Original Paper

Polymer Bulletin

, Volume 69, Issue 2, pp 137-147

First online:

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

  • Yusuke WashinoAffiliated withDepartment of Organic and Polymeric Materials, Tokyo Institute of Technology
  • , Kimie MurataAffiliated withGlobal Edge Institute, Tokyo Institute of Technology
  • , Tsuyoshi MichinobuAffiliated withGlobal Edge Institute, Tokyo Institute of TechnologyPRESTO, Japan Science and Technology Agency (JST) Email author 

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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