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Ultrafast Dynamics and Mechanisms of One-Photon and Multiphoton Photochromic Reactions

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Abstract

Dynamics and mechanisms of photochromic reactions of organic molecular systems, such as diarylethene, fulgide, and hexaarylbiimidazole derivatives, were investigated by time-resolved measurements in femtosecond to picosecond regions. Ultrafast cyclization and cycloreversion reactions in diarylethene derivatives were directly detected by femtosecond laser photolysis. By integrating the temperature dependence of faction of conformers, reaction yields, and dynamic behaviors, the mechanisms of these reactions in the excited states were discussed on the basis of the adiabatic potential surfaces. For the photodissociation dynamics of hexaarylbiimidazole derivatives, the role of the local excited state in the rapid reaction on the dissociative potential surface was discussed by introducing the ultrafast dynamics in these systems with different aromatic substituents. In addition to the elucidation of dynamic behaviors of cyclization, cycloreversion, and photodissociation in these systems by one-photon excitation, nonlinear photochromic reactions were also studied. Stepwise two-photon absorption leading to a specific higher excited state, which was not accessible via one-photon absorption from the ground state, induced drastic enhancement of the cycloreversion reaction (>2,500 times compared to the one-photon process). In addition, one-color reversible control of both directions of photochromic reactions was attained for a diarylethene derivative through simultaneous three-photon cyclization and two-photon cycloreversion using femtosecond near-IR laser pulse at 1.28 μm.

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Acknowledgements

This work was supported by Grand-in-Aids for Research in Priority Areas “New Frontiers in Photochromism (No. 471)” from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan. The authors appreciate the collaboration of Professors Masahiro Irie, Seiya Kobatake, Yasushi Yokoyama, Kingo Uchida, Shin-ichiro Nakamura, and Jiro Abe.

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Authors and Affiliations

  1. Graduate School of Science and Engineering, Ehime University, Matsuyama, Japan

    Yukihide Ishibashi

  2. Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Japan

    Tetsuro Katayama & Hiroshi Miyasaka

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  1. Yukihide Ishibashi
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  2. Tetsuro Katayama
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  3. Hiroshi Miyasaka
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Correspondence to Hiroshi Miyasaka .

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Editors and Affiliations

  1. Rikkyo University, Tokyo, Japan

    Masahiro Irie

  2. Yokohama National University, Yokohama, Japan

    Yasushi Yokoyama

  3. Nagoya University, Nagoya, Japan

    Takahiro Seki

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Ishibashi, Y., Katayama, T., Miyasaka, H. (2013). Ultrafast Dynamics and Mechanisms of One-Photon and Multiphoton Photochromic Reactions. In: Irie, M., Yokoyama, Y., Seki, T. (eds) New Frontiers in Photochromism. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54291-9_12

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