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Essential metal\u2010complex shows great potential in photoimmunotherapy, which however hardly generates reactive oxygen species (ROS) to active photoimmunotherapy under light irradiation due to low spin\u2013orbit coupling (SOC) resulting in intersystem crossing (ISC) being blocked. To address this challenge, we innovatively proposed the concept of essential\u2010metal ion as an electron\u2010withdrawing group to modulate the donor\u2010acceptor (D\u2010A) system, thereby significantly improving ROS generation efficiency. As a proof of concept, we designed and synthesized a series of Zn\n                    <jats:sup>2+<\/jats:sup>\n                    \u2010complexes through constructing enhanced D\u2010A systems. Zn\n                    <jats:sup>2+<\/jats:sup>\n                    coordination efficiently enhances the ISC by lowering the excited singlet\u2010triplet energy gap (\u0394E\n                    <jats:sub>S1\u2212T1<\/jats:sub>\n                    ), leading to exceptionally high ROS generation efficiency through Type I mechanisms to overcome hypoxia and the immunosuppression of tumor microenvironment. In these Zn\n                    <jats:sup>2+<\/jats:sup>\n                    \u2010complexes, Zn\u2010TPY\u2010TPA\u2010DTZ can photodynamically damage lysosomes to trigger pyroptosis, which further induce anti\u2010tumor immune responses through the promotion of immunogenic cell death (ICD), and ultimately generates a robust anti\u2010tumor immune response and curbed the proliferation of 4T1 tumors in vivo. This study provides systematic guidance for the rational design of advanced Zn\n                    <jats:sup>2+<\/jats:sup>\n                    \u2010complexes, propelling advancements in cancer treatment strategies.\n                  <\/jats:p>","DOI":"10.1002\/anie.202525200","type":"journal-article","created":{"date-parts":[[2026,1,29]],"date-time":"2026-01-29T05:24:43Z","timestamp":1769664283000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Zinc\u2010Complex Orchestrating Pyroptosis for Hypoxia\u2010Tolerant Photoimmunotherapy"],"prefix":"10.1002","volume":"65","author":[{"given":"Jinyu","family":"An","sequence":"first","affiliation":[{"name":"Key Laboratory of Advanced Technologies of Materials, Ministry of Education School of Life Science and Engineering Southwest Jiaotong University Chengdu P. R. China"},{"name":"College of Biomedical Engineering Sichuan University Chengdu Sichuan P. R. 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