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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

2015 Impact Factor: 1.043

Front. Chem. Sci. Eng.    2016, Vol. 10 Issue (4) : 552-561     DOI: 10.1007/s11705-016-1589-8
Synthesis and properties of novel organogelators functionalized with 5-iodo-1,2,3-triazole and azobenzene groups
Ziyan Li,Yaodong Huang(),Dongli Fan,Huimin Li,Shuxue Liu,Luyuan Wang
Key Laboratory of Systems Bioengineering (Ministry of Education), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
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Two series of 5-iodo-1,2,3-triazole derivatives containing azobenzene group(s) were synthesized and their gelling properties were tested. Those containing two azobenzene groups (B series) have better gelation performance than those containing one azobenzene group (A series). The microstructure of organogels and the driving force of gelation were investigated by scanning electron microscopy and 1H NMR, respectively. It was found that π-π stacking, van der Waals interaction, and dipole-dipole interaction were the main forces of gelation. All the tested organogels are photoresponsive and those from B series are smarter than that from A series. Henry δp-δh diagrams of compounds A1, A2, and B2 were constructed on the basis of their gelation performance and the Hansen solubility parameters of related solvents. The constructed Henry δp-δh diagrams can be used to estimate the behavior of three compounds in any untested solvent.

Keywords iodo triazole      azobenzene      photoresponsive organogel      gelator-solvent effect     
Corresponding Authors: Yaodong Huang   
Just Accepted Date: 19 August 2016   Online First Date: 14 November 2016    Issue Date: 29 November 2016
URL:     OR
Fig.1  Scheme 1Synthetic route for organogelators A1, A2, A3, B1, and B2

(a) DIPEA, CuI, NBS, THF, r. t., 20 h, ~60%; (b) DIPEA, CuI, NBS, THF, r. t., 28 h, ~50%

Solvent A1 A2 A3 B1 B2
Petroleum ether P 35 20 P P
Cyclohexane 30 25 15 PG 25
Hexane P 33 19 P P
Carbon tetrachloride 50 28 14 P 48
Methylene chloride S 60 16 25 4
Tetrahydrofuran PG PG 20 42 13
Ethyl acetate 20 17 8 PG 12
Chloroform S S 14 44 15
Acetone P P 47 PG Ins
Acetonitrile Ins Ins Ins Ins Ins
Dioxane P P 45 P 50
Pyridine PG PG 52 PG PG
Butyl alcohol PG PG PG 50 14
Isopropyl alcohol P P P Ins Ins
Methanol Ins Ins Ins Ins Ins
Ethanol Ins Ins Ins Ins Ins
Triethy lamine P P P P P
Benzene S S 8 50 30
Toluene PG PG 46 45 25
N,N-dimethylformamide P P P P P
Ethyl ether Ins Ins Ins 20 10
Carbon disulfide 42 36 12 11 3
1,2-dichloroethane 35 20 10 33 20
Chlorobenzene 28 15 8 40 13
Tab.1  Gelation properties of the five synthesized compounds a)
Fig.2  Scheme 2The structures of two control compounds C1 and C2
Fig.3  SEM images of xerogels of (a) A1/ethyl acetate, (b) A2/ethyl acetate, (c) A3/ethyl acetate, (d) A3/cyclohexane, (e) A3/chlorobenzene, (f) B2/methylene chloride, (g) B2/ethyl acetate, and (h) B2/n-butyl alcohol. The concentration of all the gels is 20 mg/mL
Fig.4  XRD patterns of xerogels from (a) A3/1,2-dicholoethane gel (20 mg/mL) and (b) B2/1,2-dicholoethane gel (20 mg/mL)
Fig.5  Temperature-dependent 1H NMR spectra of A3 in CDCl3 (10 mg/mL)
Fig.6  The phase transitions of A3/1,2-dichloroethane and B2/1,2-dichloroethane systems
Fig.7  UV spectra of the gel-sol and sol-gel transitions of A3/1,2-dichloroethane and B2/1,2-dichloroethane systems. The concentrations are 15 and 20 mg/mL for A3 gel and B2 gel, respectively. (a) A3/1,2-dichloroethane gel irradiated by ultraviolet light; (b) The subsequent sol of (a) irradiated by visible light; (c) B2/1,2-dichloroethane gel irradiated by ultraviolet light; (d) The subsequent sol of (c) irradiated by visible light
Solvent δd δp δh
Cyclohexane 16.7 0 0
Tetrachloromethane 16.9 0 0
1,2-Dichloroethane 18.1 5.3 4.1
?Ethyl acetate 15.2 5.3 9.2
Carbon disulfide 18.3 0 0
Chlorobenzene 18.9 4.3 2.1
Tetrahydrofuran 17.85 5.7 8.0
?Toluene 17.7 1.4 2
Dichlormethane 17.8 6.4 6.1
?Pyridine 19.5 8.8 5.9
Chloroform 17.9 3.1 5.7
Benzene 18.05 1 2
Dioxane 18.25 1.8 7.4
Butanol 16 5.7 15.8
Hexane 14.8 0 0
Acetonitrile 15.8 18.0 6.1
Methanol 15.2 12.3 22.3
Ethanol 15.8 8.8 19.5
Diethyl?ether 14.4 2.9 5.1
Dimethyl formamide 17.4 13.7 11.3
Acetone 15.5 10.4 7
Isopropanol 15.8 6.1 16.4
Tab.2  The Hansen solubility parameters of the solventsa)
Fig.8  The δp-δh diagrams for (a) A1, (b) A3, and (c) B2
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