Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field

doi:10.6023/A22010056

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 13

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

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)

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

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

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

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

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

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

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

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

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

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

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

References 42

[1]	Helal, W.; Bories, B.; Evangelisti, S.; Leininger, T.; Maynau, D. Computational Science and Its Applications, Springer, Berlin, Heidelberg, 2006, pp. 744-751.
[2]	Xiang, D.; Wang, X.; Jia, C.; Lee, T.; Guo, X. Chem. Rev. 2016, 116, 4318. doi: 10.1021/acs.chemrev.5b00680 pmid: 26979510
[3]	Jia, C.; Migliore, A.; Xin, N.; Huang, S.; Wang, J.; Yang, Q.; Wang, S.; Chen, H.; Wang, D.; Feng, B. Science 2016, 352, 1443. doi: 10.1126/science.aaf6298
[4]	zhang, J. L.; zhong, J. Q.; Lin, J. D.; Hu, W. P.; Wu, K.; Xu, G. Q.; Wee, A. T.; Chen, W. Chem. Soc. Rev. 2015, 44, 2998. doi: 10.1039/C4CS00377B
[5]	Jia, C.; Migliore, A.; Xin, N.; Huang, S.; Guo, X. Science 2016, 352, 1443. doi: 10.1126/science.aaf6298
[6]	Atesci, H.; Kaliginedi, V.; Celis Gil, J. A.; Ozawa, H.; Thijssen, J. M.; Broekmann, P.; Haga, M.-A.; van der Molen, S. J. Nat. Nanotechnol. 2018, 13, 117. doi: 10.1038/s41565-017-0016-8
[7]	Perrin, M. L.; Burzurí, E.; zant, H. Chem. Soc. Rev. 2015, 44, 902. doi: 10.1039/C4CS00231H
[8]	Song, H.; Kim, Y.; Jang, Y. H.; Jeong, H.; Reed, M. A.; Lee, T. Nature 2009, 462, 1039. doi: 10.1038/nature08639
[9]	Quek, S. Y.; Kamenetska, M.; Steigerwald, M. L.; Choi, H. J.; Louie, S. G.; Hybertsen, M. S.; Neaton, J. B.; Venkataraman, L. Nat. Nanotechnol. 2009, 4, 230. doi: 10.1038/nnano.2009.10
[10]	Perrin, M. L.; Verzijl, C. J. O.; Martin, C. A.; Shaikh, A. J.; Eelkema, R.; van Esch, J. H.; van Ruitenbeek, J. M.; Thijssen, J. M.; van der zant, H. S. J.; Dulić, D. Nat. Nanotechnol. 2013, 8, 282. doi: 10.1038/nnano.2013.26
[11]	Su, T. A.; Li, H.; Steigerwald, M. L.; Venkataraman, L.; Nuckolls, C. Nat. Chem. 2015, 7, 215. doi: 10.1038/nchem.2180
[12]	Kim, Y.; Jeong, W.; Kim, K.; Lee, W.; Reddy, P. Nat. Nanotechnol. 2014, 9, 881. doi: 10.1038/nnano.2014.209
[13]	Reddy, P.; Jang, S.-Y.; Segalman Rachel, A.; Majumdar, A. Science 2007, 315, 1568. doi: 10.1126/science.1137149
[14]	Reecht, G.; Scheurer, F.; Speisser, V.; Dappe, Y. J.; Mathevet, F.; Schull, G. Phys. Rev. Lett. 2014, 112, 047403. doi: 10.1103/PhysRevLett.112.047403
[15]	Reecht, G.; Scheurer, F.; Speisser, V.; Dappe, Y. J.; Mathevet, F.; Schull, G. Phys. Rev. Lett. 2014, 112, 047403. doi: 10.1103/PhysRevLett.112.047403
[16]	Thiele, S.; Balestro, F.; Ballou, R.; Klyatskaya, S.; Ruben, M.; Wernsdorfer, W. Science 2014, 344, 1135. doi: 10.1126/science.1249802
[17]	Natterer, F. D.; Yang, K.; Paul, W.; Willke, P.; Choi, T.; Greber, T.; Heinrich, A. J.; Lutz, C. P. Nature 2017, 543, 226. doi: 10.1038/nature21371
