Donor/π‐Bridge Manipulation for Constructing a Stable NIR‐II Aggregation‐Induced Emission Luminogen with Balanced Phototheranostic Performance**

Owing to their versatile functionality and tunable energy dissipation, aggregation-induced emission luminogens (AIEgens) have emerged as a potential platform for multimodal theranostics. Nevertheless, the construction of AIE-active phototheranostic agents in the second near-infrared window (NIR-II, 1000-1700 nm), which allows superior resolution and minimized photodamage, is still a formidable challenge. Herein, benzo[c]thiophene serves as an electron-rich and bulky donor (D)/π-bridge, which can enlarge the conjugation length and distort the backbone of an AIEgen. By precise D/π-bridge engineering, highly stable NIR-II AIEgen DPBTA-DPTQ nanoparticles are obtained with acceptable NIR-II fluorescence quantum yield and excellent photothermal conversion efficiency. In addition, the spatial conformation of DPBTA-DPTQ is determined for the first time by X-ray single crystal diffraction and theoretical simulations. DPBTA-DPTQ NPs have good biocompatibility and show efficient photothermal therapeutic effects in in vitro tests. Furthermore, DPBTA-DPTQ NPs were used in fluorescence-photoacoustic-photothermal trimodal imaging-guided photothermal eradication of tumors in HepG2 and B16-F10 tumor-xenografted mice.