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Type I pathways require a strongly reducing excited state to drive electron transfer, whereas type II pathways demand a long\u2010lived triplet state to enable efficient energy transfer to molecular oxygen. Since both originate from the same triplet manifold, optimizing one property inevitably compromises the other, limiting the oxidative potency and broad applicability of conventional photosensitizers within the heterogeneous tumor microenvironment. To overcome this limitation, in this study, the design, synthesis, and biological evaluation of a cyclometalated iridium(III) photoswitchable complex is reported, engineered to undergo photo\u2010induced intramolecular homolytic bond cleavage to generate a transient biradical intermediate. The resulting open\u2010shell species simultaneously consist of a strongly reducing radical intermediate and a quinoid\u2010stabilized long\u2010lived triplet excited state, concurrently activating type I electron\u2010transfer and type II energy\u2010transfer pathways to produce in tandem superoxide, hydroxyl radicals, and singlet oxygen. This synergistic dual\u2010pathway oxidative stress triggers PANoptosis, a coordinated cell\u2010death program concurrently engaging apoptotic, necroptotic, and pyroptotic machinery, and elicits a robust systemic antitumor immune response, establishing intramolecular biradical generation as a compelling molecular design principle for next\u2010generation photodynamic cancer immunotherapy.<\/jats:p>","DOI":"10.1002\/anie.5995290","type":"journal-article","created":{"date-parts":[[2026,7,8]],"date-time":"2026-07-08T11:00:56Z","timestamp":1783508456000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Harnessing Immunogenic PANoptosis With Iridium(III) Biradical Photosensitizers for Melanoma Photoimmunotherapy"],"prefix":"10.1002","volume":"65","author":[{"given":"Tianying","family":"Wang","sequence":"first","affiliation":[{"name":"MOE Key Laboratory of Bioinorganic and Synthetic Chemistry School of Chemistry Sun Yat\u2010Sen University  Guangzhou P. 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