AIE-active Ir(III) complexes as type-I dominant photosensitizers for efficient photodynamic therapy

The ability of a photosensitizer (PS) to generate reactive oxygen species (ROS) including type I oxygen free radicals and type II ¹O₂ is pivotal for photodynamic therapy. Luminescent Ir(III) complexes are effective PSs with high ¹O₂ generation ability owing to their high intersystem crossing ability and effective energy transfer to ³O₂. However, so far, reports on type I ROS based on ˙OH generation induced by Ir(III) PS are still rare. In this work, four novel aggregation-induced emission (AIE)-active Ir(III) PSs, namely MFIriqa, MFIrqa, SFIriqa, and SFIrqa have been designed and synthesized, which show highly efficient emission in the aggregated state. Cell imaging experiment results indicate that all four Ir(III) PSs can effectively improve the signal-to-noise ratio of imaging by reducing the interference from the background due to their fascinating AIE properties. Importantly, in vitro, Ir(III) PSs MFIrqa, SFIriqa, and SFIrqa nanoparticles show obvious photodynamic activity toward cancer cells upon irradiation accompanied by type I ˙OH generation, which may be attributed to the unique excited-state characteristics of Ir(III) complexes. This work will provide guidance for the construction of a type I photosensitizer based on the AIE-active Ir(III) complex, which offers great advantages for potential clinical applications under hypoxic conditions.