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Light-driven molecular switching of atropisomeric polymers containing azo-binaphthyl groups in their side chains


Light-driven atropisomeric polymers containing azo and binaphthyl units with a conjugated structure were designed and synthesized. The polymers exhibit a glass transition temperature higher than 75 °C with thermal stability above 280 °C and form uniform and smooth thin films without grain boundaries. The trans-cis isomerization is efficiently reversible upon alternating photoirradiation with UV and visible light or with heat. The photoisomerization of the chiral polymer results in photomodulation of the ellipticity and optical rotation (\([\alpha ]_{\mathrm{D}}^{25}\)), owing to a chiroptical switching behavior. The maximum changes in the dihedral angle and \([\alpha ]_{\mathrm{D}}^{25}\) are 21% and 700°, respectively, from the initial state owing to a photoinduced molecular twisting motion of the binaphthyl moiety. The polymer also displays photoswitchable fluorescence with a maximum at 409 nm. A photoinduced change in the refractive index of the formed film is also observed after irradiation with linearly polarized light at 532 nm according to the anisotropic molecular orientation. These results suggest that atropisomeric polymers are potential candidates for light-driven chiroptical switches.

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This work was partially supported by a Grant-in-Aid for Scientific Research (C) (No. 15K05639) for MK from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. We thank Prof. Yu Nagase and Mr. Ryota Ueno of Tokai University for GPC measurements. We acknowledge the Support Unit of Bio-Material Analysis, Research Resources Center, RIKEN Brain Science Institute for the high-resolution mass spectrometry. We are grateful to the Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science (CEMS), for the elemental analysis. We thank Dr. Zhaomin Hou and Dr. Masayoshi Nishiura of the Organometallic Chemistry Laboratory, RIKEN, for the DSC and TGA measurements. We acknowledge Dr. Mikiko Sodeoka and Dr. Yoshihiro Sohtome of the Synthetic Organic Chemistry Laboratory, RIKEN, for the optical rotation measurements. We also thank Dr. Keisuke Tajima and Dr. Kyohei Nakano of the Emergent Functional Polymers Research Team of RIKEN CEMS for the measurements of film thickness. We thank the Edanz Group ( for editing a draft of this manuscript.

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Correspondence to Yoshihiro Ito or Masuki Kawamoto.

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Hassan, F., Sassa, T., Hirose, T. et al. Light-driven molecular switching of atropisomeric polymers containing azo-binaphthyl groups in their side chains. Polym J 50, 455–465 (2018).

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