Wavelength selective photoactivated autocatalytic oxidation of 5,12-dihydrobenzo[b]phenazine and its application in metal-free synthesis

Abstract

Photochemical stability of 5,12-dihydrobenzo[b]phenazine (DHBP) was investigated with LEDs with central emission wavelengths in a range of 365 to 595 nm. Photochemical conversion of DHBP to benzo[b]phenazine (BP) was observed with wavelengths upto 516 nm. Light of 490 and 516 nm is not absorbed by DHBP, but photoactivated autocatalytic oxidation of DHBP to BP with these wavelengths was confirmed. The reaction rate is in a range of 111–208 μg min⁻¹ with these LEDs. The mechanism of the reaction was examined and the experimental results exclude the intermolecular interaction such as the Förster resonance energy transfer, the intermolecular charge transfer, the photoinduced electron transfer and the formation of an exciplex. The formation of the reactive oxygen species was verified with electron paramagnetic resonance, which indicates its potential in the synthesis. When sunlight was used as the light source, the oxidation rate of 1 mg mL⁻¹ DHBP was 393 μg min⁻¹. Same autocatalytic oxidation was also observed on similar compounds and it can be used for producing metal-free organic substances for semiconductors.