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Rational Design of Conjugated Small Molecules for Superior Photothermal Theranostics in the NIR‐II Biowindow

Extensive recent progress has been made on the design and applications of organic photothermal agents for biomedical applications because of their excellent biocompatibility comparing with inorganic materials. One major hurdle for the further development and applications of organic photothermal agents is the rarity of high‐performance materials in the second near‐infrared (NIR‐II) window, which allows deep tissue penetration and causes minimized side effects. Up till now, there have been few reported NIR‐II‐active photothermal agents and their photothermal conversion efficiencies are relatively low. Herein, optical absorption of π‐conjugated small molecules from the first NIR window to the NIR‐II window is precisely regulated by molecular surgery of substituting an individual atom. With this technique, the first demonstration of a conjugated oligomer (IR‐SS) with an absorption peak beyond 1000 nm is presented, and its nanoparticle achieves a record‐high photothermal conversion efficiency of 77% under 1064 nm excitation. The nanoparticles show a good photoacoustic response, photothermal therapeutic efficacy, and biocompatibility in vitro and in vivo. This work develops a strategy to boost the light‐harvesting efficiency in the NIR‐II window for cancer theranostics, offering an important step forward in advancing the design and application of NIR‐II photothermal agents.