Citation: SONG Xiumei, FENG Zongcai, WANG Zhaoyang, CHEN Xiaoling, LIANG Zhimei, LIANG Yanyu. Synthesis, Characterization and Photoisomerization Properties of Pseudostilbene Azobenzenes[J]. Chinese Journal of Applied Chemistry, ;2016, 33(4): 442-451. doi: 10.11944/j.issn.1000-0518.2016.04.150282 shu

Synthesis, Characterization and Photoisomerization Properties of Pseudostilbene Azobenzenes

1.
a Development Center for New Materials Engineering & Technology in Universities of Guangdong, Industrial Technology Research Institute, Lingnan Normal University, Zhanjiang, Guangdong 524048, China;
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b School of Chemistry and Chemical Engineering, Lingnan Normal University, Zhanjiang, Guangdong 524048, China;
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c School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China

Corresponding author: FENG Zongcai,
Received Date: 6 August 2015
Available Online: 19 November 2015
Fund Project:

A series of novel pseudostilbene azobenzenes was synthesized and their structures were characterized by FT-IR, NMR, MS(ESI) and elemental analysis. The photoisomerization properties and reversible cis/trans isomerization rate constants in solvent were measured via UV-Vis spectroscopy, as well as the fatigue resistance property in polymethyl methacrylate(PMMA) film was performed. The azobenzenes in ethyl acetate have the two bands of π-π^* and n-π^* inverted on the energy scale and π-π^* and n-π^* bands are practically superimposed. The isomerization rate constants range from 10^-1 to 10⁰ s^-1. The trans to cis isomerization rate constants depend on the dipole-dipole interactions and molecular steric hindrance, with the dipole-dipole interactions having larger impact on monobromo-azobenzenes than dibromo-azobenzenes, and a reverse impact from molecular steric hindrances. The faster trans to cis transformation corresponds to the slower cis to trans transformation. The azobenzene has a good fatigue resistance to some extent in PMMA film.
- pseudostilbene azobenzenes,
- azo coupling,
- photochromic,
- cis/trans isomerization,
- rate constant
1. [1]
  [1] Jaunet-Lahary T,Chantzis A,Chen K J,et al. Designing Efficient Azobenzene and Azothiophene Nonlinear Optical Photochromes[J]. J Phys Chem C,2014,118(49):28831-28841.
2. [2]
  [2] Liaros N,Couris S,Maggini L,et al. NLO Response of Photoswitchable Azobenzene-based Materials[J]. Chem Phys Chem,2013,14(13):2961-2972.
3. [3]
  [3] Ouazzani H E,Iliopoulos K,Pranaitis M,et al. Second- and Third-order Nonlinearities of Novel Push-pull Azobenzene Polymers[J]. J Phys Chem B,2011,115(9):1944-1949.
4. [4]
  [4] Hosseini S H,Hoshangi V. Preparation of Poly(2-anilinoethanol) Containing Azobenzene Group under Electrical Field and Its Liquid Crystalline Properties Investigation[J]. Polym Adv Technol,2015,26(1):10-18.
5. [5]
  [5] Lyu J A,Wang W R,Xu J X,et al. Photoinduced Bending Behavior of Cross-linked Azobenzene Liquid-crystalline Polymer Films with a Poly(oxyethylene) Backbone[J]. Macromol Rapid Commun,2014,35(14):1266-1272.
6. [6]
  [6] Bogdanov A V,Vorobiev A K. Photo-orientation of Azobenzene-containing Liquid-crystalline Materials by Means of Domain Structure Rearrangement[J]. J Phys Chem B,2013,117(44):13936-13945.
7. [7]
  [7] He X H,Gao C Y,Sun W Q,et al. Synthesis and Photoresponsive Behavior of Azobenzene-containing Side-chain Liquid Crystalline Diblock Polymers with Polypeptide Block[J]. J Polym Sci Part A:Polym Chem,2013,51(5):1040-1050.
8. [8]
  [8] Amer W A,Wang L,Amin A M,et al. Liquid-crystalline Azobenzene-containing Ferrocene-based Polymers:Study on Synthesis and Properties of Main-chain Ferrocene-based Polyesters with Azobenzene in the Side Chain[J]. Polym Adv Technol,2013,24(2):181-190.
9. [9]
  [9] Lee K M,White T J. Photochemical Mechanism and Photothermal Considerations in the Mechanical Response of Monodomain, Azobenzene-functionalized Liquid Crystal Polymer Networks[J]. Macromolecules,2012,45(17):7163-7170.
10. [10]
