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Issue 7, 2015
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Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives

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Abstract

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials.

Graphical abstract: Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives

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Supplementary files

Article information


Submitted
16 Mar 2015
Accepted
15 Apr 2015
First published
21 May 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 4160-4173
Article type
Edge Article
Author version available

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives

P. Pandit, K. Yamamoto, T. Nakamura, K. Nishimura, Y. Kurashige, T. Yanai, G. Nakamura, S. Masaoka, K. Furukawa, Y. Yakiyama, M. Kawano and S. Higashibayashi, Chem. Sci., 2015, 6, 4160
DOI: 10.1039/C5SC00946D

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    [Original citation] - Published by The Royal Society of Chemistry.

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