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

doi:10.6023/cjoc202604049

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基于n→π*相互作用调控偶氮苯光开关顺式异构体的热稳定性

石可添^a,b, 韦相宇^a,b, 海宇^*,a,b, 刘丽娟^a,b, 占田广^a,b, 章康达^*,a,b

^a先进催化材料教育部重点实验室,化学与材料科学学院,浙江师范大学金华 321004;
^b全省先进催化与吸附材料重点实验室,化学与材料科学学院,浙江师范大学金华 321004

收稿日期:2026-04-29 修回日期:2026-06-26
基金资助:
国家自然科学基金(No. 22271255)和浙江省自然科学基金(Nos. LR22B020001, LQ24B020007)资助项目.

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

Ke-Tian Shi^a,b, Xiang-Yu Wei^a,b, Yu Hai^a,b,*, Li-Juan Liu^a,b, Tian-Guang Zhan^a,b, Kang-Da Zhang^a,b,*

^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:2026-04-29 Revised:2026-06-26
Contact: ^*E-mail: haiyuyu@zjnu.edu.cn; Kangda.Zhang@zjnu.cn
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, doi: 10.6023/cjoc202604049.

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基于n→π*相互作用调控偶氮苯光开关顺式异构体的热稳定性

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

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