Synthesis, Properties and Redox Behavior of Tris[1-azulenyltetracyanobetadiene and 1-azulenylbis(tetracyanobetadiene)s] Connected with 1,3,5-Tri(1-azulenyl)benzene Core
Synthesis, Properties and Redox Behavior of Tris[1-azulenyltetracyanobetadiene and 1-azulenylbis(tetracyanobetadiene)s] Connected with 1,3,5-Tri(1-azulenyl)benzene Core
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1,3,5-三(1-薁基)苯核连接的三[1-薁基四氰基β二烯和1-薁基双(四氰基β二烯)s]的合成、性能及氧化还原行为
DOI：
10.1002/ejoc.201403556
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发表时间：
2015
影响因子：
2.8
通讯作者：
and Kozo Toyota
中科院分区：
文献类型：
--
作者：
Taku Shoji,* Akifumi Maruyama;Erika Shimomura;Daichi Nagai;Shunji Ito;Tetsuo Okujima;and Kozo Toyota
在Sonogashira-Hagihara交叉偶联条件下，通过Pd催化的1-乙炔基甘菊环与三（3-碘-1-甘菊环）苯或被1-甘菊环乙炔基取代的碘芳烃衍生物与三（3-乙炔基-1-甘菊环）苯的炔基化反应，制备了连接到1，3，5-三（1-甘菊环）苯核的三（1-甘菊环乙炔基）和三（1-甘菊环乙炔基芳基乙炔基）发色团。这些化合物与四氰基乙烯进行[2+2]环加成-逆电环化反应，以优异的产率得到相应的三（1-甘菊环基四氰基丁二烯）和三[1-甘菊环基双（四氰基丁二烯）]发色团。采用循环伏安法（CV）和微分脉冲伏安法（DPV）研究了四氰基丁二烯（TCBD）衍生物的氧化还原行为，揭示了它们的多步电化学还原特性。此外，在电化学还原条件下，通过可见光谱观察到显着的颜色变化。
Tris(1‐azulenylacetylene) and tris(1‐azulenylethynylarylacetylene) chromophores connected to a 1,3,5‐tri(1‐azulenyl)benzene core have been prepared by the Pd‐catalyzed alkynylations of 1‐ethynylazulene with tris(3‐iodo‐1‐azulenyl)benzene or iodoarene derivatives substituted with a 1‐azulenylethynyl group with tris(3‐ethynyl‐1‐azulenyl)benzene under Sonogashira–Hagihara cross‐coupling conditions. These compounds reacted with tetracyanoethylene in formal [2+2] cycloaddition–retroelectrocyclization reactions to afford the corresponding tris(1‐azulenyltetracyanobutadiene) and tris[1‐azulenylbis(tetracyanobutadiene)] chromophores in excellent yields. The redox behavior of the tetracyanobutadiene (TCBD) derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.