Photoswitching Behavior of 5-Phenylazopyrimidines: In Situ Irradiation NMR and Optical Spectroscopy Combined with Theoretical Methods

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F18%3A00490912" target="_blank" >RIV/61388963:_____/18:00490912 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.joc.8b00569" target="_blank" >http://dx.doi.org/10.1021/acs.joc.8b00569</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.8b00569" target="_blank" >10.1021/acs.joc.8b00569</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Photoswitching Behavior of 5-Phenylazopyrimidines: In Situ Irradiation NMR and Optical Spectroscopy Combined with Theoretical Methods

Popis výsledku v původním jazyce

The photoswitching behavior of 5-phenylazopyrimidines was investigated by optical methods and NMR spectroscopy with in situ irradiation sustained by mathematical modeling and DFT calculations. Irradiation of various compounds with electron-donating groups on the pyrimidine ring and substituents with electron-withdrawing as well as electron-donating substituent in the para-position of the phenyl ring were examined. All compounds could be successfully converted to the cis isomer, this isomerization and the subsequent thermal fading were studied. Switching cycles can be repeated without signs of photodegradation for most of the compounds, which makes them adept to molecular photoswitches. Interestingly, the chloro and cyano derivatives can be switched without UV light, which makes them vis(pi -> pi) vis(n -> pi*) photoswitches. Surprisingly equal trans-to-cis photoisomerization quantum yields for pi -> pi* and n -> pi* excitation indicate the blocking of the inversion pathway following pi -> pi* excitation. In contrast to that, DFT computations suggest the inversion mechanism for the reverse thermal cis-to-trans isomerization of 5-phenylazopyrimidines.

Název v anglickém jazyce

Photoswitching Behavior of 5-Phenylazopyrimidines: In Situ Irradiation NMR and Optical Spectroscopy Combined with Theoretical Methods

Popis výsledku anglicky

The photoswitching behavior of 5-phenylazopyrimidines was investigated by optical methods and NMR spectroscopy with in situ irradiation sustained by mathematical modeling and DFT calculations. Irradiation of various compounds with electron-donating groups on the pyrimidine ring and substituents with electron-withdrawing as well as electron-donating substituent in the para-position of the phenyl ring were examined. All compounds could be successfully converted to the cis isomer, this isomerization and the subsequent thermal fading were studied. Switching cycles can be repeated without signs of photodegradation for most of the compounds, which makes them adept to molecular photoswitches. Interestingly, the chloro and cyano derivatives can be switched without UV light, which makes them vis(pi -> pi) vis(n -> pi*) photoswitches. Surprisingly equal trans-to-cis photoisomerization quantum yields for pi -> pi* and n -> pi* excitation indicate the blocking of the inversion pathway following pi -> pi* excitation. In contrast to that, DFT computations suggest the inversion mechanism for the reverse thermal cis-to-trans isomerization of 5-phenylazopyrimidines.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA18-11851S" target="_blank" >GA18-11851S: Intermolekulární interakce studované pomocí NMR spektroskopie a pokročilých kvantově chemických výpočtů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

—

Svazek periodika

83

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

5986-5998

Kód UT WoS článku

000434367700010

EID výsledku v databázi Scopus

2-s2.0-85046541952