Polysubstituted 5-Phenylazopyrimidines: Extremely Fast Non-ionic Photochromic Oscillators.

DFT calculations azopyrimidines photochromic oscillators ultrafast spectroscopy

Journal

Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543

Informations de publication

Date de publication:
01 Sep 2020
Historique:
received: 15 05 2020
pubmed: 21 5 2020
medline: 21 5 2020
entrez: 21 5 2020
Statut: ppublish

Résumé

Photochromic systems with an ultrahigh rate of thermal relaxation are highly desirable for the development of new efficient photochromic oscillators. Based on DFT calculations, we designed a series of 5-phenylazopyrimidines with strong push-pull character in silico and observed very low energy barriers for the thermal (Z)-to-(E) isomerization. The structure of the (Z)-isomer of the slowest isomerizing derivative in the series was confirmed by NMR analysis with in situ irradiation at low temperature. The substituents can tune the lifetime of thermal back isomerization from hundreds of microseconds to several nanoseconds (8 orders of magnitude). The photoswitching parameters were extracted from transient absorption techniques and a dominant rotation mechanism of the (Z)-to-(E) thermal fading was proposed based on DFT calculations.

Identifiants

pubmed: 32433814
doi: 10.1002/anie.202007065
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

15590-15594

Subventions

Organisme : Grantová Agentura České Republiky
ID : 18-11851S
Organisme : Deutsche Forschungsgemeinschaft
ID : WA 1850/4-2
Organisme : Center for Urban Science and Progress
ID : ITMS 26240220086

Informations de copyright

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Auteurs

Lucie Čechová (L)

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610, Prague, Czech Republic.

Juraj Filo (J)

Institute of Chemistry, Comenius University, Ilkovičova 6, 84215, Bratislava, Slovakia.

Martin Dračínský (M)

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610, Prague, Czech Republic.

Chavdar Slavov (C)

Institute of Physical and Theoretical Chemistry, Goethe University, Max-von-Laue Straße 7, 60438, Frankfurt am Main, Germany.

Dazhong Sun (D)

Institute of Physical and Theoretical Chemistry, Goethe University, Max-von-Laue Straße 7, 60438, Frankfurt am Main, Germany.

Zlatko Janeba (Z)

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610, Prague, Czech Republic.

Tomáš Slanina (T)

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610, Prague, Czech Republic.

Josef Wachtveitl (J)

Institute of Physical and Theoretical Chemistry, Goethe University, Max-von-Laue Straße 7, 60438, Frankfurt am Main, Germany.

Eliška Procházková (E)

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610, Prague, Czech Republic.

Marek Cigáň (M)

Institute of Chemistry, Comenius University, Ilkovičova 6, 84215, Bratislava, Slovakia.

Classifications MeSH