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

Čechová, Lucie, Kind, Jonas, Dračínský, Martin, Filo, Juraj, Janeba, Zlatko, Thiele, Christina M., Cigáň, Marek, Procházková, Eliška
Journal of organic chemistry 2018 v.83 no.11 pp. 5986-5998
cis-trans isomers, irradiation, mathematical models, nuclear magnetic resonance spectroscopy, organic chemistry, organic compounds, photoisomerization, photolysis, ultraviolet radiation
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(π → π*)–vis(n → π*) photoswitches. Surprisingly equal trans-to-cis photoisomerization quantum yields for π → π* and n → π* excitation indicate the blocking of the inversion pathway following π → π* excitation. In contrast to that, DFT computations suggest the inversion mechanism for the reverse thermal cis-to-trans isomerization of 5-phenylazopyrimidines.