Synthesis of Nonplanar Push–Pull Chromophores with Various Heterocyclic Moieties via [2 + 2] Cycloaddition-Retroelectrocyclization Reaction

A series of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives with various heterocyclic moieties, including pyridine, carbazole, indole, and benzothiadiazole, was newly synthesized through a [2 + 2] cycloaddition-retroelectrocyclization reaction. Symmetric electron-rich 1,3-butadiynes with end-capped heterocyclic substituents were reacted with tetracyanoethylene (TCNE), yielding the target TCBD products in 60-80% yields under ambient or mild heating conditions. The thermal stability and optical and electrochemical properties of both 1,3-butadiyne precursors and the corresponding TCBD derivatives were investigated by using thermogravimetric analysis (TGA), UV-vis spectroscopy, and cyclic voltammetry (CV). The TCBD derivatives featured narrow bandgaps due to the intramolecular charge transfer interactions of push-pull chromophores. In addition, the optimized structures and frontier molecular orbitals with their energy levels were determined by density functional theory (DFT) calculations.