Absence of Electrostatic Rigidity in Conjugated Polyelectrolytes with Pendant Charges

The delocalization of electrons in conjugated polymers impacts their chain shape, affecting their local ordering, self-assembly, and ultimately charge transport. Conjugated polyelectrolytes introduce electrostatic interactions as a molecular design parameter to potentially tune chain rigidity by combining the π-conjugated polymer backbone with pendant ionic groups. In conventional polyelectrolytes, the self-repulsion of the bound charges induce extended rod-like chain configurations. Here, we leverage small-angle neutron scattering to measure the chain shapes of model conjugated polymers in dilute solution with controlled fractions of randomly distributed pendant charges. We find these model polythiophenes are semiflexible, with a persistence length of approximately 3 nm, regardless of charge fraction, suggesting the effective absence of electrostatic rigidity in conjugated polyelectrolytes. While the overall persistence length is negligibly impacted by pendant charges, optical spectroscopy indicates that the pendant charges increase the backbone torsion between thiophene rings without significantly impacting the π-conjugation length (the length of electron delocalization along a nearly planar backbone) in dilute solution. These results indicate the effective decoupling of the pendant ionic charges from the overall chain conformation with implications for solution processing of organic semiconductors.