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Structurally and electronically modulated spin interaction of transient biradicals in two photon-gated stepwise photochromism

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Abstract

The development of two-photon induced photochromic compounds is important for advanced photo-responsive materials. The utilization of the long-lived transient states or species for two-photon absorption is one of the efficient strategies to realize the advanced photochemical behavior beyond a one-photon photochemical reaction. We have synthesized bi-photochromic compounds composed of two photochromic phenoxyl-imidazolyl radical complex units. The biphotochromic compounds generate two biradical units when the two photochromic units absorb photons with a stepwise manner. The interaction between the two biradicals through the central bridging phenyl ring is the key feature to control the step-wise photochromic reaction. Here, we introduced aromatic spacers in order to modulate the distance and the dihedral angle between the biradical units. The color and the rate of the thermal back reaction of the stepwise photochromism can be regulated by the control of the central bridging part. These results give important insights to develop desirable advanced photoresponsive compounds.

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Acknowledgements

This work was supported partly by the Core Research for Evolutionary Science and Technology (CREST) program of the Japan Science and Technology Agency (JST) and JSPS KAKENHI Grant Number JP26107010 in Scientific Research on Innovative Areas “photosynergetics” and MEXT KAKENHI Grant Number JP17K14475 for K. M. Financial assistance for this research was also provided by the MEXT-Supported Program for the Strategic Research Foundation at Private Universities, 2013-2017.

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Authors and Affiliations

  1. Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa, 252-5258, Japan

    Izumi Yonekawa, Katsuya Mutoh & Jiro Abe

  2. Department of Applied Chemistry, College of Life Sciences, Ritsumeikan University, 1-1-1 Noji-higashi, Kusatsu, Shiga, 525-8577, Japan

    Yoichi Kobayashi

Authors
  1. Izumi Yonekawa
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  2. Katsuya Mutoh
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  3. Yoichi Kobayashi
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  4. Jiro Abe
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Correspondence to Jiro Abe.

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Yonekawa, I., Mutoh, K., Kobayashi, Y. et al. Structurally and electronically modulated spin interaction of transient biradicals in two photon-gated stepwise photochromism. Photochem Photobiol Sci 17, 290–301 (2018). https://doi.org/10.1039/c7pp00420f

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