Hamatani Shota, Kitagawa Daichi, Kobatake Seiya
Department of Chemistry and Bioengineering, Graduate School of Engineering, Osaka Metropolitan University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka, 558-8585, Japan.
J Phys Chem Lett. 2023 Sep 21;14(37):8277-8280. doi: 10.1021/acs.jpclett.3c02207. Epub 2023 Sep 7.
Gaining insight into the dynamics of electrocyclic reactions is very important from both fundamental and application perspectives. In this study, we developed novel diarylethene photoswitches that undergo 6π azaelectrocyclic reaction. We found that they exhibit fast thermally reversible type (T-type) photochromism, in contrast to the fact that common diarylethenes exhibit photochemically reversible type (P-type) photochromism. The quantum chemical calculations revealed that the fast T-type photochromism originates from the unprecedented disrotatory thermal cycloreversion of the closed-ring isomer. Our results provide useful information not only for the dynamics of the 6π azaelectrocyclic reaction but also for the further development of diarylethene photoswitches utilizing the 6π azaelectrocyclic reaction.
从基础和应用的角度深入了解电环化反应的动力学都非常重要。在本研究中，我们开发了新型的二芳基乙烯光开关，其经历6π氮杂电环化反应。我们发现它们表现出快速的热可逆型（T型）光致变色，这与常见二芳基乙烯表现出的光化学可逆型（P型）光致变色不同。量子化学计算表明，快速的T型光致变色源于闭环异构体前所未有的顺旋热环化逆转。我们的结果不仅为6π氮杂电环化反应的动力学提供了有用信息，也为利用6π氮杂电环化反应的二芳基乙烯光开关的进一步发展提供了有用信息。