[18]	Liu, Z.; Ren, S.; Guo, X. Molecular-Scale Electronics 2019, 173.
[19]	Yin, X.; Zang, Y.; Zhu, L.; Low, J. Z.; Liu, Z. F.; Cui, J.; Neaton, J. B.; Venkataraman, L.; Campos, L. M. Sci. Adv. 2017, 3, eaao2615. doi: 10.1126/sciadv.aao2615
[20]	Liu, X.; Qin, L.; Zhan, Y.; Chen, M.; Yu, Y. Acta Chim. Sinica 2020, 78, 478. (in Chinese) doi: 10.6023/A20040103
	(刘晓珺, 秦朗, 詹媛媛, 陈萌, 俞燕蕾, 化学学报, 2020, 78, 478.) doi: 10.6023/A20040103
[21]	Wang, C.; Li, B.; Wang, C.; Wu, B. Acta Chim. Sinica 2022, 80, 101. (in Chinese) doi: 10.6023/A21120564
	(王冲, 李宝林, 王春儒, 吴波, 化学学报, 2022, 80, 101.) doi: 10.6023/A21120564
[22]	Zhai, Y.; Xu, W.; Meng, X.; Hou, H. Acta Chim. Sinica 2020, 78, 256. (in Chinese) doi: 10.6023/A19120427
	(翟亚丽, 许文娟, 孟祥茹, 侯红卫, 化学学报, 2020, 78, 256.) doi: 10.6023/A19120427
[23]	Isac, D. L.; Airinei, A.; Homocianu, M.; Fifere, N.; Cojocaru, C.; Hulubei, C. J. Photoch. Photobio. A. 2020, 390, 112300. doi: 10.1016/j.jphotochem.2019.112300
[24]	Sun, J.; Wu, Q.; Weng, W.; Liu, X.; Tan, P.; Sun, L. Acta Chim. Sinica 2020, 78, 1082. (in Chinese) doi: 10.6023/A20070316
	(孙静静, 吴仇荣, 翁文强, 刘晓勤, 谈朋, 孙林兵, 化学学报, 2020, 78, 1082.) doi: 10.6023/A20070316
[25]	Zang, Y.; Zou, Q.; Fu, T.; Ng, F.; Fowler, B.; Yang, J.; Li, H.; Steigerwald, M. L.; Nuckolls, C.; Venkataraman, L. Nat. Commun. 2019, 10, 4482. doi: 10.1038/s41467-019-12487-w
[26]	Huang, X.; Tang, C.; Li, J.; Chen, L.-C.; Zheng, J.; Zhang, P.; Le, J.; Li, R.; Li, X.; Liu, J.; Yang, Y.; Shi, J.; Chen, Z.; Bai, M.; Zhang, H.-L.; Xia, H.; Cheng, J.; Tian, Z.-Q.; Hong, W. Sci. Adv. 2019, 5, eaaw3072. doi: 10.1126/sciadv.aaw3072
[27]	Dutta, B. J.; Bhattacharyya, P. K. Int. J. Quantum Chem. 2015, 115, 1459. doi: 10.1002/qua.24950
[28]	Shaik, S.; Ramanan, R.; Danovich, D.; Mandal, D. Chem. Soc. Rev. 2018, 47, 5125. doi: 10.1039/C8CS00354H
[29]	Avdic, I.; Kempfer-Robertson, E. M.; Thompson, L. M. J. Phys. Chem. A 2021, 125, 8238. doi: 10.1021/acs.jpca.1c06102 pmid: 34494847
[30]	Yogitha, S. N.; Kumar, B.; Raghavendra; Imranpasha; Gupta, S. K. Mater. Sci. Eng. B 2021, 267, 115094. doi: 10.1016/j.mseb.2021.115094
[31]	Alemani, M.; Peters, M. V.; Hecht, S.; Rieder, K.-H.; Moresco, F.; Grill, L. J. Am. Chem. Soc. 2006, 128, 14446. pmid: 17090013
[32]	Lu, T.; Chen, Q. ChemPhysChem 2021, 22, 386. doi: 10.1002/cphc.202000903
[33]	Meng, L.; Xin, N.; Hu, C.; Wang, J.; Gui, B.; Shi, J.; Wang, C.; Shen, C.; Zhang, G.; Guo, H.; Meng, S.; Guo, X. Nat. Commun. 2019, 10, 1450. doi: 10.1038/s41467-019-09120-1
[34]	Stark, J. Nature 1913, 92, 401.
[35]	Fried, S. D.; Boxer, S. G. Annu. Rev. Biochem. 2017, 86, 387. doi: 10.1146/annurev-biochem-061516-044432
[36]	Murgida, D. H.; Hildebrandt, P. Acc. Chem. Res. 2004, 37, 854. doi: 10.1021/ar0400443
[37]	Bruot, C.; Hihath, J.; Tao, N. Nat. Nanotechnol. 2012, 7, 35. doi: 10.1038/nnano.2011.212
[38]	Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615. doi: 10.1039/b810189b
[39]	Hratchian, H. P.; Schlegel, H. B. J. Chem. Phys. 2004, 120, 9918. pmid: 15268010
[40]	Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.22885
[41]	Legault, C. Y. CYLview, 1.0b, Université de Sherbrooke, 2009, http://www.cylview.org.
[42]	Humphrey, W.; Dalke, A.; Schulten, K. J. Mol. Graph. Model. 1996, 14, 33.

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