Effect of N-α Substitution on the Electropolymerization of N-Substituted Pyrroles: Structure–Reactivity Relationship Studies
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- 作者：Sunil Kumar ; Sada Krishnakanth ; Jomon Mathew ; Zvika Pomerantz ; Jean-Paul Lellouche ; Subrata Ghosh
- 刊名：Journal of Physical Chemistry C
- 出版年：2014
- 出版时间：February 6, 2014
- 年：2014
- 卷：118
- 期：5
- 页码：2570-2579
- 全文大小：619K
- ISSN：1932-7455
文摘
Structure鈥搑eactivity relationship (SRR) studies to understand the effect of N-伪 substitution toward electroactive poly(pyrrole) film formation have carefully been performed. To conduct these SRR studies, a selected chemical library of 21 different N-substituted pyrrole derivatives has been developed using the key well-known Clauson鈥揔ass synthetic reaction from corresponding amine precursors. While investigating electropolymerization features of these novel N-substituted pyrroles, we observed that the steric factor due to 伪-substitution, one among other factors, plays the most significant role in preventing electropolymerization of these oxidizable chemical species. Interestingly, even a sterically small chemical group like a CH3 one present at 伪-position is large enough to prevent monomer electropolymerization. Density functional theory calculations were carried out to analyze the polymerization of substituted pyrrole molecules and to understand the effect of N-substituents on electropolymerization toward the formation of functional conductive film. This systematic study paves the way to effectively design the right N-substitution for the obtainment of corresponding modified functional electrodes for further related applications.