Molecular Programming of NIR‐IIb‐Emissive Semiconducting Small Molecules for In Vivo High‐Contrast Bioimaging Beyond 1500 nm

Materials with long-wavelength second near-infrared (NIR-II) emission are highly desired for in vivo dynamic visualizating of microstructures in deep tissues. Herein, by employing an atom-programming strategy, a series of highly fluorescent semiconducting oligomers (SOMs) with tunable NIR-IIb emissions are developed for bioimaging applications. After self-assembly into nanoparticles (NPs), they show good brightness, high photostability, and satisfactory biocompatibility. The SOM NPs are applied as probes for high-resolution imaging of whole-body and hind-limb blood vessels, biliary tract, and bladder with their emissions over 1500 nm. This work demonstrates an atom-programming strategy for constructing semiconducting small molecules with enhanced NIR-II fluorescence for deep-tissue imaging, affording new insight for advancing molecular design of NIR-II fluorophores.