Organogel and Photo-responsive Behaviour of Hydrazide Derivatives Containing Azobenzene Groups†

doi:10.7503/cjcu20170019

Abstract

Abstract:

The hydrazide derivatives containing azobenzene groups N-(3,4-n-oxyphenyl)-N'-4-(azophenyl)- benzohydrazide Dn(n=7, 8, 10) with different terminal alkyl chain lengths were designed and synthesized. Dn can form a stable organogel and the terminal alkyl chains play crucial roles in improving the gel ability and thermodynamic stability. The main driving forces of gel formation are intermolecular hydrogen bonds between amide groups, π-π interactions among azobenzene groups and van der Waals forces between alkyl chains. Irradiation of the solution by UV light can lead to trans-cis isomerization of the azobenzene units. Although the conversion efficiency of cis-azobenzene in solution is notable, the photo-induced trans-cis isomerization of azobenzene in the gel cannot induce gel-sol.

Key words: Azobenzene, Hydrazide, Organogel, Photo-responsive

CLC Number:

O63
O648.17

TrendMD:

LI Zhiming, DING Qiang, GU Xiaojun, XIN Hong, BAI Binglian, LI Min. Organogel and Photo-responsive Behaviour of Hydrazide Derivatives Containing Azobenzene Groups^†[J]. Chem. J. Chinese Universities, 2017, 38(9): 1695.

Figures/Tables 12

Fig.1 Molecular structure of compounds Dn(n=7,8,10)

Table 1 Gelation properties of Dn*

Solvent	D7(CGC, mg/mL)	D8(CGC, mg/mL)	D10(CGC, mg/L)
Cyclohexane	G(2.0)	G(2.0)	G(1.0)
1,2-Dichloroethane	S	G(17.5)	G(12.5)
DMSO	S	S	G(8.0)
Ethanol	P	P	P

Fig.2 Plots of Tgel versus the concentration of D10(a), D8(b) and D7(c) in cyclohexane

Fig.3 Amplitude dependencies of storage modulus(G', a) and lose moulus(G″, b) of D7(A), D8(B) and D10(C) gel in cyclohexane The frequency is 1 Hz and the strain is 0.1%, 10 mg/mL.

Fig.4 SEM images of D10(A—C), D7(D) and D8(E) xerogels in different solvents(A) Cyclohexane, 1 mg/mL; (B) DMSO, 8 mg/mL; (C) 1,2-dichloroethane, 13 mg/mL; (D, E)cyclohexane, 4 mg/mL.

Fig.5 X-Ray diffraction patterns of D7(a), D8(b) and D10(c) xerogels in cyclohexane

Fig.6 Temperature-dependent FTIR spectra of D10 xerogel in cyclohexaneFrom bottom to top: 30 to 190 ℃, 10 ℃ intervel.

Fig.7 FTIR spectra of D7(a), D8(b) and D10(c) xerogels in cyclohexane

Fig.8 Temperature-dependent UV-Vis absorption spectra of D10 solution in cyclohexane(0.6 mg/mL)

Fig.9 UV-Vis spectra of 1×10-3 mol/L D10 solution in cyclohexane(A), DMSO(B) and 1,2-dichloroethane(C) under UV light irradiation

Fig.10 UV-Vis spectra of 1×10-3 mol/L D7(A) and D8(B) solutions in cyclohexane under UV light irradiation

Fig.11 UV-Vis spectra of 1 mg/mL D10 gel in cyclohexane

References 24

[1]	Lehn J. M., Science, 1993, 260, 1762—1763
[2]	Terech P., Weiss R. G., Chem. Rev., 1997, 97, 3133—3160
[3]	George M., Weiss R. G., Accounts Chem. Res., 2006, 39, 489—497
[4]	Yagai S., Karatsu T., Kitamura A., Chem. Eur. J., 2005, 11, 4054—4063
[5]	Klajn R., Pure Appl. Chem., 2010, 82, 2247—2279
[6]	Uchida K., Yamaguchi S., Yamada H., Akazawa M., Miyasaka H.,Chem. Commun., 2009, 4420—4422
[7]	Matsuzawa Y., Tamaoki N., J. Phys. Chem. B, 2010, 114(4), 1586—1590
[8]	Wang C., Chen Q., Sun F., Zhang D., Zhang G., Huang Y., Zhao R., Zhu D., J. Am. Chem. Soc., 2010, 132(9), 3092—3096
[9]	Li X., Gao Y., Kuang Y., Xu B., Chem. Commun., 2010, 46, 5364—5366
[10]	Yang R. M., Dong G. X., Zhao D. J., Yang Y. L., Liu Y. H., Chem. Ind. Eng. Pro., 2015, 34(6), 1661—1671
	(杨润苗, 董观秀, 赵德建, 杨雁玲, 刘玉海.化工进展,2015, 34(6), 1661—1671)
[11]	Ran X., Wang H. T., Zhang P., Bai B. L., Zhao C. X., Yu Z. X., Li M., Soft Matter, 2011, 7, 8561—8566
[12]	Zhang X., Li M., J. Mol. Struct., 2008, 892, 490—494
[13]	Zhang P., Wang H. T., Liu H. M., Li M., Langmuir,2010, 26(12), 10183—10190
[14]	Zhao C. X., Wang H. T., Bai B. L., Qu S. N., Song J. X., Ran X., Zhang Y., Li M., New J. Chem., 2013, 37, 1454—1460
[15]	Samanta S. K., Pal A., Bhattacharya S., Rao C., J. Mater. Chem., 2010, 20, 6881—6890
[16]	Zhang Y., Wang H. T., Zhao C. X., Bai B. L., Li M., Soft Mater., 2014, 12, 230—236
[17]	Bai B. L., Wei J., Kummetha R. R., Ozaki Y., Wang H. T., Li M., Vib. Spectrosc., 2014, 73, 150—157
[18]	Bai B. L., Mao X. Y., Xi Z. H., Ma J., Lin X. L., Wang H. T., Li M., Liq. Cryst., 2014, 41, 214—221
[19]	Xue C., Jin S., Weng X., Ge J. J., Shen Z., Shen H., Graham M. J., Jeong K. U., Huang H., Zhang D., Guo M., Harris F. W., Cheng S. Z. D., Li C. Y., Zhu L., Chem. Mater., 2004, 16, 1014—1025
[20]	Bai B. L., Mao X. Y., Wei J., Wei Z. H., Li M., Sensors Actuat. B Chem., 2015, 211, 268—274
[21]	Pritam C., Krishnendu D., Kumar D. P., Langmuir,2017, 33, 4500—4510
[22]	Wang F. J., Hashimoto K., Tajima K., Adv. Mater., 2015, 27, 6014—6020
[23]	Ghosh S., Li X. Q., Stepanenko V., Wurthner F., Chem. Eur. J., 2008, 14, 11343—11357
[24]	Li H. M., Wang J., Ni Y. Z., Zhou Y. F., Yan D. Y., Acta Chim. Sinica, 2016, 74, 415—421
	(李惠梅, 王洁, 倪云洲, 周永丰, 颜德岳.化学学报, 2016, 74, 415—421)