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Diarylethene Molecular Photoswitches. Masahiro IrieЧитать онлайн книгу.

Diarylethene Molecular Photoswitches - Masahiro Irie


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12 ps at room temperature and finally leads to the photoproduct via 2A/1ACI(o). Both cyclization and cycloreversion reactions take place via the common CI(o). The cyclization reaction in solution completes within 1 ps, as described before. Therefore, the staying time in the 2Ao state is considered to be less than 1 ps. The time constant of 12 ps reflects the time taken to overcome the barrier 2ATS1.

      Inferring from the experimental results, the cycloreversion dynamics of 20c is summarized as follows. The 1B state produced by the excitation of the closed‐ring isomer undergoes internal conversion into the 2Ac state with the time constant of 200 fs, which is followed by geometrical rearrangement with vibrational cooling in 3.0 ps. The resultant 2Ac state goes over the activation barrier (2ATS1) into the 2Ao state with the time constant of 12 ps and finally leads to the open‐ring isomer via the 2A/1ACI(o).

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      5 5 Mendive‐Tapia, D., Perrier, A., Bearpark, M.J. et al. (2014). New insights into the by‐product fatigue mechanism of the photo‐induced ring‐opening in diarylethenes. Phys. Chem. Chem. Phys. 16: 18463–18471.

      6 6 Irie, M., Fukaminato, T., Matsuda, K., and Kobatake, S. (2014). Photochromism of diarylethene molecules and crystals: memories, switches and actuators. Chem. Rev. 114: 12174–12277.

      7 7 Irie, M., Lifka, T., Kobatake, S., and Kato, N. (2000). Photochromism of 1,2‐bis(2‐methyl‐5‐phenyl‐3‐thienyl)perfluorocyclopentene in a single‐crystalline phase. J. Am. Chem. Soc. 122 (20): 4871–4876.

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      9 9 Jean‐Ruel, H., Cooney, R.R., Gao, M. et al. (2011). Femtosecond dynamics of ring closing process diarylethene: a case study of electrocyclic reactions in photochromic single crystals. J. Phys. Chem. A 115: 13158–13168.

      10 10 Hania, P.R., Pugzlys, A., Lucas, L.N. et al. (2005). Ring closure dynamics of BTE‐based photochromic switch: perfluoro‐ versus perhydrocyclopentene derivatives. J. Phys. Chem. A 109 (42): 9437–9442.

      11 11 Ishibashi, Y., Fujiwara, M., Umesato, T. et al. (2011). Cyclization reaction dynamics of a photochromic diarylethene derivative as revealed by femtosecond to microsecond time‐resolved spectroscopy. J. Phys. Chem. C 115: 4265–4272.

      12 12 Ishibashi, Y., Fujiwara, M., Umesato, T. et al. (2017). Cycloreversion reaction of a diarylethene derivative at higher excited states attained by two‐color, two‐photon femtosecond pulsed excitation. J. Am. Chem. Soc. 139: 17159–17167.

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