电场下偶氮苯衍生物分子顺反异构化反应机理的理论研究

doi:10.6023/A22010056

摘要/Abstract

本工作采用密度泛函理论(DFT)方法计算研究了不同电场强度下偶氮苯衍生物2'-对甲苯偶氮基-1,1':4,4'-三苯基- 4,4''二羧酸(TTDA)顺反异构化反应的机理. TTDA经过C—N¹=N²角度顺反异构化过程存在三种可能的异构化模式 (N=N偶氮基团中与大取代基相连的N原子称为N², 与小取代基相连的N原子称为N¹), 绕N¹或N²原子的反转和绕N¹=N²键旋转. 计算结果表明, 加入沿z轴的电场(以三联苯侧链C¹→C²方向为z轴正方向), 旋转路径为反应最优路径. 此外, 还研究了沿N=N键方向加入电场(以N²→N¹方向为z轴正方向), 在电场强度F_z=0.00 V•Å^-1时, N1反转路径能垒较N2反转路径高. 当–0.62 V•Å^-1<F_z≤0.93 V•Å^-1时, 旋转路径为优势路径. 当加入沿z轴的反向电场–0.93 V•Å^-1≤F_z≤–0.62 V•Å^-1时, N2反转为优势路径.

关键词: 电场, 偶氮苯衍生物, 异构化, 反应机理, 密度泛函理论

In this paper, the trans-cis isomerization mechanism of azobenzene derivative 2'-p-tolyldiazenyl-1,1':4,4'- terphenyl-4,4''-dicarboxylic acid (TTDA) under different electric field intensity was calculated and studied by symmetry destruction density functional theory (DFT). There are three possible isomerization modes of TTDA through C—N¹=N² angle trans-cis isomerization (N² connected to large substituents and N¹ connected to small substituents in azo groups), inversion around N¹ or N² atoms and rotation around N¹=N² bonds. The calculation results show that the electric field can significantly reduce the energy barrier of isomerization reaction. After adding the electric field, the electrons in trans-TTDA molecule have obvious transfer, the π orbit is polarized, and the energy level difference of HOMO (highest occupied molecular orbital) and LUMO (the lowest unoccupied molecular orbital) is significantly reduced, which also shows that the trans configuration of TTDA molecule is easier to convert to cis configuration. When the forward electric field along the z axis is added (taking the C¹→C² direction as the positive direction of the z axis), the rotation path is the optimal path. The rotation isomerization pathway around the N=N bond owns a lower free energy barrier compared to the inversion pathways. The steric effect is more important than the electrostatic effect for the isomerization of TTDA under the electric field along the C¹→C² direction. In addition, we also studied adding an electric field along the N=N bond (taking the N²→N¹ direction as the positive direction of the z axis). When the electric field intensity is 0.00 V•Å^-1, the inversion barrier of N1 is higher than that of N2. When –0.62 V•Å^-1≤F_z≤0.93 V•Å^-1, the rotation path is the dominant path. When –0.93 V•Å^-1≤F_z≤–0.62 V•Å^-1, N2 inversion path is the dominant path. When F_z≤–1.03 V•Å^-1, the terphenyl of cis-TTDA along the N²→N¹ direction is deformed. The molecular polarizability increases with the increase of electric field intensity. The electric field greatly promotes electron transfer in the isomerizaiton of TTDA as well as their electronic structures.

Key words: electric field, azobenzene derivatives, isomerization, reaction mechanism, density functional theory

引用此文

王珞聪, 李哲伟, 岳彩巍, 张培焕, 雷鸣, 蒲敏. 电场下偶氮苯衍生物分子顺反异构化反应机理的理论研究[J]. 化学学报, 2022, 80(6): 781-787.

Luocong Wang, Zhewei Li, Caiwei Yue, Peihuan Zhang, Ming Lei, Min Pu. Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field[J]. Acta Chimica Sinica, 2022, 80(6): 781-787.

