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Ion valence-gated photochromism of an aza-crowned diarylethene

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Abstract

A non-photochromic diarylethene 2o with an N-phenylaza-15-crown-5 was synthesized. When the nitrogen atom in the aza-crown ring was protonated, it became photochromic due to the prevention of a twisted intramolecular charge transfer (TICT). Although addition of a monovalent metal cation (Li+, Na+, K+, Rb+, Cs+, Cu+, Ag+) in acetonitrile could not stop the TICT so that it was not photochromic, the addition of a multivalent metal cation (Mg2+, Ca2+, Sr2+, Ba2+, Fe2+, Ni2+, Al3+, Sb5+) changed 2o to be photochromic due to the strong attraction of the lone pair on the nitrogen atom. In the presence of excess Cu2+, 2o was oxidized to be EPR-detectable 2o·+, which was thermally unstable as well as inert towards visible-light irradiation. However, 2o·+ was further oxidized to be fairly stable 2o2+ by the irradiation of 365-nm light in the presence of Cu2+. ESI–MS measurements strongly suggested the generation of 2o·+ by mixing 2o with Cu(ClO4)2 in acetonitrile, and the transformation of 2o·+ to 2o2+ by successive 365-nm light irradiation. Fe3+ similarly worked as the oxidant, but the two-step oxidation of 2o to 2o2+ occurred more easily.

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The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported in part by JSPS KAKENHI Grant Number JP26107009 in Scientific Research on Innovative Areas “Photosynergetics.” The authors are grateful to the Instrumental Analysis Center of Yokohama National University for its support in the NMR and MS measurements. Thanks are also extended to Mr. Tsuyoshi Ito, Yokohama National University, for his support in the spectral measurements for the characterization of compounds. We are indebted to the Zeon Corp. for their generous donation of octafluorocyclopentene. Part of this study was presented at the 9th International Symposium on Photochromism (ISOP2019), September 2019, Paris.

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Authors and Affiliations

  1. Department of Chemistry and Life Science, Graduate School of Engineering Science, Yokohama National University, 79-5, Tokiwadai, Hodogaya, Yokohama, 240-8501, Japan

    Ayaka Takeguchi, Azusa Kikuchi, Kazuhide Ueno, Aki Nitta, Tetsuya Nakagawa, Takashi Ubukata & Yasushi Yokoyama

  2. Instrumental Analysis Center, Yokohama National University, 79-5, Tokiwadai, Hodogaya, Yokohama, 240-8501, Japan

    Shinji Ishihara

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Takeguchi, A., Kikuchi, A., Ueno, K. et al. Ion valence-gated photochromism of an aza-crowned diarylethene. Photochem Photobiol Sci 23, 133–151 (2024). https://doi.org/10.1007/s43630-023-00508-z

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