Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene

Abstract Singlet fission (SF), a promising mechanism of multiple exciton generation, has only recently been engineered as a fast, efficient, intramolecular process (iSF). The challenge now lies in designing and optimizing iSF materials that can be practically applied in high‐performance optoelectronic devices. However, most of the reported iSF systems, such as those based on donor–acceptor polymers or pentacene, have low triplet energies, which limits their applications. Tetracene‐based materials can overcome significant challenges, as the tetracene triplet state is practically useful, ≈1.2 eV. Here, the synthesis and excited state dynamics of a conjugated tetracene homopolymer are studied. This polymer undergoes ultrafast iSF in solution, generating high‐energy triplets on a sub‐picosecond time scale. Magnetic‐field‐dependent photocurrent measurements of polytetracene‐based devices demonstrate the first example of iSF‐generated triplet extraction in devices, exhibiting the potential of iSF materials for use in next‐generation devices.