Polymer Bulletin

, Volume 69, Issue 2, pp 137–147 | Cite as

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

Original Paper


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.


Aromatic polyamine Charge transfer Electrochemistry Postfunctionalization 



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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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Yusuke Washino
    • 1
  • Kimie Murata
    • 2
  • Tsuyoshi Michinobu
    • 2
    • 3
  1. 1.Department of Organic and Polymeric MaterialsTokyo Institute of TechnologyTokyoJapan
  2. 2.Global Edge InstituteTokyo Institute of TechnologyTokyoJapan
  3. 3.PRESTO, Japan Science and Technology Agency (JST)KawaguchiJapan

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