UV-Vis-NIR Full-Range Responsive Carbon Dots with Large Multiphoton Absorption Cross Sections and Deep-Red...

Carbon dots (CDs), with excellent optical property and cytocompatibility, are an ideal class of nanomaterials applied in the field of biomedicine. However, the weak response of CDs in the near-infrared (NIR) region impedes their practical applications. Here, UV-vis-NIR full-range responsive fluorine and nitrogen doped CDs (N-CDs-F) are designed and synthesized that own a favorable donor-π-acceptor (D-π-A) configuration and exhibit excellent two-photon (λ_ex = 1060 nm), three-photon (λ_ex = 1600 nm), and four-photon (λ_ex = 2000 nm) excitation upconversion fluorescence. D-π-A-conjugated CDs prepared by solvothermal synthesis under the assistance of ammonia fluoride are reported and are endowed with larger multiphoton absorption (MPA) cross sections (3PA: 9.55 × 10^-80 cm⁶ s² photon^-2 , 4PA: 6.32 × 10^-80 cm⁸ s³ photon^-3 ) than conventional organic compounds. Furthermore, the N-CDs-F show bright deep-red to NIR fluorescence both in vitro and in vivo, and can even stain the nucleoli of tumor cells. A plausible mechanism is proposed on the basis of the strong inter-dot and intra-dot hydrogen bonds through NH···F that can facilitate the expanding of conjugated sp² domains, and thus not only result in lower highest occupied molecular orbital-lowest unoccupied molecular orbital energy level but also larger MPA cross sections than those of undoped CDs.