WO2018127245A1 - 一种光响应三稳态手性分子材料及其制备方法和应用 - Google Patents

一种光响应三稳态手性分子材料及其制备方法和应用 Download PDF

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WO2018127245A1
WO2018127245A1 PCT/CN2018/076547 CN2018076547W WO2018127245A1 WO 2018127245 A1 WO2018127245 A1 WO 2018127245A1 CN 2018076547 W CN2018076547 W CN 2018076547W WO 2018127245 A1 WO2018127245 A1 WO 2018127245A1
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liquid crystal
chiral
group
tristable
light
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俞燕蕾
秦朗
韦嘉
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Fudan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/10—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems

Definitions

  • the invention belongs to the technical field of photoresponsive materials, and in particular relates to a photoresponsive tristable chiral molecular material and a preparation method and application thereof.
  • the periodic helical structure of the chiral nematic liquid crystal makes it selectively reflective and becomes a material that can produce a structural color.
  • the selective reflection of chiral nematic liquid crystals can be regulated by various external stimuli such as light, heat, electric field, and mechanical field.
  • external stimuli such as light, heat, electric field, and mechanical field.
  • light stimulation has the advantages of rapid response, remote and precise regulation, clean and pollution-free, and simple operation. Therefore, the development of photoreactive chiral nematic liquid crystal materials has become popular in recent years, and has great application prospects in the fields of color reflectors, color filter, tunable liquid crystal laser, and light-controlled flexible display.
  • the most common method for obtaining photoresponsive chiral nematic liquid crystals is to add a small amount of photoresponsive chiral molecules to the non-responsive nematic liquid crystal host.
  • the molecular chirality is amplified, and the liquid crystal host is induced to self-assemble to form a helical superstructure, that is, a chiral nematic liquid crystal.
  • the photo-reactive isomerization reaction of the photoreactive molecule changes its own configuration, so that the helical twisting force changes, and the pitch of the helical superstructure changes to achieve the purpose of regulating selective reflection.
  • existing photoresponsive chiral molecules are bistable and have only two stable configurations under illumination.
  • the bistable chiral molecule makes the chiral nematic liquid crystal selective reflection mode control mode single, only a single band, and the regulation range is generally narrow, which seriously hinders the development and practical application of photoreactive chiral nematic liquid crystal. .
  • the chiral molecule has two azobenzene structural units of different light-responsive properties, and three different stable configurations can be formed under the driving of three wavelengths of light.
  • Another object of the present invention is to provide an application of the above-described photoresponsive tristable chiral molecule, which is applied to the field of optics, particularly in the fields of display, sensor, anti-counterfeiting and the like.
  • the object of the present invention is achieved by a photoresponsive tristable chiral molecular material having azobenzene structural units having two different photoresponsive properties, the structural formula of which is:
  • the X is selected from any one of the following structural types I;
  • Y and Z are each selected from one or more of the following structural types I or II, and the types of Y and Z cannot be the same:
  • type I -F, -Cl, -OCH 3 ;
  • Type II -H, -CH 3 .
  • the R 1 may be any one of the linking groups, preferably one or more of the following structural formulas:
  • n is an integer from 1-12.
  • the R 2 is H or is selected from C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 hydrocarbyl or alkane.
  • An oxy group, or a terminal group having a polarity selected from the group consisting of a cyano group, an isocyano group, a hydroxyl group, a halogen group, an ester group (-COOC 1 -C 12 alkyl group), a carboxyl group (-COOH), a nitro group
  • the photoresponsive tristable chiral molecular material of the present invention after being dissolved in a solvent or a liquid crystal, is driven by three wavelengths of light to form a tristable state that can be reversibly changed.
  • the solvent is one or a mixture of several organic solvents, and may be selected from, but not limited to, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane. Ethyl acetate, methanol, ethanol, toluene or N,N-dimethylformamide.
  • the liquid crystal is a single crystal or a mixed crystal of a nematic phase or a smectic phase, and may be selected from, but not limited to, p-pentylbenzonitrile, p-heptylbenzonitrile or p-octylbenzonitrile.
  • the preferred embodiment of the liquid crystal is mixed crystal E7.
  • the three wavelengths of light are any one of 300-400 nanometers, any of 400-480 nanometers, any of 500-560 nanometers or 600-650 nanometers.
