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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Synthesis of Nonplanar Push-Pull Chromophores with Various Heterocyclic Moieties via [2 + 2]
1Department of Materials Science and Engineering, Institute of Science Tokyo, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8552, Japan.
Abstract:
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.
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