z E isomerization. Combined with light-controlled E Z isomerization, this enables controllable fractional tuning of the two configurational isomers.

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