  • the binaphthylazobenzene structure was synthesized by diazotization-coupling reaction with binaphthyldiamine, and then the X-structured azobenzene and binaphthylazobenzene were massaged under argon gas (2 -3): 1 is dissolved in an organic solvent, and a target chiral molecule is obtained by a coupling reaction;
  • an azobenzene containing a Y structure and a Z structure is prepared by a diazotization-coupling reaction, respectively, and then an azobenzene containing a Z structure and a binaphthyl molar ratio (2-3) are first protected under argon gas.
  • ): 1 is dissolved in an organic solvent and coupled with binaphthene by a coupling reaction, and then the azobenzene containing the Y structure is dissolved in an organic solvent with a molar ratio of the above product (2-3):1, and a coupling reaction is carried out.
  • the photoresponsive tristable chiral molecule prepared by the invention is dissolved in a solvent or a liquid crystal, and is driven by three wavelengths of light to form a tristable state capable of reversible change.
  • the solvent involved is one or a mixture of organic solvents, which may be selected from, but not limited to, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane, ethyl acetate. Methanol, ethanol, toluene or N,N-dimethylformamide.
  • the liquid crystal involved is a single crystal or a mixed crystal of a nematic phase or a smectic phase, and may be selected from, but not limited to, p-butyl benzonitrile, p-heptyl benzonitrile or p-octyl benzonitrile.
  • the prepared photo-responsive tristable chiral molecule and the liquid crystal are uniformly mixed, and then poured into a liquid crystal cell, and the three-wavelength optical radiation can be used to realize the segmental regulation of the reflected light band of the liquid crystal cell.
  • a preferred embodiment of the liquid crystal involved is mixed crystal E7.
  • the three wavelengths of light are any one of 300-400 nanometers, any of 400-480 nanometers, any of 500-560 nanometers or 600-650 nanometers.
  • the photoresponsive tristable chiral molecular material provided by the present invention can be applied to the field of optics, especially in the fields of display, sensor, anti-counterfeiting and the like.
  • An advantage of the present invention is that the present invention connects two different photoresponsive properties of azobenzene structural units to a chiral center, making the chiral molecule tristable, with three stable configurations, breaking through
  • the limitation of the bistable chiral molecule is a novel photoresponsive chiral molecular material; at the same time, the chiral molecular material obtained by the invention is uniformly mixed with the liquid crystal and then poured into the liquid crystal cell, and the reflection can be realized by using three wavelengths of light.
  • the segmental regulation of the optical band breaks through the limitations of the original bistable chiral molecular single regulation band.
  • Figure 1 is a chart showing the ultraviolet-visible absorption spectrum in Example 2 of the present invention.
  • Fig. 2 is a photograph of a polarizing microscope in Example 3 of the present invention.
  • Figure 3 is a reflection spectrum diagram of Example 4 of the present invention.
  • Fig. 4 shows three states of the cholesteric liquid crystal formed by the chiral molecule of the present invention and liquid crystal.
  • Figure 5 shows three configurations of the chiral molecules of the invention.
  • Fig. 6 shows the results of imaging with a mask after mixing the chiral molecules of the present invention and liquid crystals.
  • Figure 7 illustrates that the chiral molecules of the present invention have good fatigue resistance in liquid crystals.
  • Figure 8 shows the color change process of the chiral molecules of the present invention mixed with liquid crystals in a liquid crystal cell or in a capillary.
  • Figure 9 shows the change in wavelength of the chiral molecule of the present invention after mixing with a liquid crystal.
  • the chiral molecule of the present invention also referred to as the tristable chiral molecule of the present invention, has a structure represented by Formula 1 or Formula 2, which has two azobenzene structural units having different light-responsive properties, in three Driven by a variety of wavelengths of light, three different stable configurations can be formed separately.
  • the chiral molecules of the present invention have tristable properties in both solution and liquid crystal, while reversible changes can occur under the driving of three wavelengths.
  • the tristable chiral molecules of the present invention undergo a change in configuration under illumination of light of different wavelengths. Taking a compound represented by Formula 1-1 as an example,
  • the chiral molecules and the liquid crystal are uniformly mixed to form a cholesteric liquid crystal, which is poured into a parallel-oriented liquid crystal cell.
  • the spiral direction of the cholesteric liquid crystal is perpendicular to the plane of the liquid crystal cell.
  • the cholesteric The phase liquid crystal also has three states, State I, State II and State III, which also correspond to the configurations I, II and III of the chiral molecule, respectively.
  • the reflection wavelength change between State I and II falls within the visible range, and the reflection wavelength variation between State II and III falls in the near-infrared region. In this way, the cholesteric liquid crystal can display red, green, blue and black, as shown in FIG.
  • the chiral molecules of the present invention can be applied to the field of optics, especially in the fields of display, sensors, anti-counterfeiting and the like.
