Exploring a new class of singlet fission fluorene derivatives with high-energy triplets

In this study, we report strong experimental evidence for singlet fission (SF) in a new class of fluorene-based molecules, exhibiting two-branched donor–acceptor structures. The time-resolved spectroscopic results disclose ultrafast formation of a double triplet state (occurring in few picoseconds) and efficient triplet exciton separation (up to 145% triplet yield). The solvent polarity effect and the role of intramolecular charge transfer (ICT) on the SF mechanism have been thoroughly investigated with several advanced spectroscopies. We found that a stronger push–pull character favors SF, as long as the ICT does not act as a trap by opening a competitive pathway. Within the context of other widely-known SF chromophores, the unconventional property of generating high-energy triplet excitons (ca. 2 eV) via SF makes these materials outstanding candidates as photosensitizers for photovoltaic devices.