Molecular design of an electropolymerized copolymer with carboxylic and sulfonic acid functionalities

Abstract

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is the most researched conjugated polymer in the field of organic bioelectronics. The conjugated PEDOT backbone features good redox stability in aqueous electrolyte, and low oxidation potential. However, PEDOT:PSS has two major drawbacks. The PEDOT backbone lacks biofunctionality, limiting the fine tuning of its interface with the biological environment. The dopant PSS is insulating, resulting in a decrease in the capacitance of the polymer. Here, we describe the design of a random copolymer, P(EDOTCOOH-co-EDOTS), based on EDOT monomers functionalized with sulfonic and carboxylic acid groups. The copolymer was successfully synthesized by electropolymerization as confirmed by X-ray photoelectron spectroscopy. Contact angle measurements illustrated the high hydrophilicity of the P(EDOTCOOH-co-EDOTS) (28 ± 6º), attributed to the sulfonate group in the side chains. This in turn led to a higher water penetration into the copolymer film, enhancing significantly its volumetric capacitance (69 ± 4 F cm−3), and thereby, its performance when used as an active channel in an organic electrochemical transistor. Of note, we incorporated the sulfonate group in its sodium salt form retaining its highly ionized properties. This is the first instance of utilizing an uncapped, ionized sulfonate group covalently bound to the backbone of a polymer, where the resultant polymer is oxidized at very low potentials, as well as stable and electroactive in aqueous electrolytes. Furthermore, our molecular design to incorporate carboxylic acid groups paves the way for the development of conjugated polymers that can be tailored for bioelectronic applications.