  • optics especially in the fields of display, sensors, anti-counterfeiting and the like.
  • the chiral molecules of the invention are dissolved in the liquid crystal, they are poured into the liquid crystal cell in parallel orientation, and the tristable nature of the chiral molecule can be used to realize the segmental regulation of the reflected light band of the liquid crystal cell, and break through the original bistable state.
  • a solution of 1.0 g of 1,1'-binaphthyl-2,2'-diamine and hydrochloric acid was added to the beaker, and the beaker was placed in an ice water bath.
  • 20 mL of a 4.1 g aqueous solution of sodium nitrite was added dropwise to the beaker, and stirring was continued for 3 hours to obtain a diazonium salt solution.
  • a separate beaker 3.8 g of phenol, 5.0 g of sodium hydroxide and 30 mL of an aqueous solution were added, stirred and dissolved, and the beaker was placed in an ice water bath.
  • the prepared diazonium salt solution was added dropwise to the system, stirring was continued for 2 hours, and then stirred at room temperature for 1 hour.
  • the pH was adjusted to be acidic, the reaction solution was filtered, and the filter cake was washed with distilled water to give a crude product which was crystallized from methanol to give product.
  • Step (4) synthesis of the target compound, adding 2.0 g to a three-necked flask
  • the chiral molecule prepared in Example 1 was dissolved in a dichloromethane solution, and its absorption spectrum was measured by ultraviolet-visible absorption spectrometry at room temperature under 530 nm green light, 470 nm blue light, and 365 nm ultraviolet light. The change.
  • the test results are shown in Figure 1.
  • the absorption spectra are different under different wavelengths of light. Under the green light of 530 nm, the absorption peak of 350 nm is in the middle position; under the ultraviolet light of 365 nm, the absorption peak of 350 nm is the lowest; under the blue light of 470 nm, the absorption peak of 350 nm is the highest. It is indicated that the chiral molecule prepared has three steady states in solution.
  • the chiral molecule prepared in Example 1 was mixed with the mixed liquid crystal E7 and uniformly poured into a wedge box, and the wedge box was irradiated with 530 nm green light, 470 nm blue light, and 365 nm ultraviolet light at room temperature. The width between the defect lines was observed using a polarizing microscope, and the value of the spiral twisting force was calculated.
  • the test results are shown in Figure 2.
  • the values of the spiral twisting force are different under different wavelengths of light. Under the green light of 530 nm, the spiral twisting force is 112 ⁇ m -1 ; under the ultraviolet light of 365 nm, the spiral twisting force is 36 ⁇ m -1 ; and under the blue light of 470 nm, the spiral twisting force is 160 ⁇ m -1 . It is indicated that the chiral molecules prepared have three steady states in the liquid crystal.
  • Example 1 The chiral molecule prepared in Example 1 was mixed with the mixed liquid crystal E7 and uniformly poured into a wedge box. At room temperature, a wedge box was used with 530 nm green light, 470 nm blue light, and 365 nm ultraviolet light. The cycle irradiation was performed, and the width between the defect lines was observed using a polarizing microscope, and the value of the spiral twist force was calculated.
  • Example 1 The chiral molecule prepared in Example 1 was mixed with the mixed liquid crystal E7 uniformly and poured into a parallel-oriented liquid crystal cell or a capillary tube, and at room temperature, a green light of 530 nm and a blue light of 470 nm were used for the liquid crystal cell. Irradiation was performed, and the change in the reflected color was observed using a polarizing microscope.
  • Example 1 the chiral molecule prepared in Example 1 and the mixed liquid crystal E7 were uniformly mixed and poured into a parallel-oriented liquid crystal cell, and the liquid crystal cell was irradiated with 530 nm green light and 365 nm ultraviolet light at room temperature. The position of the reflection peak was detected using a reflectance spectrometer.
  • the chiral molecule prepared in Example 1 was mixed with the mixed liquid crystal E7 and uniformly poured into a parallel-oriented liquid crystal cell, and the liquid crystal cell was irradiated with 530 nm green light, 470 nm blue light, and 365 nm ultraviolet light at room temperature. Irradiation, using a reflectance spectrometer to detect the position of the reflection peak.
  • the test results are shown in Figure 3.
  • the use of 530 nm green light and 470 nm blue light can adjust the reflection wavelength of the liquid crystal cell (440-670 nm) in the visible light range; 365 nm UV light and 530 nm green light can be in the near infrared
  • the optical band adjusts the reflection wavelength of the liquid crystal cell (670-2100 nm). It is indicated that the segmentation regulation of the reflected light band of the liquid crystal cell can be realized by utilizing the properties of the tristable state of the chiral molecule prepared.
