From Exciton Dynamics to Cell Fate: A Carbon Dot Based NIR Photocatalytic Platform for Pyroptosis via Self‐Trapped Excitons

Near‐infrared (NIR) light‐triggered photocatalytic therapy remains a critical challenge in efficient reactive oxygen species (ROS) generation due to limited exciton utilization. Herein, a new kind of carbon dots (CDs) system is reported with tailored self‐trapped excitons (STE) that enable effective NIR‐responsive ROS production for pyroptosis induction. The engineered NIR‐photoactive CDs derived from red‐emissive CDs through formic acid‐mediated surface engineering and defects construction. Specifically, charge transfer state formed by the balanced electron‐withdrawing/donating groups, enabling NIR‐induced electron transition. Crucially, the resultant excitons in the defects enhance electron–phonon coupling, thereby inducing lattice distortion through strong electron–phonon coupling, leading to the formation of STE. The spatial separation of electrons and holes within STE suppresses recombination losses and extends electron transfer process, thereby amplifying superoxide radicals production, while the NIR light induced holes react with water to generate hydroxyl radical via phonon assisted hole transmission. The optimized system induces gasdermin‐E‐mediated pyroptosis through radical storm generation and initiates antitumor immunity, achieving efficiency tumor suppression with recurrence prevention in murine models. The work establishes a structure‐property paradigm for excitons regulation in CDs based photocatalysis and provides a theranostic platform for non‐invasive tumor phototherapy.