Conjugation Length Dependence of Intramolecular Singlet Fission in a Series of Regioregular Oligo 3-Alkyl(thienylene-vinylene)s

Activated intramolecular singlet fission is known to occur in the conjugated polymer polythienylene-vinylene (P3TV). Instead, efficient intersystem crossing has been observed in a short 3-alkyl(thienylene-vinylene) dimer. Here, we investigate a series of oligomers covering the conjugation length gap between the dimer and polymer. We confirm that the polymer and longer oligomers undergo activated intramolecular singlet fission, while the shorter oligomers with less than 3 units predominantly undergo efficient intersystem crossing. For the longer oligomers, the intermediate state of singlet fission is assigned to the 3A_g^- covalent state of triplet pair character, as predicted by several computational studies. Our results point to potential pitfalls when assigning triplet production pathways solely with transient absorption spectroscopy.