Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field
Received date: 2022-01-30
Online published: 2022-04-06
Supported by
National Natural Science Foundation of China(22073005)
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≤Fz≤0.93 V•Å-1, the rotation path is the dominant path. When –0.93 V•Å-1≤Fz≤–0.62 V•Å-1, N2 inversion path is the dominant path. When Fz≤–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.
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 . DOI: 10.6023/A22010056
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