In contrast to Type-II photodynamic therapy (PDT), Type-I PDT with less oxygen consumption has shown great potential against tumor hypoxia. However, there are limited strategies available for designing Type-I photosensitizers (PSs). Herein, we present a promising strategy for synthesizing Type-I PSs () using Tröger's base (TB) framework. The TB framework can promote intersystem crossing efficiency and create an electron-rich environment, making it the most likely site for electron transfer to O to generate Type-I ROS. As anticipated, demonstrates Type-I ROS generation capability and their impressive visible light-harvesting ability significantly enhances this capability. Among them, demonstrates outstanding biocompatibility and PDT efficiency in vitro under both normoxia and hypoxia. Furthermore, effectively inhibits tumor growth in vivo, with negligible side effects. This is attributed to 's efficient generation of Type-I ROS and endoplasmic reticulum targeting ability. This study thus offers useful insights into developing Type-I PSs.
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