Synthesis, Properties, and Redox Behavior of Tetracyanobutadiene and Dicyanoquinodimethane Chromophores Bearing Two Azulenyl Substituents

作者：Taku Shoji, Mitsuhisa Maruyama, Erika Shimomura, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita · 发表于：The Journal of Organic Chemistry · 年份：2013 · DOI：10.1021/jo402104n · 被引用次数：45 · 研究领域：Synthesis and Properties of Aromatic Compounds、Luminescence and Fluorescent Materials、Photochromic and Fluorescence Chemistry

Acetylene derivatives with an azulenyl group at both terminals have been prepared by palladium-catalyzed alkynylation under Sonogashira-Hagihara conditions. These alkynes reacted with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane in a formal [2 + 2] cycloaddition-retroelectrocyclization reaction to afford the corresponding new tetracyanobutadienes (TCBDs) and dicyanoquinodimethanes (DCNQs), respectively, in excellent yields. Intramolecular CT absorption bands were found in the UV-vis spectra of the novel chromophores, and CV and DPV showed that they exhibited a reversible two-stage reduction wave, due to the electrochemical reduction of TCBD and DCNQ moieties. Color changes were also observed during the electrochemical reduction.