Hydrogen-Bonding-Directed Ordered Assembly of Carboxylated Poly(3-Alkylthiophene)s

[Image: see text] Hydrogen-bonding-induced ordered assembly of poly(3-alkylthiophene)s derivatives bearing carboxylic acid groups has been investigated from diluted and concentrated solutions to solid films using ultraviolet–visible absorption spectroscopy, polarized optical microscopy, and four-point probe conductivity measurements. In dilute solutions, the polymer undergoes a spontaneous structural transition from disordered coil-like to ordered rodlike conformations, which is evidenced by time-dependent chromism. Many factors such as alkyl-chain length, types of solvents, and temperature are studied to understand the assembly behavior. Transition kinetics of the assembly process reveals a universal second-order rate law, indicating an intermolecular origin due to hydrogen bonding. When more concentrated, hydrogen bonding drives nematic liquid-crystalline gelation above a critical concentration and the gels are thermally reversible. Under an appropriate balance of mechanical and thermal stresses, uniform liquid-crystalline monodomains are obtained through the application of a mechanical shear force. The dried films made from the sheared solutions display both optical and electrical anisotropies, with a more than 200% increase in charge transport parallel to the direction of shear as opposed to that in the perpendicular one.