Aza-BODIPY derivatives: Enhanced quantum yields of triplet excited states and the generation of singlet oxygen and their role as facile sustainable photooxygenation catalysts

摘要

A new series of aza-BODIPY derivatives (4 a-4 c, 5 a,c, and 6 b,c) were synthesized and their excited-state properties, such as their triplet excited state and the yield of singlet-oxygen generation, were tuned by substituting with heavy atoms, such as bromine and iodine. The effect of substitution has been studied in detail by varying the position of halogenation. The core-substituted dyes showed high yields of the triplet excited state and high efficiencies of singlet-oxygen generation when compared to the peripheral-substituted systems. The dye 6 c, which was substituted with six iodine atoms on the core and peripheral phenyl ring, showed the highest quantum yields of the triplet excited state (φ _T=0.86) and of the efficiency of singlet-oxygen generation (φ _Δ=0.80). Interestingly, these dyes were highly efficient as photooxygenation catalysts under artificial light, as well as under normal sunlight conditions. The uniqueness of these aza-BODIPY systems is that they are stable under irradiation conditions, possess strong red-light absorption (620-680 nm), exhibit high yields of singlet-oxygen generation, and act as efficient and sustainable catalysts for photooxygenation reactions. Aza-BODIPY derivatives were synthesized and their triplet excited states and yields of singlet-oxygen generation were tuned by halogenation. The dye that was substituted with six iodine atoms showed the highest quantum yields of the triplet excited state (φ _T=0.86) and singlet oxygen (φ _Δ=0.80). These systems were stable to irradiation, had strong NIR absorption, exhibited high yields of singlet oxygen, and acted as catalysts for photooxygenation reactions (see figure).