Modulation of Donor in Purely Organic Triplet Harvesting AIE‐TADF Photosensitizer for Image‐guided Photodynamic Therapy

Image-guided photodynamic therapy is acknowledged as one of the most demonstrative therapeutic modalities for cancer treatment because of its high precision, non-invasiveness, and improved imaging ability. A series of purely organic photosensitizers denoted as BTMCz, BTMPTZ, and BTMPXZ, have been designed and synthesized and are found to exhibit both thermally activated delayed fluorescence and aggregation-induced emission simultaneously. Experimental and theoretical studies are combined to reveal that modulation of the donor of the photosensitizer enables distinct thermally activated delayed fluorescence via a second-order spin-orbit perturbation mechanism involving lowest singlet charge-transfer and higher-lying triplet locally excited states, respectively. Further, different donor strengths and unique aggregations (H-, J- and X-type packings) greatly influence their color-tunable up-converted luminescence and endow them with superb dispersibility in water. The confocal microscopy-based cellular uptake study confirms the successful internalization of the nano-probes, while BTMCz enables the generation of reactive oxygen species (singlet oxygen) under white-light irradiation, enabling the efficient killing of cancer cells.