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

David W. Bilger, Jose A. Figueroa, Neil D. Redeker, Amrita Sarkar, Morgan Stefik, Shanju Zhang

Research output: Contribution to journalArticlepeer-review

19 Scopus citations


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.

Original languageEnglish
Pages (from-to)8526-8535
Number of pages10
JournalACS Omega
Issue number11
StatePublished - 30 Nov 2017


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