  • Example 1 The chiral molecules prepared in Example 1 were mixed with the mixed liquid crystal E7 and uniformly poured into a parallel-oriented liquid crystal cell. The liquid crystal cell was irradiated with green light of 530 nm to obtain a desired color, and then 365 nm ultraviolet light was used. The liquid crystal cell was irradiated through a mask to observe the color change.

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Abstract

本发明属于光响应材料技术领域，具体为一种光响应三稳态手性分子材料及其制备方法和应用。本发明提供的手性分子具有两个不同光响应性质的偶氮苯结构单元，在三种波长光的驱动下，能够分别形成三种不同的稳定构型。本发明的手性分子在溶液和液晶中均具有三稳态性质，同时在三种波长的驱动下可发生可逆变化。本发明的手性分子在液晶中溶解后，灌入平行取向的液晶盒中，利用手性分子三稳态的性质，可实现液晶盒反射光波段的分段调控，突破了原有双稳态手性分子单一调控波段的局限。本发明可应用于显示、传感器、防伪等众多领域。

Description

一种光响应三稳态手性分子材料及其制备方法和应用 技术领域
本发明属于光响应材料技术领域，具体涉及一种光响应三稳态手性分子材料及其制备方法和应用。
背景技术
手性向列相液晶周期性的螺旋结构使其具有选择性反射的特点，成为可以产生结构色的材料。手性向列相液晶的选择性反射可由光、热、电场、机械场等多种外界刺激调控。在众多外界刺激中，光刺激具有快速响应、可远程精确调控、清洁无污染、操作简单等优点。因此，光响应手性向列相液晶材料的研发近年来成为热门，在颜色反射器、变色滤镜、可调控液晶激光、光控柔性显示等领域有巨大的应用前景。
目前获得光响应手性向列相液晶最常用的方法是：在非响应的向列相液晶主体中添加少量的光响应手性分子。分子手性被放大，诱导液晶主体自组装形成螺旋超结构，即手性向列相液晶。在特定波长光的照射下，光响应手性分子会发生异构化反应，改变自身的构型，从而使得螺旋扭曲力发生改变，螺旋超结构的螺距发生改变，达到调控选择性反射的目的。然而，现有的光响应手性分子都是双稳态，在光照下只具有两种稳定构型。双稳态的手性分子使得手性向列相液晶选择性反射的调控模式单一，仅为单波段，而且调控范围都普遍较窄，这严重阻碍了光响应手性向列相液晶的发展和实际应用。
发明内容
本发明的目的是提供一种光响应三稳态手性分子及其制备方法。该手性分子具有 两个不同光响应性质的偶氮苯结构单元，在三种波长光的驱动下，能够分别形成三种不同的稳定构型。
本发明的另一目的在于提供上述光响应三稳态手性分子的应用，应用于光学领域，特别是显示、传感器、防伪等领域。
本发明的目的是这样实现的：一种光响应三稳态手性分子材料，具有两种不同光响应性质的偶氮苯结构单元，其结构通式为：
Figure PCTCN2018076547-appb-000001
或者
Figure PCTCN2018076547-appb-000002
对于通式1，所述的X选自下列结构类型I中的任意一种；
对于通式2，所述的Y、Z分别选自下列结构类型I或II中的一种或几种，且Y和Z的类型不能相同：
其中，类型I：-F、-Cl、-OCH 3；
类型II：-H、-CH 3。
所述的R 1可以是任意一种连接基团，优选自以下结构通式中的一种或一种以上：
Figure PCTCN2018076547-appb-000003
其中：n为1-12的整数。
所述的R 2是H，或者是选择于C 1、C 2、C 3、C 4、C 5、C 6、C 7、C 8、C 9、C 10、C 11、C 12烃基或烷氧基，或者是具有极性的端基，该端基选自于氰基、异氰基、羟基、卤素、酯基(-COOC 1-C 12烷基)、羧基(-COOH)、硝基、氨基或酰胺基中的一种。
