Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures

doi:10.1007/s40242-024-4185-3

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (1): 33-39.doi: 10.1007/s40242-024-4185-3

Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures

WANG Yaxin¹, CHEN Yulan²

1. Key Laboratory of Organic Integrated Circuit, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, P. R. China;
2. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China

收稿日期:2024-09-01 出版日期:2025-02-01 发布日期:2025-01-18
通讯作者: CHEN Yulan,yulanchen@jlu.edu.cn E-mail:yulanchen@jlu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (Nos. 22275068 and 21975178) and the Open Project of the State Key Laboratory of Supramolecular Structure and Materials of China.

Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures

WANG Yaxin¹, CHEN Yulan²

1. Key Laboratory of Organic Integrated Circuit, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, P. R. China;
2. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China

Received:2024-09-01 Online:2025-02-01 Published:2025-01-18
Contact: CHEN Yulan,yulanchen@jlu.edu.cn E-mail:yulanchen@jlu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos. 22275068 and 21975178) and the Open Project of the State Key Laboratory of Supramolecular Structure and Materials of China.

摘要/Abstract

摘要： We design and synthesize five novel diazocine derivatives, using diazocine as the core, amide or imine bonds as the connecting units attached with different peripheral substituents. The photoisomerization yield and thermal stability of these derivatives are tested by ¹H NMR and UV-Vis absorption spectroscopy. Among them, the imine-linked derivative exhibits the lowest photoisomerization efficiency, while the amide-linked ones show an elevated switching efficiency in transitioning from the cis to the trans configuration, compared to the unmodified 3,3'-diamino-diazocine. Furthermore, based on experiments together with density functional theory (DFT) calculations, we find that the thermal stability of these derivatives is associated with the electron cloud density and steric hindrance of their substituents. Owing to these unique photophysical properties, diazocine derivatives provide a foundation for the development and application of molecular optical switches.

关键词: Diazocine, Photoisomerization, Thermal stability

Abstract: We design and synthesize five novel diazocine derivatives, using diazocine as the core, amide or imine bonds as the connecting units attached with different peripheral substituents. The photoisomerization yield and thermal stability of these derivatives are tested by ¹H NMR and UV-Vis absorption spectroscopy. Among them, the imine-linked derivative exhibits the lowest photoisomerization efficiency, while the amide-linked ones show an elevated switching efficiency in transitioning from the cis to the trans configuration, compared to the unmodified 3,3'-diamino-diazocine. Furthermore, based on experiments together with density functional theory (DFT) calculations, we find that the thermal stability of these derivatives is associated with the electron cloud density and steric hindrance of their substituents. Owing to these unique photophysical properties, diazocine derivatives provide a foundation for the development and application of molecular optical switches.

Key words: Diazocine, Photoisomerization, Thermal stability

WANG Yaxin, CHEN Yulan. Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures[J]. 高等学校化学研究, 2025, 41(1): 33-39.

WANG Yaxin, CHEN Yulan. Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures[J]. Chemical Research in Chinese Universities, 2025, 41(1): 33-39.

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Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures

Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures

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