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首页> 外文期刊>RSC Advances >Restriction of the conrotatory motion in photo-induced 6 pi electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization
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Restriction of the conrotatory motion in photo-induced 6 pi electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization

机译：限制光诱导的6 pi电循环反应中的同胞运动：在环化中形成闭环异构体的激发状态

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摘要

The electrocyclic reaction dynamics of a photochromic dithiazolylarylene derivative, 2,3-dithiazolylbenzothiophene (DTA) was investigated by using time-resolved transient absorption and fluorescence spectroscopies. The closed-ring isomer of DTA undergoes cycloreversion through the conical intersection mediating the potential energy surfaces of the excited and ground states, which is in agreement with the Woodward-Hoffmann rules for the electrocyclic reactions of 6 pi electron systems. On the other hand, a large portion of the open-ring isomer undergoes cyclization along the distinct reaction scheme, in which the cyclization takes place in the excited state manifold leading to the formation of the excited state of the closed-ring isomer. The suppression of the geometrical motion of DTA due to the intramolecular interaction could open a new efficient reaction pathway resulting in the formation of the electronically excited state of the product.
机译：通过使用时间分辨的瞬态吸收和荧光光谱研究了光致变色二亚吡喃氨基甲酰基衍生物的电循环反应动力学，2,3-二唑基噻吩（DTA）。 DTA的闭环异构体通过介导兴奋和地态的潜在能量表面的锥形交叉点进行环形转化，这与Woodward-Hoffmann规则一致的6个PI电子系统的电宽。 另一方面，沿着不同的反应方案经历了一大部分的开环异构体，其中在激发状态歧管中进行环化，导致闭环异构体的激发状态。 由于分子内相互作用导致DTA的几何运动抑制了新的高效反应途径，导致产品的电子激发状态的形成。

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  • 来源
    《RSC Advances》 |2020年第34期|共8页
  • 作者

    Nagasaka Tatsuhiro; Sotome Hikaru; Morikawa Soichiro; Uriarte Lucas Martinez; Sliwa Michel; Kawai Tsuyoshi; Miyasaka Hiroshi;

  • 作者单位

    Osaka Univ Grad Sch Engn Sci Div Frontier Mat Sci Toyonaka Osaka 5608531 Japan;

    Osaka Univ Grad Sch Engn Sci Div Frontier Mat Sci Toyonaka Osaka 5608531 Japan;

    Osaka Univ Grad Sch Engn Sci Div Frontier Mat Sci Toyonaka Osaka 5608531 Japan;

    Univ Lille CNRS UMR 8516 LASIR Lab Spectrochim Infrarouge &

    Raman F-59000 Lille France;

    Univ Lille CNRS UMR 8516 LASIR Lab Spectrochim Infrarouge &

    Raman F-59000 Lille France;

    Nara Inst Sci &

    Technol Grad Sch Sci &

    Technol Div Mat Sci Ikoma Nara 6300192 Japan;

    Osaka Univ Grad Sch Engn Sci Div Frontier Mat Sci Toyonaka Osaka 5608531 Japan;

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  • 正文语种 eng
  • 中图分类 化学;
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