本发明的光响应三稳态手性分子材料溶解于溶剂或液晶后，在三种波长的光的驱动下，形成能够可逆变化的三稳态。
优选地，所述的溶剂是有机溶剂中的一种或者几种的混合，可以选择但不局限于二氯甲烷、三氯甲烷、四氯化碳、四氢呋喃、1,4-二氧六环，乙酸乙酯，甲醇，乙醇，甲苯或者N,N-二甲基甲酰胺。
优选地，所述的液晶是向列相或者近晶相的单晶或者混晶，可以选择但不局限于对戊基联苯氰，对庚基联苯氰或者对辛基联苯氰。所述的液晶优选方案为混晶E7。
优选地，所述的三种波长的光，分别为300-400纳米波段中的任意一段、400-480纳米波段中的任意一段、500-560纳米或600-650纳米波段中的任意一段。
本发明提供的上述三光响应三稳态手性分子材料的制备方法，分两种情形：
对于通式I，具体步骤如下：
Figure PCTCN2018076547-appb-000004
首先，用联萘二胺通过重氮化-偶联反应合成联萘偶氮苯结构，然后，在氩气保护下，将含X结构的偶氮苯与联萘偶氮苯按摩尔比(2-3)：1溶解在有机溶剂中，通过偶联反应得到目标手性分子；
对于通式II，具体步骤如下：
Figure PCTCN2018076547-appb-000005
首先，分别通过重氮化-偶联反应制备含有Y结构和Z结构的偶氮苯，然后，在氩气保护下，先将含有Z结构的偶氮苯与联萘按摩尔比(2-3)：1溶解在有机溶剂中通过偶联反应与联萘偶联，再将含有Y结构的偶氮苯与上述产物按摩尔比(2-3)：1溶解在有机溶剂中，通过偶联反应联得到目标手性分子。
本发明制备得到的光响应三稳态手性分子溶解于溶剂或液晶后，在三种波长光的驱动下，形成能够可逆变化的三稳态。涉及的溶剂是有机溶剂中的一种或者几种的混合，可以选择但不局限于二氯甲烷、三氯甲烷、四氯化碳、四氢呋喃、1,4-二氧六环，乙酸乙酯，甲醇，乙醇，甲苯或者N,N-二甲基甲酰胺。涉及的液晶是向列相或者近晶相的单晶或者混晶，可以选择但不局限于对戊基联苯氰，对庚基联苯氰或者对辛基联苯氰。
将制备得到的光响应三稳态手性分子与液晶混合均匀后，灌入液晶盒中，利用三种波长光辐射，可实现液晶盒反射光波段的分段调控。涉及的液晶优选方案为混晶E7。
所述的三种波长的光，分别为300-400纳米波段中的任意一段、400-480纳米波段中的任意一段、500-560纳米或600-650纳米波段中的任意一段。
基于上述特性，本发明提供的光响应三稳态手性分子材料可应用于光学领域，特别是显示、传感器、防伪等领域。
本发明的优势在于：本发明将两种不同光响应的性质的偶氮苯结构单元连接在一个手性中心上，使该手性分子变成三稳态，具有三个稳定构型，突破了以往双稳态手性分子的限制，是一种新型的光响应手性分子材料；同时本发明得到的手性分子材料与液晶混合均匀后灌入液晶盒，能够利用三种波长光实现其反射光波段的分段调控，突破了原有双稳态手性分子单一调控波段的局限。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
附图说明
图1为本发明实施例2中的紫外可见吸收光谱图。
图2为本发明实施例3中的偏光显微镜照片。
图3为本发明实施例4中的反射光谱图。
图4显示了本发明手性分子和液晶形成的胆甾相液晶具有的三个状态。
图5显示了本发明手性分子的三个构型。
图6显示了本发明手性分子和液晶混合后，利用掩模成像的结果。
图7说明本发明的手性分子在液晶中具有良好的抗疲劳性能。
图8显示了本发明的手性分子与液晶混合后在液晶盒中或毛细管中颜色变化过程。
图9显示了本发明的手性分子与液晶混合后波长的变化。
具体实施方式
本发明人通过广泛而深入的研究，首次意外地发现了一类光响应三稳态手性分子 化合物，其在三种波长光的驱动下，能够分别形成三种不同的稳定构型，且在三种波长的驱动下可发生可逆变化。在此基础上完成了本发明。
本发明的手性分子
本发明的手性分子，也称为本发明的三稳态手性分子，具有通式1或通式2所示的结构，其具有两个不同光响应性质的偶氮苯结构单元，在三种波长光的驱动下，能够分别形成三种不同的稳定构型。本发明的手性分子在溶液和液晶中均具有三稳态性质，同时在三种波长的驱动下可发生可逆变化。
