Computational Investigation into Photoswitching Efficiency of Diarylethene Derivatives: An Insight Based on the Decay Constant of Electron Tunneling

详细信息    查看全文

• 作者：Shohei Nishizawa ; Jun-ya Hasegawa ; Kenji Matsuda
• 刊名：Journal of Physical Chemistry C
• 出版年：2015
• 出版时间：August 27, 2015
• 年：2015
• 卷：119
• 期：34
• 页码：20169-20178
• 全文大小：584K
• ISSN：1932-7455

文摘

The switching efficiency (SE) of the intramolecular exchange interaction J between the open- and the closed-ring isomers of diarylethenes (DAEs) was investigated using DFT calculations of DAE biradicals with different core structures: DAEs with 3-thienyl, thiophene-S,S-dioxide-3-yl, 2-thienyl, or thiophene-S,S-dioxide-2-yl rings. The SE of DAE with a 3-thienyl ring is calculated to be around 400-fold, which is the largest among the four calculated DAEs. The decay constant 尾 of the exchange interaction J for the DAE molecular wires was evaluated by calculating J for biradicals with different lengths of wires. For the wires of the closed-ring isomers of DAE with 3-thienyl- and thiophene-S,S-dioxide-3-yl rings, which are supposed to take a quinoid structure, allyl nitronyl nitroxide radical was successfully employed. The calculated 尾 values showed a significant difference between the open- and the closed-ring isomers, and this difference of 尾 is considered to be the origin of photoswitching of J. The difference of 尾 upon isomerization, 螖尾, is in good agreement with SE, and the largest 螖尾 was obtained for the DAE with a 3-thienyl ring. We can understand the switching of J as the switching of electron tunneling efficiency 尾 between the open- and the closed-ring isomers.