How Long are Polymer Chains in Poly(3,4-ethylenedioxythiophene):Tosylate Films? An Insight from Molecular Dynamics Simulations

D Kim and JF Franco-Gonzalez and I Zozoulenko, JOURNAL OF PHYSICAL CHEMISTRY B, 125, 10324-10334 (2021).

DOI: 10.1021/acs.jpcb.1c04079

Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most important conductive polymers utilized in a variety of applications in organic electronics and bioelectronics and energy storage. PEDOT chains are believed to be rather short, but detailed knowledge of their length is missing because of the challenges in its experimental determination due to insolubility of PEDOT films. Here, we report a molecular dynamics (MD) study of in situ oxidative chemical polymerization and simultaneous crystallization of molecularly doped PEDOT focusing on the determination of its chain lengths at different polymerization temperatures. We find the average chain length to be 6, 7, and 11 monomers for 298, 323 and 373 K, respectively. At the same time, the length distribution is rather broad, for example, between 2 and 16 monomer units for T = 323 K. We demonstrate that the limiting factor determining the chain length is the diffusivity of the reactants (PEDOT monomers and oligomers). We also study the polymer film formation during solvent evaporation, and we find that although crystallization starts and proceeds already during the polymerization and doping phases, it mostly occurs during the evaporation phase. Finally, we believe that our results providing the oligomer chain length and polymerization and crystallization mechanisms obtained by means of MD "computational microscopy" provide an important insight into the morphology of PEDOT that cannot be obtained by other means.

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