Naslov
Competing processes in the photochemistry of picolines and their N-methyl salts: photoinduced charge transfer, phototransposition and photohydration

Autori
Blažek Bregović, Vesna ; Basarić, Nikola

Izvornik
Research on chemical intermediates (0922-6168) 43 (2017), 2; 859-871

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
pyridine ; pyridinium salt ; excited state proton transfer ; excited state charge transfer ; phototransposition ; photohydration

Sažetak
Photochemical reactivity of a series of picolines and their N-methylated salts has been investigated by preparative irradiations and UV-vis spectroscopy. Understanding competing photochemical processes and knowledge of their relative efficiencies is important in the application of pyridines as photocages or in the synthesis of complex polycycles. Contrary to previous reports for the gas phase, picolines are not reactive in the phototransposition, presumably due to protonation of the pyridine nitrogen in the excited state. Deuterium exchange was observed upon irradiation in CD3CN-D2O, but it was rationalized by photoionization and radical formation. On the other hand, N-methylated picoline salts are not protonated upon excitation. They undergo photohydration and phototransposition (ΦR =0.01-0.06). Upon irradiation of iodides, azabicyclic[3.1.0] hydration products were obtained. A difference in product distribution was observed between iodides and perchlorates, due to photoelimination of perchloric acid leading to the thermal aziridine ring opening. Moreover, excitation of iodide derivatives gives rise to change transfer transition forming iodide radicals that eventually give I3- with the quantum efficiency ΦR = 0.015-0.02.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA