Exciton Diffusion in Highly-Ordered One Dimensional Conjugated Polymers: Effects of Back-Bone Torsion, Electronic Symmetry, Phonons and Annihilation

Many optoelectronic devices based on organic materials require rapid and long-range singlet exciton transport. Key factors controlling exciton transport include material structure, exciton–phonon coupling and electronic state symmetry. Here, we employ femtosecond transient absorption microscopy to study the influence of these parameters on exciton transport in one-dimensional conjugated polymers. We find that excitons with 21Ag– symmetry and a planar backbone exhibit a significantly higher diffusion coefficient (34 ± 10 cm2 s–1) compared to excitons with 11Bu+ symmetry (7 ± 6 cm2 s–1) with a twisted backbone. We also find that exciton transport in the 21Ag– state occurs without exciton–exciton annihilation. Both 21Ag– and 11Bu+ states are found to exhibit subdiffusive behavior. Ab initio GW-BSE calculations reveal that this is due to the comparable strengths of the exciton–phonon interaction and exciton coupling. Our results demonstrate the link between electronic state symmetry, backbone torsion and phonons in exciton transport in π-conjugated polymers.