Correlating Molar Mass, π‐Conjugation, and Optical Properties of Narrowly Distributed Anionic Polythiophenes in Aqueous Solutions

Abstract Polythiophene‐based conjugated polyelectrolytes (CPE) are attracting increasing attention as sensor or interface materials in chemistry and biology. While cationic polythiophenes are better understood, limited structural information is available on their anionic counterparts. Limited access to well‐defined polymers has made the study of structure‐property relationships difficult and clear correlations have remained elusive. By combining controlled Kumada catalyst transfer polymerization with a polymer‐analog substitution, regioregular and narrowly distributed poly(6‐(thiophen‐3‐yl)hexane‐1‐sulfonate)s (PTHS) with tailored chain length are prepared. Analysis of their aqueous solution structures by small‐angle neutron scattering (SANS) revealed a cylindrical conformation for all polymers tested, with a length close to the contour length of the polymer chains, while the estimated radii remain too small (<1.5 nm) for extensive π‐stacking of the chains. The latter is particularly interesting as the longest polymer exhibits a concentration‐independent structured absorption typical of crystalline polythiophenes. Increasing the ionic strength of the solution diminishes these features as the Coulomb repulsion between the charged repeat units is shielded, allowing the polymer to adopt a more coiled conformation. The extended π‐conjugation, therefore, appears to be a key parameter for these unique optical features, which are not present in the corresponding cationic polythiophenes.