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

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How Long are Polymer Chains in Poly(3,4-ethylenedioxythiophene):Tosylate Films? An Insight from Molecular Dynamics Simulations
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2021-09-02 , DOI: 10.1021/acs.jpcb.1c04079
Donghyun Kim ₁ , Juan Felipe Franco-Gonzalez ₂ , Igor Zozoulenko ₁

Affiliation

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.

中文翻译：

聚（3,4-亚乙基二氧噻吩）：甲苯磺酸盐薄膜中的聚合物链有多长？分子动力学模拟的见解

聚（3,4-乙撑二氧噻吩）（PEDOT）是最重要的导电聚合物之一，用于有机电子、生物电子和能量存储的各种应用。PEDOT 链被认为是相当短的，但由于 PEDOT 薄膜的不溶性在其实验测定中存在挑战，因此缺少对其长度的详细了解。在这里，我们报告了分子掺杂 PEDOT 的原位氧化化学聚合和同步结晶的分子动力学 (MD) 研究，重点是在不同聚合温度下确定其链长。我们发现平均链长分别为 6、7 和 11 个单体，分别为 298、323 和 373 K。同时，长度分布相当广泛，例如在 2 到 16 个单体单元之间T = 323 K。我们证明决定链长的限制因素是反应物（PEDOT 单体和低聚物）的扩散率。我们还研究了溶剂蒸发过程中聚合物膜的形成，我们发现虽然结晶已经在聚合和掺杂阶段开始并进行，但它主要发生在蒸发阶段。最后，我们相信我们的结果提供了通过 MD“计算机显微镜”获得的低聚物链长度和聚合和结晶机制，提供了对 PEDOT 形态的重要洞察，这是其他方式无法获得的。

更新日期：2021-09-16

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