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0 202604049

DOI: https://doi.org/10.6023/cjoc202604049

ARTICLE

Modulating the Thermal Stability of cis Isomers of Azobenzene Photoswitches via n→π* Interactions

  • Ke-Tian Shi ,
  • Xiang-Yu Wei ,
  • Yu Hai ,
  • Li-Juan Liu ,
  • Tian-Guang Zhan ,
  • Kang-Da Zhang
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  • aKey Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua, 321004;
    bZhejiang Key Laboratory of Advanced Catalysis and Adsorption Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua, 321004

Received date: 2026-04-29

  Revised date: 2026-06-26

  Online published: 2026-07-24

Supported by

National Natural Science Foundation of China (No. 22271255) and the Natural Science Foundation of Zhejiang Province (Nos. LR22B020001, LQ24B020007).

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Abstract

Azobenzenes are a class of important molecular photoswitches with wide-ranging applications in energy storage, supramolecular assembly, biomedicine and beyond. However, it remains a significant challenge to effectively tune the thermal stability of their cis-isomers without compromising the key photoswitching properties such as absorption wavelength and isomerization efficiency. In this research, we deccribe a unique n→π* interaction based noncovalent strategy for tuning the cis-isomer’s thermal stability of azobenzene photoswitches, for which a series of azo molecules were designed and synthesized by introducing a methoxy group (providing n electron) and different carbonyl units (providing π* orbital) at the meta positions of azo double bond, respectively. The UV-Vis and 1H NMR experiments revealed these photoswitches could undergo reversible E⇄Z photoisomerization upon 365 nm UV and 430 nm visible light irradiation. The FT-IR spectra verified the existence of n→π* interactions in the cis-isomers, which could be enhanced by reducing the electron-withdrawing nature of the carbonyl units or increasing the solvent polarity, thereby improving the thermal stability of the photoswitches. These findings provide new insights for the design of new molecular photoswitches with tunable thermal stability.

Key words： photoswitches; azobenzene; n→π* interaction; thermal stability.

Cite this article

Ke-Tian Shi , Xiang-Yu Wei , Yu Hai , Li-Juan Liu , Tian-Guang Zhan , Kang-Da Zhang . Modulating the Thermal Stability of cis Isomers of Azobenzene Photoswitches via n→π* Interactions[J]. Chinese Journal of Organic Chemistry, 0 : 202604049 . DOI: 10.6023/cjoc202604049

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