A NIR‐II Organic Dendrimer with Superb Photothermal Performance Based on Electron‐Donor Iteration for Photothermal Immunotherapy

Abstract Organic photothermal materials have attracted extensive attention due to their designable molecular structure, tunable excited‐state properties, and excellent biocompatibility, however, the development of near‐infrared II (NIR‐II) absorbing organic photothermal materials with high photothermal conversion efficiency (PTCE) and molar extinction coefficient (ɛ) remains challenging. Herein, a novel “electron‐donor iteration” strategy is proposed to construct organic photothermal dendrimers (CR‐DPA‐T, CR‐(DPA)₂‐T and CR‐(DPA)₃‐T) with donor‐π‐acceptor‐π‐donor (D‐π‐A‐π‐D) features and diradical characteristics. Owing to the enhanced D–A effect and intramolecular motions, their absorption and photothermal capacity increase as the generation grows. Surprisingly, an excellent photothermal performance (ɛ₁₀₆₄ × PTCE₁₀₆₄) with a superb value of 2.85 × 10⁴ in the NIR‐II region is achieved for CR‐(DPA)₃‐T nanoparticles (CR‐(DPA)₃‐T NPs) compared to most reported counterparts. Besides, CR‐(DPA)₃‐T NPs exhibit superior antitumor efficacy by the synergistic effect of photothermal therapy (PTT) and immunotherapy, efficiently inhibiting the growth of both primary and distant tumors. To the best knowledge, organic photothermal dendrimer is for the first time reported, and a universal donor engineering strategy is offered to develop NIR‐II‐absorbing organic photothermal materials for photothermal immunotherapy.