  [10] Benassi E,Corni S. Quenching of the Photoisomerization of Azobenzene Self-assembled Monolayers by the Metal Substrate[J]. J Phys Chem C,2014,118(45):25906-25917.
11. [11]
  [11] Benassi E,Corni S. Exciton Transfer of Azobenzene Derivatives in Self-assembled Monolayers[J]. J Phys Chem C,2013,117(47):25026-25041.
12. [12]
  [12] Mba M,Mazzier D,Silvestrini S,et al. Photocontrolled Self-assembly of a Bis-azobenzene-containing α-Amino Acid[J]. Chem Eur J,2013,47(18):15841-15846.
13. [13]
  [13] Zheng X Y,Wang D,Shuai Z G,et al. Molecular Dynamics Simulations of the Supramolecular Assembly Between an Azobenzene-containing Surfactant and α-Cyclodextrin:Role of Photoisomerization[J]. J Phys Chem B,2012,116(2):823-832.
14. [14]
  [14] Goldau T,Murayama K J,Brieke C,et al. Reversible Photoswitching of RNA Hybridization at Room Temperature with an Azobenzene C-Nucleoside[J]. Chem Eur J,2015,21(7):2845-2854.
15. [15]
  [15] Hu X Y,Jia K K,Cao Y,et al. Dual Photo- and pH-responsive Supramolecular Nanocarriers Based on Water-soluble Pillar
16. [16]
  [6] arene and Different Azobenzene Derivatives for Intracellular Anticancer Drug Delivery[J]. Chem Eur J,2015,21(3):1208-1220.
17. [17]
  [16] Samanta S,Woolley A G. Bis-azobenzene Crosslinkers for Photocontrol of Peptide Structure[J]. Chem Bio Chem,2011,12(11):1712-1723.
18. [18]
  [17] Korbus M,Back S,Meyer-Almes F J. The Cis-state of an Azobenzene Photoswitch Is Stabilized through Specific Interactions with a Protein Surface[J]. J Mol Recognit,2015,28(3):201-209.
19. [19]
  [18] Azov V A,Cordes J,Schl ter D,et al. Light-controlled Macrocyclization of Tetrathiafulvalene with Azobenzene:Designing an Optoelectronic Molecular Switch[J]. J Org Chem,2014,79(23):11714-11721.
20. [20]
  [19] Izquierdo-Serra M,Gasc n-Moya M,Hirtz J J,et al. Two-photon Neuronal and Astrocytic Stimulation with Azobenzene-based Photoswitches[J]. J Am Chem Soc,2014,136(24):8693-8701.
21. [21]
  [20] Cafeo G,Kohnke F H,Mezzatesta G,et al. Host-guest Chemistry of a Bis-calix
22. [22]
  [4] pyrrole Derivative Containing a Trans/cis-switchable Azobenzene Unit with Several Aliphatic Bis-carboxylates[J]. Chem Eur J,2015,21(14):5323-5327.
23. [23]
  [21] Deng J,Liu X Y,Shi W B,et al. Light-triggered Switching of Reversible and Alterable Biofunctionality via β-Cyclodextrin/Azobenzene-based Host-guest Interaction[J]. Macro Lett,2014,3(11):1130-1133.
24. [24]
  [22] Yamada M,Kondo M,Mamiya J,et al. Photomobile Polymer Materials: towards Light-driven Plastic Motors[J]. Angew Chem Int Ed Eng,2008,47(27):4986-4988.
25. [25]
  [23] Ya Q,Dong X Z,Chen W Q,et al. The Synthesis of Aminoazobenzenes and the Effect of Intermolecular Hydrogen Bonding on Their Photoisomerization[J]. Dyes Pigm,2008,79:159-165.
26. [26]
  [24] Wang Y,Tang X Z,Tang X,et al. Synthesis and Properties of Two Novel Azo-benzene Chromophores[J]. Chem J Chinese Univ,2011,32(10):2327-2330.
27. [27]
  [25] G mez J A,Koslowski A,Thiel W. Enhanced E/Z Photoisomerisation in 2-Ami-noazobenzene[J]. RSC Adv,2014,4:1886-1889.
28. [28]
  [26] Stephanie H,James M T. Synthesis of Anthropomorphic Molecules:The NanoPutians[J]. J Org Chem,2003,68(23):8750-8766.
29. [29]
  [27] Kubiczak G A,Franz O,Borlakoglu J T,et al. A Unique Approach to the Synthesis of 2,3,4,5-Substituted Polybrominated Biphenyls:Quantitation in Fire Master FF-1 and Fire Master BP-6[J]. Agric Food Chem,1989,37(4):1160-11649.
30. [30]
  [28] WANG Hui. Studies on Synthesis and Photochromic Properties of Substituded Azobenzene Compounds[D]. Wuhan:Central China Normal University,2004(in Chinese).王辉. 取代偶氮苯化合物的合成及其光致变色性能研究[D]. 武汉:华中师范大学,2004.
31. [31]
  [29] TIAN Demei. Preparation and Photochromism Properties of Polystyrene with Azobenzene Group[D]. Wuhan:Wuhan University of Technology,2008(in Chinese).田德美. 含偶氮苯基团的聚苯乙烯合成及光致变色性能研究[D]. 武汉:武汉理工大学,2008.
32. [32]
  [30] Conti I,Marchioni F,Credi A,et al. Cyclohexenylphenyldiazene:A Simple Surrogate of the Azobenzene Photochromic Unit[J]. J Am Chem Soc,2007,129(11):3198-3210.
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