Photochemical properties of substituted tetraazachlorins

Abstract

The photochemical properties of water-insoluble metal-free tetraazachlorin derivatives in organic solvents and aqueous micellar solutions of nonionic surfactants were investigated. The quantum yields of fluorescence, singlet oxygen generation and photodegradation were evaluated in benzene. The highest photostability and singlet oxygen quantum yield (ΦΔ = 0.7) was found for 2,2,3,3-tetramethyl-7,8,12,13,17,18-hexaphenyltetraazachlorin. The moderate ΦΔ values (0.21–0.35) of triarenotetraazachlorins in benzene were established. Expansion of tetraazachlorin π-system by fusion of three aromatic rings leads to reduction of efficiency of singlet oxygen generation. The study of photodegradation mechanism shows that radical photooxidation apparently is most plausible, though 1 O 2 may partly contribute to photodestruction of some tetraazachlorins. In aqueous colloidal solution of nonionic surfactant (Cremophor EL) the same, as in benzene, effect of sensitizer structure upon efficacy of singlet oxygen production was observed. It was shown that 1 O 2 diffusion from micelle core into solution and then to target slows its oxidation rate substantially in comparison to the case where sensitizer and target are localized in the same micelle.