Proximal Oblique-Packing of Heptamethine Cyanines through Spiro-Connection Boosts Triplet State Generation in Near-Infrared

Near-infrared (NIR) triplet dyes are the cornerstones of cutting-edge biomedical and material applications. The difficulty in rational development of triplet dyes increases exponentially as the absorption wavelength shifts deeper into the NIR range. Although classical H-/J-typed packing of NIR dyes has the potential to enhance intersystem crossing (ISC) compared with that in single-chromophore dyes, the triplet state quantum yields remain limited in such strategy. Herein, proximal oblique-packed (V-shaped) heptamethine cyanines (SZ780) through spiro-connection were achieved. Multi-channel ultrafast ISC were direct observed in SZ780 and a record high ISC rate constant (up to ~10¹¹ s⁻¹) is registered among all the reported NIR triplet dyes. SZ780 exhibits a triplet state quantum yield of 18.9 % upon excitation at 750 nm, which is almost an order of magnitude higher than that of the monomer (IR780, 2.1 %) and nearly threefold increase compared to that of the H-packed dimer (SC780) (6.7 %). Moreover, SZ780 efficiently generates singlet oxygen under 808 nm light irradiation, inducing cancer cell apoptosis in vivo. These findings demonstrate that constructing V-aggregated dyes system by spiro-connection offers a powerful approach for the design of high-performance NIR triplet sensitizers.