Dicationic Heteroacenes Containing Thio- or Selenopyrylium Moieties
Dicationic Heteroacenes Containing Thio- or Selenopyrylium Moieties
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含有硫代或硒代吡啶鎓部分的双阳离子杂并苯
DOI：
10.1021/acs.organomet.9b00100
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Okuma Kentaro
中科院分区：
文献类型：
--
作者：
Nagahora Noriyoshi;Kushida Tomoko;Shioji Kosei;Okuma Kentaro
带有硫代或硒代吡喃鎓部分的双阳离子杂并苯是通过相应的二酮与格氏试剂的加成反应，然后通过所得二醇与布朗斯台德酸的脱水反应合成的。或者，这些双阳离子杂并苯从相应的含硫或硒的醌类化合物的双电子氧化获得。这些双阳离子杂并苯的电子结构进行了研究，通过NMR和UV-vis-NIR光谱结合密度泛函理论计算。这种结合实验和理论方法的结果强烈暗示了分布在整个并五苯框架上的系统中的22个π电子的有效共轭。
Dicationic heteroacenes that bear thio- or selenopyrylium moieties were synthesized by addition reactions of the corresponding diones with a Grignard reagent, followed by a dehydration reaction of the resulting diols with Brønsted acid. Alternatively, these dicationic heteroacenes were obtained from two-electron oxidations of the corresponding sulfur- or selenium-containing quinoids. The electronic structures of these dicationic heteroacenes were examined by NMR and UV–vis–NIR spectroscopy in conjunction with density functional theory calculations. The results of this combined experimental and theoretical approach strongly imply effective conjugation of 22π-electrons in a system that is distributed over the entire pentacene framework.