Electron-acceptor density adjustments for preparation conjugated polymers with NIR-II absorption and brighter NIR-II...

Designing conjugated polymers (CPs) with both efficient second near-infrared wavelength (NIR-II) fluorescence and NIR-II photothermal therapy performance remains a huge challenge, as the introduction of excessively strong electron donor and acceptor units significantly increase non-radiative decay. Herein, we describe an "electron acceptor density adjustment" strategy to address this problem, since a lower electron acceptor density in the conjugated polymer backbone can enhance the radiative rate constant and improve NIR-II fluorescence brightness. We used quaterthiophene (4T) with four repeated thiophene chain units and bithiophene (2 TC) modified with long alkyl side chains to reduce the electron acceptor density in the conjugated polymer backbone. The resultant 1064 nm absorption polymer, TTQ-2TC-4T displayed approximately 7.30-folds enhancement in NIR-II emission intensity compared to that of undoped TTQ-1T at the same mass concentration in toluene solution. Furthermore nanoparticles (TTQ-MnCO NPs) based on TTQ-2TC-4T and CO donors (Mn₂(CO)₁₀) were developed to realize NIR-II FI-guided 1064 nm laser-triggered NIR-II PTT/Gas synergistic therapy. The TTQ-MnCO NPs nanoparticles exhibited high photothermal conversion efficiency (η) of 44.43% at 1064 nm and high specific NIR-II fluorescence imaging of the cerebral vasculature of live mice. The in vivo results demonstrate that TTQ-MnCO NPs nanoparticles have excellent PTT/Gas synergistic therapeutic effects in MCF-7 tumor-bearing mice under 1064 nm laser irradiation. This study provides a new approach for optimizing both NIR-II fluorescence and NIR-II photothermal performance of NIR-II absorption conjugated polymers.