Thermal isomerization of phenylazoindoles: Inversion or rotation? That is the question

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F23%3A73622047" target="_blank" >RIV/61989592:15640/23:73622047 - isvavai.cz</a>

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/10.1002/qua.27120" target="_blank" >https://onlinelibrary.wiley.com/doi/10.1002/qua.27120</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/qua.27120" target="_blank" >10.1002/qua.27120</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thermal isomerization of phenylazoindoles: Inversion or rotation? That is the question

Popis výsledku v původním jazyce

Azoheteroarenes represent an attractive group of photochromes exhibiting a large structural variability and tunability of photoswitching characteristics. The thermal back-isomerization can proceed via inversion or rotation mechanisms, depending on the functionalization and environment. However, the distinction between the two remains a challenge for both experiment and theory. Here, four experimentally fully characterized phenylazoindoles are studied to establish the mechanism of back-reaction in solvent using density functional theory (DFT), spin-flip time-dependent (TD-)DFT, mixed-reference TD-DFT, and restricted ensemble Kohn-Sham approaches as well as CASPT2 and CCSD(T). While the inversion is consistently described by all methods, the rotation mechanism requires multireference approaches including dynamic correlation. The balanced description of both pathways becomes even more important in solvent which apparently affects the mechanism. For the present set, the range-separated functionals combined with continuum models appear to be the most consistent with experiment in terms of the substitutional and solvent effects on thermal halftimes.

Název v anglickém jazyce

Thermal isomerization of phenylazoindoles: Inversion or rotation? That is the question

Popis výsledku anglicky

Azoheteroarenes represent an attractive group of photochromes exhibiting a large structural variability and tunability of photoswitching characteristics. The thermal back-isomerization can proceed via inversion or rotation mechanisms, depending on the functionalization and environment. However, the distinction between the two remains a challenge for both experiment and theory. Here, four experimentally fully characterized phenylazoindoles are studied to establish the mechanism of back-reaction in solvent using density functional theory (DFT), spin-flip time-dependent (TD-)DFT, mixed-reference TD-DFT, and restricted ensemble Kohn-Sham approaches as well as CASPT2 and CCSD(T). While the inversion is consistently described by all methods, the rotation mechanism requires multireference approaches including dynamic correlation. The balanced description of both pathways becomes even more important in solvent which apparently affects the mechanism. For the present set, the range-separated functionals combined with continuum models appear to be the most consistent with experiment in terms of the substitutional and solvent effects on thermal halftimes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

21002 - Nano-processes (applications on nano-scale); (biomaterials to be 2.9)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

ISSN

0020-7608

e-ISSN

1097-461X

Svazek periodika

123

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

—

Kód UT WoS článku

000960460800001

EID výsledku v databázi Scopus

2-s2.0-85151476454