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

作者：Washino Yusuke; Murata Kimie; Michinobu Tsuyoshi^*

来源：Polymer Bulletin, 2012, 69(2): 137-147.

DOI：10.1007/s00289-011-0693-7

• Aromatic polyamine
• Charge transfer
• Electrochemistry
• Postfunctionalization

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). H-1 NMR studies were used to optimize the reaction conditions. Mild heating to %26gt;50 degrees 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 pi-pi 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.

• 出版日期2012-7