The Balance Effect of - Electronic Coupling on NIR-II Emission and Photodynamic Properties of Highly Hydrophobic Conjugated Photosensitizers

Deep NIR organic phototheranostic molecules generally have large pi-conjugation structures and show highly hydrophobic properties, thus, forming strong pi-pi stacking in the aqueous medium, which will affect the phototheranostic performance. Herein, an end-group strategy is developed to lift the performance of NIR-II emitting photosensitizers. Extensive characterizations reveal that the hydrogen-bonding interactions of the hydroxyl end group can induce a more intense pi-pi electronic coupling than the chlorination-mediated intermolecular forces. The results disclose that pi-pi stacking will lower fluorescence quantum yield but significantly benefit the photodynamic therapy (PDT) efficiency. Accordingly, an asymmetrically substituted derivative (BTIC-delta OH-2Cl) is developed, which shows balanced phototheranostic properties with excellent PDT efficiency (14.6 folds of ICG) and high NIR-II fluorescence yield (2.27%). It proves the validity of the end-group strategy on controlling the pi-pi interactions and rational tuning the performance of NIR-II organic phototheranostic agents.