Enhancement of photoinduced reactive oxygen species generation in open-cage fullerenes

Photodynamic therapy is an important tool in modern medicine due to its effectiveness, safety, and the ability to provide targeted treatment for a range of diseases. Photodynamic therapy utilizes photosensitizers to generate reactive oxygen species (ROS). Fullerenes can be used as photosensitizers to produce ROS in high quantum yields. Open-cage fullerenes are a subclass of fullerenes characterized by a partially open structure, with one or more openings or apertures. The promising electrochemical properties of open-cage fullerenes motivated us to investigate their use for DNA-cleavage and ROS generation under visible light irradiation through type I electron transfer and type II energy transfer reactions. Our results show that open-cage C₆₀ fullerenes are more efficient for photoinduced cleavage of DNA and ROS generation via both the type I electron transfer and type II energy transfer pathways than pristine C₆₀ or a C₆₀ pyrrolidine derivative without open-cage. The greater efficiency of ROS generation by open-cage C₆₀ fullerene in type I and type II reactions can be attributed to the increased rate of the initial intersystem crossing process, resulting from larger total reorganization energies, as indicated by computationally calculated relative rates using the Marcus equation, and the lower reduction potential of the open-cage derivative 3, as determined by CV, which facilitates a more efficient generation of the corresponding radical anion (C₆₀˙^-).