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Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

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Abstract

Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2+2] cycloaddition, followed by retro-cyclization with the electron-accepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). 1H NMR studies were used to optimize the reaction conditions. Mild heating to >50 °C afforded the postfunctionalized aromatic polyamines with the desired acceptor amounts. The quantitative TCNQ addition was demonstrated by the MALDI-TOF mass spectrum and elemental analysis. Introduction of the cyano-based acceptor moieties into the polymer side chains resulted in unusually strong intermolecular interactions. In addition to the π–π interactions of the extended acceptor moieties, these intermolecular forces were supposed to improve the thermal stability of the aromatic polymers. Furthermore, the donor–acceptor chromophores formed by this postfunctionalization displayed low energy charge-transfer bands and redox activities in both the anodic and cathodic directions. The straightforward postfunctionalization technique using the alkyne–TCNQ addition is useful for the preparation of narrow band gap polymers in one step.

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Acknowledgments

This work was supported, in part, by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, Japan.

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Authors and Affiliations

  1. Department of Organic and Polymeric Materials, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8552, Japan

    Yusuke Washino

  2. Global Edge Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550, Japan

    Kimie Murata & Tsuyoshi Michinobu

  3. PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Japan

    Tsuyoshi Michinobu

Authors
  1. Yusuke Washino
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  2. Kimie Murata
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  3. Tsuyoshi Michinobu
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Correspondence to Tsuyoshi Michinobu.

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Washino, Y., Murata, K. & Michinobu, T. Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes. Polym. Bull. 69, 137–147 (2012). https://doi.org/10.1007/s00289-011-0693-7

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  • DOI: https://doi.org/10.1007/s00289-011-0693-7

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