PET-based bisBODIPY photosensitizers for highly efficient excited triplet state and singlet oxygen generation: tuning photosensitizing ability by dihedral angles.

Herein, four covalent BODIPY heterodimers that differ by dihedral angles were shown to be highly efficient excited triplet state (T) photosensitizers (PSs) for singlet oxygen formation with a quantum yield (Φ) of up to 0.94 as compared to their respective monomers, which had only negligible Φ of ca. 0.060. More interestingly, these PSs generate Tvia charge recombination mechanism rather than traditional inter-system crossing. The photosensitizing ability of dimers is easily tuned by either the dihedral angle (between the two linked BODIPYs) or solvent polarity. Laser flash photolysis, time-resolved and steady state fluorescence, quantum chemical calculation, as well as thermodynamic analysis were employed to study the associated photophysical process to reveal the T formation mechanism: photo-induced electron transfer (PET) followed by charge recombination. Due to its heavy-atom-free nature, polarity selectivity, high efficiency, and easy tunability, this PET-based PS and its mechanism are very useful in developing new PS for photodynamic therapy of tumors, photobiology, and organic photochemistry.