Application of Alkyne-TCNQ Addition Reaction to Polymerization

The polymerization using a high‐yielding addition reaction between electron‐rich alkynes and 7,7,8,8‐tetracyanoquinodimethane (TCNQ) derivatives is described. The bifunctional monomer containing two TCNQ moieties and the counter comonomer bearing two dialkylaniline (DAA)‐substituted alkynes are reacted in 1,2‐dichloroethane under mild heating conditions. At the high monomer concentrations, high molecular weight linear polymers are obtained, while the reaction at the low monomer concentrations produces a significant amount of the cyclic compounds. A clear relationship between the monomer concentration and the cyclic compound amount is demonstrated. The obtained polymers feature a sufficient thermal stability with the decomposition temperature exceeding 300 °C as well as strong charge‐transfer (CT) bands and redox activities ascribed to the produced donor–acceptor moieties. These features are also used to optimize the polymerization conditions and to estimate the chemical structures. A high‐yielding addition reaction between dialkylaniline‐substituted alkynes and 7,7,8,8‐tetracyanoquinodimethane (TCNQ) moieties is for the first time employed to synthesize linear polymers and cyclic compounds. The ratio of linear polymers and cyclic compounds can be controlled by the monomer concentration. The products showed a high thermal stability, well‐defined charge‐transfer (CT) bands, and redox activities.