Additive‐dependent iptycene incorporation in polyanilines: Insights into the pentiptycene clipping effect and the polymerization mechanism. Issue 9 (5th August 2019)

• Record Type: Journal Article
• Authors: Tan, Wei Shyang; Lee, Ting‐Yin; Tseng, Sheng‐Fang; Hsu, Ying‐Feng; Ebina, Masanori; Taketsugu, Tetsuya; Huang, Shing‐Jong; Yang, Jye‐Shane
• Is Part Of: Journal of the Chinese Chemical Society. Volume 66:Issue 9(2019)
• Page Start: 1141
• Page End: 1156
• Publication Date: 2019-08-05
• Subjects: clipping effect -- pentiptycene -- polyaniline; Chemistry -- Periodicals; Electronic journals; 540.5
• DOI: 10.1002/jccs.201900194
• Languages: English
• ISSNs: 0009-4536

Abstract

Abstract: 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. Abstract : A terminal planar p ‐phenylenediamine (ppda) group has been identified to be the key component of an effective nucleate for the oxidative polymerization of aniline under acidic conditions on the basis of the distinct reactivity of three pentiptycene‐derived additives. In addition, the clipping effects of the iptycene substituents have been further investigated by DFT calculations and with new polymers.