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Additive‐dependent iptycene incorporation in polyanilines: Insights into the pentiptycene clipping effect and the polymerization mechanism
Author(s) -
Tan Wei Shyang,
Lee TingYin,
Tseng ShengFang,
Hsu YingFeng,
Ebina Masanori,
Taketsugu Tetsuya,
Huang ShingJong,
Yang JyeShane
Publication year - 2019
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201900194
Subject(s) - polyaniline , chemistry , aniline , polymerization , substituent , polymer chemistry , electrochemistry , polymer , stereochemistry , organic chemistry , electrode
Despite the long history of polyaniline chemistry, backbone‐substituted polyanilines are limited. Here, we report the synthesis of pentiptycene‐incorporated polyanilines through acidic aniline oxidative polymerization with three pentiptycene derivatives, TA, DA, and TP, as nucleate additives. The reactivity of TA > DA ≫ TP, as evidenced by structural and property analysis of the corresponding polyaniline products, demonstrates a radical coupling mechanism and the formation of Dewar π‐complex intermediates for the chain propagation. In addition, the iptycene substituent effect on enhancing the electrochemical stability and charge storage capability of polyaniline are discussed with a clip model, namely, the threading of neighboring polyaniline chains through the U‐ and V‐shaped cavities of pentiptycene restricts lateral motions of the polymer chains and promotes interchain conductivity. Density function theory (DFT) calculations suggest a larger clipping effect for the U versus V cavities. Both the conclusion of a terminal planar p ‐phenylenediamine (ppda) group being the key component of an effective nucleate and the concept of interchain clipping for enhanced electrochemical performance should facilitate the design and synthesis of novel polyanilines for electronic applications.

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