本发明的三稳态手性分子在不同波长光的照射下构型会发生变化。以通式1-1所示的化合物为例，
Figure PCTCN2018076547-appb-000006
在530nm(绿)光的照射下，氟取代偶氮苯发生trans-cis异构化反应，而普通偶氮苯保持trans异构体，所以此时的手性分子对应构型II。在365nm(紫外)光的照射下，氟取代偶氮苯和普通偶氮苯均发生trans-cis异构化反应，此时的手性分子对应构型III。在470nm(蓝)光的照射下，氟取代偶氮苯和普通偶氮苯均发生cis-trans异构化反应，此时手性分子对应构型I。如图5所示。
将手性分子和液晶混合均匀后形成胆甾相液晶，灌入平行取向的液晶盒中，胆甾相液晶的螺旋方向垂直于液晶盒平面，由于手性分子具有三稳态，所以该胆甾相液晶也具有三个状态，State I，State II和State III，也分别对应手性分子的构型I，II和III。State I和II之间的反射波长变化落于可见光范围内，State II和III之间的反射波长变化落于近红外区域。这样，胆甾相液晶就能显示红绿蓝黑，如图4所示。
应用
本发明的手性分子可应用于光学领域，特别是显示、传感器、防伪等领域。例如，彩色电子书，光控液晶黑板，可擦写手写板；可调控波长滤镜，多重变色防伪编码等。
本发明的手性分子在液晶中溶解后，灌入平行取向的液晶盒中，利用手性分子三稳态的性质，可实现液晶盒反射光波段的分段调控，突破了原有双稳态手性分子单一调控波段的局限。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数是重量百分比和重量份数。
以下实施例中所用的实验材料和试剂如无特别说明均可从市售渠道获得。
实施例1
制备符合通式1-1结构的分子，如下图所示：
Figure PCTCN2018076547-appb-000007
步骤(1)
1-(4-溴-2,6-二氟苯基)-2-(2,6-二氟-4-(壬氧基)苯基)二氮烯的合成
Figure PCTCN2018076547-appb-000008
在圆底烧瓶中加入10g 4-溴-2,6-二氟苯胺和盐酸溶液，低温搅拌下向体系中加入亚硝酸钠3.3g的水溶液50mL，反应5h。加入3,5-二氟苯酚7.25g、氢氧化钠2g的水溶液60mL，调节pH为碱性，继续反应3h，然后在室温下搅拌1h。调节pH为酸 性后，将反应液过滤，滤饼用蒸馏水洗涤，得到中间产物。在圆底烧瓶中加入中间产物、2.9g 1-溴壬烷、3.1g碳酸钾和少量碘化钾，再加入30mL DMF搅拌溶解，油浴加热至130℃，反应12h。反应结束后，蒸去溶剂，以石油醚和二氯甲烷的混合溶剂为洗脱剂进行柱层析，再用甲醇重结晶后得到产物。
步骤(2)
(4'-((2,6-二氟-4-(壬氧基)苯基)二氮烯基)-3',5'-二氟-[1,1'-联苯基]-4-基)-甲醇的合成
Figure PCTCN2018076547-appb-000009
在三颈瓶中加入5g上步产物、2.6g 4-羟甲基苯硼酸和30mL甲苯溶液，搅拌溶解后加入碳酸钾6.8g水溶液50mL和相转移剂。在氩气保护下加入少量双三苯基磷二氯化钯。加热反应液至100℃，反应24h。反应结束后，蒸去溶剂，以乙酸乙酯为洗脱液进行柱层析后得到产物。
步骤(3)
4,4'-(-[1,1'-联二萘]-2,2'-二基二(二氮烯-2,1-二基))二苯酚的合成
Figure PCTCN2018076547-appb-000010
在烧杯中加入1.0g 1,1’-联萘-2,2’-二胺和盐酸溶液，将烧杯置于冰水浴中。向烧杯内滴加亚硝酸钠4.1g水溶液20mL，滴加完成后继续搅拌3h，得到重氮盐溶液。在另一烧杯中加入3.8g苯酚、5.0g氢氧化钠和30mL水溶液，搅拌溶解后将烧杯置于冰水浴中。将制备好的重氮盐溶液滴加到该体系中，继续搅拌2h，然后在室温下搅拌1h。调节pH为酸性，将反应液过滤，滤饼用蒸馏水洗涤，得到粗产物，用甲醇重结晶得到产物。
步骤(4)、目标化合物的合成，在三口烧瓶中加入2.0g
4,4'-(-[1,1'-联二萘]-2,2'-二基二(二氮烯-2,1-二基))二苯酚、6.0g三苯基膦和40mL THF溶液。在氩气保护下，滴加7.0g(4'-((2,6-二氟-4-(壬氧基)苯基)二氮烯基)-3',5'-二氟-[1,1'-二苯基]-4-基)甲醇和7.0g偶氮二甲酸二异丙酯的THF溶液40mL，升温至回流反应24h。反应结束后，用二氯甲烷和水萃取3次，取有机层用无水硫酸镁干燥，以石油醚为洗脱液进行柱层析得到产物。
