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Photo-Activated Motion of Layered Hybrids Induced by the High-Order Architecture of Azobenzene Assembly on Niobate Nanosheets and the Microenvironment

  • Yu Nabetani*
    Yu Nabetani
    Department of Applied Chemistry, Faculty of Engineering, University of Miyazaki, Gakuen-kibanadai-nishi 1-1, Miyazaki-city, Miyazaki 889-2192, Japan
    *Email: [email protected]
    More by Yu Nabetani
  • Syed Zahid Hassan
    Syed Zahid Hassan
    Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-osawa 1-1, Hachioji, Tokyo 192-0397, Japan
  • Haruo Horiguchi
    Haruo Horiguchi
    Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-osawa 1-1, Hachioji, Tokyo 192-0397, Japan
  • Hiroshi Tachibana
    Hiroshi Tachibana
    Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-osawa 1-1, Hachioji, Tokyo 192-0397, Japan
  • Haruo Inoue
    Haruo Inoue
    Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-osawa 1-1, Hachioji, Tokyo 192-0397, Japan
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  • , and 
  • Tsutomu Shiragami
    Tsutomu Shiragami
    Department of Applied Chemistry, Faculty of Engineering, University of Miyazaki, Gakuen-kibanadai-nishi 1-1, Miyazaki-city, Miyazaki 889-2192, Japan
Cite this: J. Phys. Chem. C 2024, 128, 3, 1423–1432
Publication Date (Web):January 10, 2024
https://doi.org/10.1021/acs.jpcc.3c06989
Copyright © 2024 American Chemical Society

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    Abstract

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    A layered nanosheet hybrid composed of niobate nanosheet and polyfluoroalkyl azobenzene derivative (C3F-Azo-C6H) can undergo three-dimensional morphology change upon photo-irradiations. The unique photo-activated motion is based on the interlayer distance change and nanosheet sliding induced by the photo-isomerization of C3F-Azo-C6H which is presumably caused by the subsequent changes of the nanostructure in the hybrid. However, the mechanism of the morphological change at a molecular level has not yet been fully understood. The nanostructure and its delicate change in the layered hybrid should be closely related to the mechanism. Here, the nanostructure has been investigated in detail by X-ray diffraction, thermogravimetric/differential thermal analysis, and UV–vis and IR spectroscopy to get deeper insights into the mechanism of the photo-activated motion. Based on the intercalation amount, the molecular size, the clearance space, and the tilting angles, C3F-Azo-C6Hs are considered to align on the nanosheet and form an interdigitated bilayer structure in their terminal alkyl chains. The intercalated C3F-Azo-C6Hs also form a two-dimensional network having intermolecular hydrogen bonding among their amide groups and π–π interaction of azobenzene. Furthermore, it was revealed that the terminal alkyl chains located in the center of the bilayer are swung by the swayback motion of the isomerized azobenzene to induce the morphology change. The high-order architecture formed on the nanosheets should be a key factor in inducing the cooperative reaction and conformational change of C3F-Azo-C6H on the niobate nanosheet microenvironment.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.3c06989.

    • Reversible change of interlayer distance upon repeated cycles of photo-irradiation; photo-induced interlayer distance change of the layered hybrid fabricated by the intercalation at r. t.; polarization spectroscopic analysis of the layered hybrid; angular dependence of the dichroic ratio at 2920 cm–1 before and after UV and visible light irradiation; and angular dependence of the dichroic ratio at 2926 cm–1 before and after UV and visible light irradiation (PDF)

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