BODIPY‐Based Photodynamic Agents for Exclusively Generating Superoxide Radical over Singlet Oxygen

Developing Type-I photosensitizers is considered as an efficient approach to overcome the deficiency of traditional photodynamic therapy (PDT) for hypoxic tumors. However, it remains a challenge to design photosensitizers for generating reactive oxygen species by the Type-I process. Herein, we report a series of α,β-linked BODIPY dimers and a trimer that exclusively generate superoxide radical (O₂^-. ) by the Type-I process upon light irradiation. The triplet formation originates from an effective excited-state relaxation from the initially populated singlet (S₁ ) to triplet (T₁ ) states via an intermediate triplet (T₂ ) state. The low reduction potential and ultralong lifetime of the T₁ state facilitate the efficient generation of O₂^-. by inter-molecular charge transfer to molecular oxygen. The energy gap of T₁ -S₀ is smaller than that between ³ O₂ and ¹ O₂ thereby precluding the generation of singlet oxygen by the Type-II process. The trimer exhibits superior PDT performance under the hypoxic environment.