高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

1,4-二氢吡啶衍生物光物理性质的理论研究

李浩静1,葛常威1,钟启迪2,闫红1,孙国辉1   

  1. 1. 北京工业大学化学与生命科学学院 2. 华北理工大学药学院

  • 收稿日期:2025-09-08 修回日期:2025-10-30 出版日期:2025-11-10 发布日期:2025-11-10
  • 通讯作者: 闫红 E-mail:hongyan@bjut.edu.cn

Study on the photophysical properties of 1,4-dihydropyridine derivatives

LI Haojing1, GE Changwei1, ZHONG Qidi2, YAN Hong1, SUN Guohui   

  1. 1. College of Chemistry and Life Sciences, Beijing University of Technology 2. College of Pharmacy, North China University of Science and Technology
  • Received:2025-09-08 Revised:2025-10-30 Online:2025-11-10 Published:2025-11-10
  • Contact: YAN Hong E-mail:hongyan@bjut.edu.cn

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摘要： 本文采用密度泛函理论(Density functional theory, DFT)及含时密度泛函理论(Time-dependent density functional theory, TDDFT)方法，在M06-2X/def2-TZVP计算水平下，首次系统揭示了1,4-二氢吡啶-3,5-二羧酸乙酯衍生物（1a-1h）中N-1位取代基对其光物理性质及光环加成反应的调控机制。结果表明，1,4-二氢吡啶衍生物（1a-1h）的N-1位取代基类型具体显著影响分子激发特性，电子激发主要表现为1,4-二氢吡啶环的π→π *跃迁；激发态电荷分布高度重叠且局域于环内C=C双键区域，呈现典型的局域激发特征，促使分子在激发态下保持近平面构型，加之关键反应位点的键长的显著变化，均有利于光环加成反应的发生。本研究首次从理论层面建立了1,4-二氢吡啶衍生物光物理性质与光环加成反应之间的系统性关联，为设计高效光化学反应体系和多环骨架构建提供了重要的理论依据与创新指导。

关键词: 1,4-二氢吡啶衍生物, 光物理性质, 密度泛函理论, 光环加成反应

Abstract: This study employs density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods at the M06-2X/def2-TZVP level to systematically reveal, for the first time, the regulatory mechanism of N-1 substituents on the photophysical properties and photocycloaddition reactions of ethyl 1,4-dihydropyridine-3,5-dicarboxylate derivatives (1a-1h). The results demonstrate that the type of N-1 substituent significantly influences the molecular excitation characteristics. Electronic excitations are predominantly characterized by π→π * transitions within the 1,4-dihydropyridine ring. The excited-state charge distribution is highly overlapping and localized in the C=C double bond region of the ring, exhibiting typical localized excitation features. This promotes a nearly planar molecular conformation in the excited state, accompanied by significant bond length changes at key reactive sites, both of which facilitate the occurrence of photocycloaddition reactions. This work establishes, for the first time, a systematic theoretical correlation between the photophysical properties and photocycloaddition reactivity of 1,4-dihydropyridine derivatives, providing important theoretical insights and innovative guidance for designing efficient photochemical reaction systems and constructing polycyclic frameworks.

Key words: 1,4-Dihydropyridine derivatives, Photophysical properties, Density functional theory, Photocycloaddition

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