Optimizing the Thermodynamics and Kinetics of the Triplet-Pair Dissociation in Donor–Acceptor Copolymers for Intramolecular Singlet Fission

[Image: see text] Singlet fission (SF) is a two-step process in which a singlet splits into two triplets throughout the so-called correlated triplet-pair ((1)TT) state. Intramolecular SF (iSF) materials, in particular, have attracted growing interest as they can be easily implemented in single-junction solar cells and boost their power conversion efficiency. Still, the potential of iSF materials such as polymers and oligomers for photovoltaic applications has been partially hindered by their ability to go beyond the (1)TT intermediate and generate free triplets, whose mechanism remains poorly understood. In this work, the main aspects governing the (1)TT dissociation in donor–acceptor copolymers and the key features that optimize this process are exposed. First, we show that both thermodynamics and kinetics play a crucial role in the intramolecular triplet-pair separation and second, we uncover the inherent flexibility of the donor unit as the fundamental ingredient to optimize them simultaneously. Overall, these results provide a better understanding of the intramolecular (1)TT dissociation process and establish a new paradigm for the development of novel iSF active materials.