High-spin states in molecular systems hold significant interest for applications ranging from optoelectronics to quantum technologies. Spin states generated in intramolecular singlet fission are of particular relevance, yet the mechanisms controlling triplet-pair formation are not fully understood – especially the involvement of quintet states in luminescence at room temperature remains experimentally elusive. Here, we investigate high-spin state formation and emission in dimers and trimers comprising multiple diphenylhexatriene units. We demonstrate the formation of pure quintet states in all these oligomers, with quintet-mediated emission dominating delayed fluorescence up to room temperature. By distinguishing between the formation of weakly exchange-coupled triplet pairs and triplet excitons generated by intersystem crossing, we identify the methylated trimer as the only oligomer exhibiting exclusively the desired singlet fission route. These findings establish quintet-mediated delayed emission as a distinct spin-selective pathway and show how molecular structure directs high-spin formation, opening opportunities for room-temperature molecular quantum technologies.
