Advancing Two‐Photon Photodynamic Therapy Over NIR‐II Excitable Conjugated Microporous Polymer with NIR‐I Emission

The availability of second near-infrared (NIR-II) excitable two-photon photosensitizers with NIR-I emission for efficient photodynamic therapy (PDT) is limited by challenges in molecular design. In this study, a NIR-II light-excitable two-photon conjugated microporous polymer (Tph-Dbd) with emission in the NIR-I region is developed. The large conjugated system and delocalized electronic structures endow Tph-Dbd with a large two-photon absorption cross-section under NIR-II light excitation. Moreover, the efficient electron acceptor and donor units within the π-conjugated backbones result in NIR-I emission for high signal-to-background ratio imaging, as well as separated highest occupied molecular orbital and lowest unoccupied molecular orbital distributions for excellent singlet oxygen generation ability. The excellent NIR-II excitable two-photon absorption activity, NIR-I emission, good biocompatibility, and high photostability allow Tph-Dbd to be used for efficient in vitro fluorescence imaging guided PDT. Moreover, the impressive photothermal effect of Tph-Dbd can overcome the limitations of PDT in the treatment of hypoxic tumors. This study highlights a strategy for designing NIR-II excitable two-photon photosensitizers for advanced PDT.