实施例2
将实施例1中制备的手性分子溶解于二氯甲烷溶液中，在室温下，利用紫外可见吸收光谱仪检测其吸收光谱在530纳米的绿光、470纳米的蓝光、365纳米的紫外光照射下的变化。
测试结果如图1所示，在不同波长光的照射下，吸收光谱曲线各不相同。530纳米的绿光照射下，350纳米吸收峰处于中间位置；365纳米的紫外光照射下，350纳米吸收峰位置最低；470纳米的蓝光照射下，350纳米吸收峰位置最高。说明所制备的手性分子在溶液中具有三个稳态。
实施例3
将实施例1中制备的手性分子与混合液晶E7混合均匀后灌入楔形盒中，在室温下，用530纳米的绿光、470纳米的蓝光、365纳米的紫外光对楔形盒进行照射，使用偏光显微镜观察缺陷线之间的宽度，计算出螺旋扭曲力数值。
测试结果如图2所示，在不同波长光的照射下，螺旋扭曲力数值各不相同。530纳米的绿光照射下，螺旋扭曲力为112μm -1；365纳米的紫外光照射下，螺旋扭曲力为36μm -1；470纳米的蓝光照射下，螺旋扭曲力为160μm -1。说明所制备的手性分子在液晶中具有三个稳态。
实施例4
实验过程：将实施例1中制备的手性分子与混合液晶E7混合均匀后灌入楔形盒中，在室温下，用530纳米的绿光、470纳米的蓝光、365纳米的紫外光对楔形盒进行循环照射，使用偏光显微镜观察缺陷线之间的宽度，计算出螺旋扭曲力数值。
结果说明：测试结果如图7所示，在不同波长光的循环照射下，各稳态螺旋扭曲力数值依旧保持。530纳米的绿光照射下，螺旋扭曲力保持为112μm -1；365纳米的紫外光照射下，螺旋扭曲力保持为36μm -1；470纳米的蓝光照射下，螺旋扭曲力保持为160μm -1。说明所制备的手性分子在液晶中具有良好的抗疲劳性能。
实施例5
实验过程：将实施例1中制备的手性分子与混合液晶E7混合均匀后灌入平行取向的液晶盒中或者毛细管内，在室温下，用530纳米的绿光、470纳米的蓝光对液晶盒进行照射，使用偏光显微镜观察反射颜色的变化。
结果说明：测试结果如图8所示。530纳米的绿光照射下(80mW cm -2)，液晶盒反射颜色在7秒后由蓝变绿，23秒再变红，如图8a所示；470纳米的蓝光照射下(40mW cm -2)，液晶盒反射颜色在5秒后又由红变绿，14秒后再变蓝，如图8b所示。而且，在毛细管内依然可以观察到这个变化过程，如图8c所示。
实施例6
实验过程：将实施例1中制备的手性分子与混合液晶E7混合均匀后灌入平行取向液晶盒中，在室温下，用530纳米的绿光、365纳米的紫外光对液晶盒进行照射，使用反射光谱仪检测反射峰位置。
结果说明：测试结果如图9所示。365纳米的紫外光照射下(3mW cm -2)，液晶 盒反射波长从670nm处发生红移，最终达到2100nm，如图9a所示；530纳米的蓝光照射下(20mW cm -2)，液晶盒反射波长从2100nm处发生蓝移，最终达到670nm，如图9b所示。
实施例7
将实施例1中制备的手性分子与混合液晶E7混合均匀后灌入平行取向液晶盒中，在室温下，用530纳米的绿光、470纳米的蓝光、365纳米的紫外光对液晶盒进行照射，使用反射光谱仪检测反射峰位置。
测试结果如图3所示，使用530纳米的绿光和470纳米的蓝光能够在可见光波段调节液晶盒的反射波长(440-670nm)；365纳米的紫外光和530纳米的绿光能够在近红外光波段调节液晶盒的反射波长(670-2100nm)。说明利用所制备手性分子三稳态的性质，可实现液晶盒反射光波段的分段调控。
实施例8
实验过程：将实施例1中制备的手性分子与混合液晶E7混合均匀后灌入平行取向液晶盒中，先用530nm的绿光照射液晶盒使其达到想要的颜色，再用365nm紫外光通过掩膜版照射液晶盒，观察其颜色变化。
