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Organic photosensitizers possessing efficient intersystem crossing (ISC) and forming long-living triplet excited states, play a crucial role in a number of applications. A common approach in the design of such dyes relies on the introduction of heavy atoms (e.g. transition metals or halogens) into the structure, which promote ISC via spin-orbit coupling interaction. In recent years, alternative methods to enhance ISC have been actively studied. Among those, the generation of triplet excited states through photoinduced electron transfer (PET) in heavy-atom-free molecules has attracted particular attention because it allows for the development of photosensitizers with programmed triplet state and fluorescence quantum yields. Due to their synthetic accessibility and tunability of optical properties, boron dipyrromethenes (BODIPYs) are so far the most perspective class of photosensitizers operating via this mechanism. This article reviews recently reported heavy-atom-free BODIPY donor-acceptor dyads and dimers which produce long-living triplet excited states and generate singlet oxygen. Structural factors which affect PET and concomitant triplet state formation in these molecules are discussed and the reported data on triplet state yields and singlet oxygen generation quantum yields in various solvents are summarized. Finally, examples of recent applications of these systems are highlighted.

Heavy-atom-free BODIPY photosensitizers with intersystem crossing mediated by intramolecular photoinduced electron transfer