Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity
Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity
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DOI：
10.1021/jp106082f
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发表时间：
2010-10-07
影响因子：
3.7
通讯作者：
Abruna, Hector D.
中科院分区：
文献类型：
--
作者：
Burkhardt, Stephen E.;Rodriguez-Calero, Gabriel G.;Abruna, Hector D.
导电聚合物由于具有独特的机械、光学和电子性能而具有广泛的工业应用。具体地，聚（亚烷基二氧噻吩）衍生物家族由于其固有的高导电性、环境稳定性和可调谐性而受到广泛关注。然而，尽管烷氧基部分的给电子特性是众所周知的，但这些取代之间的差异的来源仅限于基于本体性质的推测性争论。为了解决这些问题，结合电化学和密度泛函理论（DFT）的研究进行，揭示了重要的电子和几何特性负责这些材料的比较性能。发现亚烷基二氧基主链取代的几何形状调节氧的π-供给特征，并且这直接影响p-掺杂导电性的开始。这些研究还表明，该框架同样适用于其他几种杂环聚合物体系。这些材料的改进理论有望为具有增强的稳定性和光电性能的新型导电聚合物提供洞察力和知识基础。
Conducting polymers have widespread industrial applications owing to a unique combination of mechanical, optical, and electronic properties. Specifically, the family of poly(alkylenedioxythiophene) derivatives has received much attention due to its inherently high conductivity, environmental stability, and tunability. However, although the electron-donating characteristics of the alkoxy moieties are well-known, the source of the differences among these substitutions has been limited to speculative arguments based on bulk properties. To address these issues, a combined electrochemical and density functional theory (DFT) study was undertaken that reveals the significant electronic and geometric characteristics responsible for the comparative properties of these materials. It wits found that the geometry of the alkylenedioxy backbone substitution modulates the pi-donating character of the oxygen and that this directly influences the onset of p-doped conductivity. These studies also indicate that this framework equally applies to several other heterocyclic polymer systems. An improved theory for these materials is expected to provide the insight and knowledge base for new conducting polymers with enhanced stability and optoelectronic properties.