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We herein present an approach of photo‐induced disproportionation for preparation of Type‐I photodynamic agents. As a proof of concept, BODIPY‐based photosensitizers were rationally designed and prepared. The photo‐induced intermolecular electron transfer between homotypic chromophores leads to the disproportionation reaction, resulting in the formation of charged intermediates, cationic and anionic radicals. The cationic radicals efficiently oxidize the cellularimportant coenzyme, tetrahydrobiopterin (BH4), and the anionic radicals transfer electrons to oxygen to produce superoxide radicals (O2−⋅). One of our Type‐I photodynamic agents not only self‐assembles in water but also effectively targets the endoplasmic reticulum. It displayed excellent photocytotoxicity even in highly hypoxic environments (2 % O2), with a half‐maximal inhibitory concentration (IC50) of 0.96 μM, and demonstrated outstanding antitumor efficacy in murine models bearing HeLa tumors. [ABSTRACT FROM AUTHOR]

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 3O2 and 1O2 thereby precluding the generation of singlet oxygen by the Type‐II process. The trimer exhibits superior PDT performance under the hypoxic environment. [ABSTRACT FROM AUTHOR]

Keywords: BODIPY; hypoxia; photodynamic therapy; photosensitizers; superoxide radical EN BODIPY hypoxia photodynamic therapy photosensitizers superoxide radical 24134 24134 1 10/27/21 20211102 NES 211102 In this Research Article, the absorption and fluorescence spectra of compound B 2 b (Figure 6 b) were incorrect. Berichtigung: BODIPY-Based Photodynamic Agents for Exclusively Generating Superoxide Radical over Singlet Oxygen BODIPY, hypoxia, photodynamic therapy, photosensitizers, superoxide radical. [Extracted from the article]

BODIPY, photodynamic therapy, photosensitizers, superoxide radical, hypoxia Corrigendum: BODIPY-Based Photodynamic Agents for Exclusively Generating Superoxide Radical over Singlet Oxygen Keywords: BODIPY; hypoxia; photodynamic therapy; photosensitizers; superoxide radical EN BODIPY hypoxia photodynamic therapy photosensitizers superoxide radical 23938 23938 1 10/27/21 20211102 NES 211102 In this Research Article, the absorption and fluorescence spectra of compound B 2 b (Figure 6 b) were incorrect. [Extracted from the article]