Liquid Crystal Nanoparticles Containing Azobenzene：Synthesis， Supramolecular Structure and Their Applications in Light⁃Controlled Orientation

doi:10.19894/j.issn.1000-0518.210362

Chinese Journal of Applied Chemistry ›› 2021, Vol. 38 ›› Issue (10): 1353-1361.DOI: 10.19894/j.issn.1000-0518.210362

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Liquid Crystal Nanoparticles Containing Azobenzene：Synthesis， Supramolecular Structure and Their Applications in Light⁃Controlled Orientation

Yuan DENG^‡, Yao-Jian FAN^‡, Lei TAO, Zhi-Wang LUO, He-Lou XIE()

Key Lab of Environment-friendly Chemistry and Application in Ministry of Education，Universities of Hunan Province and College of Chemistry，Xiangtan University，Xiangtan 411105，China

Received:2021-07-26 Accepted:2021-09-01 Published:2021-10-01 Online:2021-10-15
Contact: He-Lou XIE
About author:He-lou@xtu.edu.cn
Supported by:
National Natural Science Foundation of China(21975215)

Abstract

Abstract:

A series of liquid crystal nanoparticles （LCNPs） contained azobenzene （denoted as Au@AzoC₆-n NPs （Sample number n=1~6）） with different sizes was successfully prepared by the two-phase Brust?Schiffrin method. The composition， phase behavior and supramolecular structure of LCNPs were characterized by proton nuclear magnetic rensonance ¹H NMR experiments， transmission electron microscopy （TEM）， thermogravimetric analyzer （TGA）， differential scanning calorimetry （DSC）， polarizing microscope （POM） and X-ray diffraction （XRD）. The results show that the sizes of the resultant LCNPs are in the range of 1.4（±0.1）~6.4（±0.3） nm. And LCNPs present excellent thermal stability. LCNPs with more azobenzene ligands grafted on the surface of the gold nanoparticles are correspondingly stacked into a supramolecular structure of layered phase， hexagonal columnar phase， and tetragonal columnar phase. Ultraviolet-visible （UV-Vis） absorption spectroscopy results show that LCNPs with larger diameter exhibit faster photoresponsibility. Furthermore， incorporating this kind of LCNPs into commercial liquid crystals can realize the light-controlled alignment of nematic liquid crystal molecules.

Key words: Azobenzene-containing liquid crystal nanoparticles, Supramolecular structure, Light-controlled alignment

CLC Number:

O631

Yuan DENG, Yao-Jian FAN, Lei TAO, Zhi-Wang LUO, He-Lou XIE. Liquid Crystal Nanoparticles Containing Azobenzene：Synthesis， Supramolecular Structure and Their Applications in Light⁃Controlled Orientation[J]. Chinese Journal of Applied Chemistry, 2021, 38(10): 1353-1361.

Figures/Tables 9

Fig.1 Synthetic route of Au@AzoC6

Table 1 Au@AzoC6?n prepared by different ratios of HAuCl4·3H2O and ligand AzoC6?SH

样品 Samples	30 mmol/L氯金酸溶液的体积 V（HAuCl₄）/mL	50 mmol/L四辛基溴化铵溶液的体积 V（TOAB）/mL	偶氮小分子配体用量 m（AzoC₆?SH）/mg	0.4 mol/L硼氢化钠的体积 V（NaBH₄）/mL
Au@AzoC₆?1	9	24	99	7.5
Au@AzoC₆?2	9	24	150	7.5
Au@AzoC₆?3	9	24	170	7.5
Au@AzoC₆?4	6	16	133	5.0
Au@AzoC₆?5	6	16	167	5.0
Au@AzoC₆?6	6	16	200	5.0

Fig.2 1H NMR spectra of the ligand AzoC6-SH and Au@AzoC6

Fig.3 （A） TEM images and （B） TGA curves of Au@AzoC6-n（n=1~6）

Table 2 Calculation results of Au@AzoC6?n（n=1~6）

样品Sample	Au@AzoC₆?1	Au@AzoC₆?2	Au@AzoC₆?3	Au@AzoC₆?4	Au@AzoC₆?5	Au@AzoC₆?6
粒径 Diameter/nm	1.4（±0.1）	2.2（±0.3）	2.7（±0.1）	3.2（±0.2）	4.1（±0.2）	6.4（±0.3）
金质量分数/% Mass fraction of Au/%	32.0	37.9	38.6	44.9	43.4	40.6
每个纳米粒子中金原子数目 Number of gold atoms per particle	84	327	605	1 008	2 121	8 069
每个纳米粒子中配体数目 Number of ligands per particle	96	287	515	662	1 482	6 312
每nm²的配体数目 Number of ligands per nm²	49	59	70	64	88	154

Fig.4 （A） DSC curves and （B） POM images （magnification 200 ×） of Au@AzoC6-n（n=1~6）

Fig.5 （A） 1D WAXD patterns of Au@AzoC6?n（n=1~6） at 30 ℃；（B） 2D Gi?WAXD patterns of Au@AzoC6?n（n=1~6）

Fig.6 UV-Vis spectra of Au@AzoC6-1 in solution after irradiated with 365 nm（A） and 470 nm（B） light for different times；（C） The relationship between the nanoparticles diameters and response time

Fig.7 POM diagrams of liquid crystal cells with different Au@AzoC6 concentrations in the initial state （A， B， C）， after ultraviolet irradiation （D， E， F）， and after visible light irradiation（G， H， I）

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Liquid Crystal Nanoparticles Containing Azobenzene：Synthesis， Supramolecular Structure and Their Applications in Light⁃Controlled Orientation

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