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图/表 13

图1. 偶氮苯顺反异构化反应的两种模式: 反转和旋转路径

Figure 1. Two modes of cis-trans isomerization of azobenzene (TAB): inversion and rotation

图2. 2'-对甲苯偶氮基-1,1':4,4'-三苯基-4,4''二羧酸(TTDA)的可能异构化路径: N1反转, N2反转和旋转路径(N=N双键中与大取代基相连的N原子称为N2, 与小取代基相连的N原子称为N1)

Figure 2. Possible trans-cis isomerization pathways of of 2'-p-tolyldiazenyl-1,1':4,4'-terphenyl-4,4''-dicarboxylic acid (TTDA): N1 inversion, N2 inversion and rotation modes (In the N=N azo group, the N atom connecting with a large substituent group is called N2, and that connecting with a small substituent group is called N1)

图3. 在沿碳链方向电场强度为Fz=0.00 V•Å-1时TTDA分子N1, N2反转和旋转异构化能垒图

Figure 3. The free energy profiles of N1 and N2 inversion and rotational isomerization of TTDA molecules under the electric field intensity Fz=0.00 V•Å-1 along the C1—C2 direction

图4. 沿碳链方向电场强度为Fz=0.00 V•Å-1时TTDA分子N1, N2反转和旋转异构化能垒及对应过渡态中N1—N2键的Mayer及Wiberg键级示意图

Figure 4. The relationship between the changes of Mayer and Wiberg bond order of transitional states and free energy barriers of N1 and N2 inversion and rotational isomerization of TTDA under Fz=0.00 V•Å-1 along the C1—C2 direction

图5. 沿碳链方向Fz=0.00, 0.93和–0.93 V•Å-1的电场强度下时TTDA分子N1, N2反转和旋转异构化能垒图

Figure 5. The free energy profiles of N1 and N2 inversion and rotational isomerization of TTDA molecules under Fz=0.00, 0.93 and –0.93 V•Å-1 along the C1—C2 direction

图6. 沿碳链方向(A) Fz=0.00 V•Å-1, (B) Fz=0.93 V•Å-1和(C) Fz= –0.93 V•Å-1的电场下trans-TTDA分子前线分子轨道能图

Figure 6. Frontier molecular orbitals of trans-TTDA under Fz=0.00 (A), 0.93 (B) and –0.93 V•Å-1 (C) along the C1—C2 direction

图7. 沿碳链方向不同电场强度下TTDA过渡态分子N1, N2反转和旋转异构化反应自由能垒变化图

Figure 7. The change of free energy barriers of N1 inversion, N2 inversion and rotational isomerization of TTDA under different electric field intensities along the C1—C2 direction

图8. 沿碳链方向不同电场强度下trans-TTDA分子的HOMO, LUMO轨道能量和HOMO-LUMO能隙的变化示意图

Figure 8. The changes of orbital energies of HOMO, LUMO and HOMO-LUMO gap of trans-TTDA under different electric field intensities along the C1—C2 direction

图9. 沿碳链方向不同电场强度下TTDA过渡态分子N1和N2原子的APT电荷

Figure 9. APT charges of N1 and N2 atoms of transition states of TTDA isomerization under different electric field intensities along the C1—C2 direction

图10. 沿反应轴方向不同电场强度下TTDA过渡态分子N1或N2反转和旋转异构化能垒图

Figure 10. The energy barrier diagrams of N1 and N2 inversion and rotational isomerization of TTDA molecules under different electric field intensities along the N2—N1 direction

图11. 沿反应轴方向不同电场强度下trans-TTDA分子N1和N2原子的APT电荷变化图

Figure 11. APT charges of N1 and N2 atoms of trans-TTDA transition state molecules under different electric field intensities along the N2—N1 direction

图12. 沿碳链方向不同电场对反式、顺式TTDA分子能量和二面角∠C3N1N2C4的影响(以Fz=0.00 V•Å-1下反式TTDA分子能量为零点)

Figure 12. The changes of free energies and $\angle$C3N1N2C4 dihedral angles of trans-TTDA and cis-TTDA under different electric field intensities along C1—C2 direction relative to that of trans-TTDA under Fz=0.00 V•Å-1

图13. 沿键轴方向不同电场对反式、顺式TTDA分子能量和二面角∠C3N1N2C4的影响(以Fz=0.00 V•Å-1下反式TTDA分子能量为零点)

Figure 13. The changes of free energies and $\angle$C3N1N2C4 dihedral angles of trans-TTDA and cis-TTDA under different electric field intensities along N2—N1 direction relative to that of trans-TTDA under Fz=0.00 V•Å-1

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