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

doi:10.6023/cjoc202604049

摘要/Abstract

偶氮苯是一类在能量存储、超分子组装、生物医学等领域具有广泛应用的光开关分子, 然而, 其顺式异构体热稳定性往往难以在不影响吸收波长、异构化效率等关键性质的前提下实现有效调控. 针对这一挑战, 本研究提出了一种基于n→π*弱相互作用调控偶氮苯顺式异构体热稳定性的新策略, 设计合成了一类苯环间位分别引入甲氧基和不同类型羰基的偶氮苯衍生物, 通过其顺反异构化可以改变甲氧基n电子与羰基π*轨道之间的弱相互作用, 进而实现调控顺式异构体的热弛豫半衰期. UV-Vis、¹H NMR实验研究表明, 这类光开关分子在365 nm紫外光和430 nm可见光照射下, 可进行E⇄Z光异构化, FT-IR实验证实其顺式异构体中存在明显的n→π*相互作用, 并且减弱羰基的电子云密度或者增加溶剂极性有利于增强该作用, 进而提高顺式异构体的热稳定性. 这些研究结果为设计具有可调控热稳定性的偶氮苯光开关提供了新思路.

关键词: 光开关, 偶氮苯, n→π*弱相互作用, 热稳定性

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, a unique n→π* interaction based noncovalent strategy is deccribed for tuning the cis-isomer 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 that 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

引用此文

石可添, 韦相宇, 海宇, 刘丽娟, 占田广, 章康达. 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[J]. 有机化学, 2026, 46(9): 3666-3675.

Ketian Shi, Xiangyu Wei, Yu Hai, Lijuan Liu, Tianguang Zhan, Kangda Zhang. Modulating the Thermal Stability of cis Isomers of Azobenzene Photoswitches via n→π* Interactions[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3666-3675.

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图/表 6

Figure 1. Previous representative strategies for modulating the thermal half-life of cis-isomeric azobenzene derivatives (a) Covalent modifications to the azobenzene core, such as the introduction of halogen atoms, electron push-pull groups, and the formation of bridged azobenzenes. (b) Introduction of non-covalent interactions such as hydrogen bonding, C—H…π interactions, and coordination interaction. (c) This work introduces a unique n→π* interaction involved strategy for tuning the thermal stability of the cis-isomers of azobenzene derivatives.

Scheme 1. Synthesis of (a) target meta-methoxy-functionalized azobenzene derivatives MeOAzoCHO, MeOAzoCOOMe, and MeOAzoCONHMe; (b) control meta-methoxy-free azobenzene derivatives AzoCHO, AzoCOOMe, and AzoCONHMe

Figure 2. Photoswitching property of the target azobenzene derivatives The UV-Vis absorption spectra (50 µmol/L in CH3CN) of MeOAzoCHO (a), MeOAzoCOOMe (b), and MeOAzoCONHMe (c) under different light irradiation conditions: at pristine (black line), after exposure to 365 nm UV light irradiation (purple light), and after irradiated by 430 nm visible light (blue line); Partial 1H NMR spectra (400 MHz, CD3CN, 5 mmol/L) of MeOAzoCHO (d), MeOAzoCOOMe (e), and MeOAzoCONHMe (f) under different light irradiation conditions.

Figure 3. Thermal relaxation and half-life analysis of azobenzene derivatives Partial time-dependent 1H NMR spectra (400 MHz, CD3CN, 298 K) for the PSSZ (430 nm) mixtures of (a) MeOAzoCHO (5.0 mmol/L), (b) MeOAzoCOOMe (5.0 mmol/L), and (c) MeOAzoCONHMe (5.0 mmol/L); Panels d~f display the fitted curves of Z-isomer fraction versus time and the corresponding t1/2 values, which are derived from the spectroscopic data in panels a~c in sequence

Figure 4. Comparison of FT-IR spectra for both isomers of (a) MeOAzoCHO, (b) MeOAzoCOOMe, and (c) MeOAzoCONHMe with the carbonyl stretching vibration being highlighted to monitor the presence of n→π* interaction All spectra were acquired using film samples.

	t_1/2(Z-to-E)^a/h
	MeOAzoCHO	MeOAzoCOOMe	MeOAzoCONHMe	AzoCHO	AzoCOOMe	AzoCONHMe
CD₃CN	427	398	350	263	273	277
DMSO-d₆	322	306	264	251	270	266
CDCl₃	162	148	123	263	259	268
Toluene-d₈	140	125	99	261	260	255

Table 1. Summary of the thermal half-lives of Z-MeOAzoCHO, Z-MeOAzoCOOMe, Z-MeOAzoCONHMe, Z-AzoCHO, Z-Azo- COOMe, and Z-AzoCONHMe in solvents with varied polarity

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