结果表明：当用80mW cm -2的绿光照射25秒后，再用5mW cm -2的紫外光透过形状为2017的掩膜版进行照射30秒，液晶盒上显示红色2017图案；当用80mW cm -2的绿光照射10秒后，再用5mW cm -2的紫外光透过形状为NATURE的掩膜版进行照射30秒，液晶盒上显示绿色NATURE图案；当用80mW cm -2的绿光照射2秒后，再用5mW cm -2的紫外光透过形状为CLC的掩膜版进行照射30秒，液晶盒上显示蓝色CLC图案；当用80mW cm -2的绿光依次对液晶盒从左往右照射2秒、10秒、25 秒后，再用5mW cm -2的紫外光透过形状为FDU的掩膜版进行照射30秒，液晶盒上显示红绿蓝FDU图案。如图6所示。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (11)

  1. 一种光响应三稳态手性分子材料，其特征在于，该手性分子具有两种不同光响应性质的偶氮苯结构单元，其结构通式为：
    Figure PCTCN2018076547-appb-100001
    或者
    Figure PCTCN2018076547-appb-100002
    对于通式1，所述的X选自下列结构类型I中的任意一种；
    对于通式2，所述的Y、Z分别选自下列结构类型I或II中的一种或几种，且Y和Z的类型不能相同：
    其中，类型I：-F、-Cl、-OCH 3；
    类型II：-H、-CH 3；
    所述的R 1是任意一种连接基团；
    所述的R 2是H，或者是选择于C 1、C 2、C 3、C 4、C 5、C 6、C 7、C 8、C 9、C 10、C 11、C 12烃基或烷氧基，或者是具有极性的端基，该端基选自于氰基、异氰基、羟基、卤素、酯基(-COOC 1-C 12烷基)、羧基(-COOH)、硝基、氨基或酰胺基中的一种。
  2. 根据权利要求1所述三光响应三稳态手性分子材料，其特征在于，所述的R 1选自以下结构通式中的一种或一种以上：
    Figure PCTCN2018076547-appb-100003
    其中：n为1-12的整数。
  3. 根据权利要求1所述三光响应三稳态手性分子材料，其特征在于，所述光响应三稳态手性分子溶解于溶剂或液晶后，在三种波长光的驱动下，形成能够可逆变化的三稳态。
  4. 根据权利要求1所述三光响应三稳态手性分子材料，其特征在于，所述的三种波长的光，分别为300-400纳米波段中的任意一段、400-480纳米波段中的任意一段、500-560纳米或600-650纳米波段中的任意一段。
  5. 一种如权利要求1所述三光响应三稳态手性分子材料的制备方法，其特征在于，对于通式I，具体步骤如下：
    Figure PCTCN2018076547-appb-100004
    首先，用联萘二胺通过重氮化-偶联反应合成联萘偶氮苯结构，然后，在氩气保护下，将含X结构的偶氮苯与联萘偶氮苯按摩尔比(2-3)：1溶解在有机溶剂中，通过偶联反应得到目标手性分子。
  6. 一种如权利要求1所述三光响应三稳态手性分子材料的制备方法，其特征在于，对于通式II，具体步骤如下：
    Figure PCTCN2018076547-appb-100005
    首先，分别通过重氮化-偶联反应制备含有Y结构和Z结构的偶氮苯，然后，在氩气保护下，先将含有Z结构的偶氮苯与联萘按摩尔比(2-3)：1溶解在有机溶剂中通过偶联反应与联萘偶联，再将含有Y结构的偶氮苯与上述产物按摩尔比(2-3)：1溶解在有机溶剂中，通过偶联反应联得到目标手性分子。
  7. 如权利要求1所述三光响应三稳态手性分子材料在显示、传感器、防伪领域的应用。
  8. 如权利要求7所述的应用，其特征在于，用于彩色电子书，光控液晶黑板，可擦写手写板；可调控波长滤镜，多重变色防伪编码。
  9. 一种液晶盒反射光波段的分段调控的方法，其特征在于，包括步骤：将权利要求1所述的光响应三稳态手性分子材料与液晶混合均匀后，灌入液晶盒中，利用三种波长光辐射，实现液晶盒反射光波段的分段调控。
  10. 如权利要求9所述的方法，其特征在于，所述的液晶为混晶E7。
  11. 如权利要求9所述的方法，其特征在于，所述的三种波长的光，分别为300-400纳米波段中的任意一段、400-480纳米波段中的任意一段、500-560纳米或600-650纳米波段中的任意一段。
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