CN115061320A - Electrochromic device with adjustable optical chiral signal and preparation method thereof - Google Patents
Electrochromic device with adjustable optical chiral signal and preparation method thereof Download PDFInfo
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
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Abstract
The invention provides an optical chiral signal adjustable electrochromic device and a preparation method thereof, belonging to the technical field of electrochromic. The electrochromic device comprises acid-responsive chiral molecules and a chiral amplification medium, wherein the chiral amplification medium comprises liquid crystal, and the acid-responsive chiral molecules are selected from one or more of formulas (1) to (3). The invention mixes the chiral amplification medium liquid crystal and the acid response chiral molecules together, changes the molecular configuration of the acid response chiral molecules by regulating and controlling the pH value of the system, induces the spiral structure of the liquid crystal molecules to change, realizes the generation and disappearance of CD and CPL signals by depending on the switch ring of the acid response chiral molecules, and has the advantages of low voltage, high contrast and high chiral signals.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to an electrochromism device with adjustable optical chiral signals and a preparation method thereof.
Background
The chiral illuminant system absorbs light at a specific wavelength, and the absorption degree and amplitude of the light are different for left-handed and right-handed circularly polarized lights, and the traveling mode of the left-handed and right-handed circularly polarized lights changes from the original circular mode to the elliptical mode with the passage of time, so that the elliptical polarized lights are generated by overlapping and superposing the left-handed and right-handed circularly polarized lights with different traveling speeds and amplitudes, and the characteristic is called Circular Dichroism (CD). On this basis, the phenomenon that the chiral luminescence system emits left-handed and right-handed circularly polarized light with difference is called Circular Polarized Luminescence (CPL). Circular dichroism can represent chiral structural information of a ground state of a compound, and circular polarized luminescence can represent chiral information of an excited state of the compound. The system with the CPL characteristic has wide application prospect in the fields of optical display, photoelectric devices, information storage and processing, biological probes, photocatalytic asymmetric synthesis and the like. The exploration and development of chiral luminescent systems with CPL characteristics has become one of the current research hotspots.
In recent years, electronically controlled CPL materials based on chiral liquid crystal systems have attracted much attention. By introducing a chiral dye into the liquid crystal solution, a chiral liquid crystal system having a highly oriented arrangement and a self-organized helical superstructure can be directly prepared, which can emit right-or left-handed circularly polarized fluorescence depending on the direction of rotation of the helical axis. The light-emitting principle is as follows: when the system is in the initial state, the CPL signal is provided, after a certain voltage is applied, the spiral state of the liquid crystal molecules such as the cholesteric liquid crystal is destroyed by the voltage, the CPL signal disappears, and after the power is cut off, the system returns to the initial state with the CPL signal. Briefly, the CPL signal is adjusted by controlling the arrangement state of liquid crystal molecules through switching on and off the materials. However, the turn-on voltage of such materials varies from 10V to 100V, and generally several tens of volts are required (see fig. 1), which directly results in the disadvantage of high energy consumption of the device, and with the increase of the cycle number, the helical structure of the liquid crystal molecule is damaged, so that the helical ability of the liquid crystal molecule is lost, and the cycle performance of the device is deteriorated (see fig. 2). How to reduce the control voltage and realize the effective improvement and regulation of the chiral luminescence performance is a major challenge in the field of chiral luminescence systems.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an electrochromic device with adjustable optical chiral signals and a preparation method thereof.
In order to achieve the purpose, the invention is specifically realized by the following technical scheme:
the invention provides an electrochromic device with adjustable optical chiral signals, which comprises acid-responsive chiral molecules and a chiral amplification medium, wherein the chiral amplification medium comprises liquid crystal, and the acid-responsive chiral molecules are selected from one or more of formulas (1) - (3);
in the formulae (1) to (3), R 1 、R 2 、R 3 And R 4 Independently selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 3 One of (1);
R 5 one selected from the group consisting of groups represented by formulas (4) to (19), wherein m and n are greater than or equal to 0;
R 6 to R 21 Independently selected from hydrogen, hydroxy, halogen, amino, C 1 -C 24 Alkyl radical, C 1 -C 24 Substituted alkyl, C 1 -C 24 Alkoxy radical, C 1 -C 24 Alkylamino radical, C 6 -C 24 Aryl radical, C containing both aromatic rings and alkanes 7 -C 24 (iii) any one of the groups in (iii).
In addition, the invention provides a preparation method of the electrochromic device with the adjustable optical chiral signal, which comprises the following steps:
s1, adding the acid response chiral molecules and the chiral amplification medium into a solvent for dissolving, and then removing the solvent to prepare a chiral amplification solution;
and S2, adding an electro-acid molecule and an electrolyte into the chiral amplification solution to prepare an electrochromic solution, and then assembling the electrochromic solution and a conductive substrate to prepare the electrochromic device.
Has the advantages that:
1. the invention mixes the chiral amplification medium liquid crystal and the acid response chiral molecules together, and the molecular configuration of the acid response chiral molecules changes by regulating the pH value of the system, such as adding acid-base solution or adding electro-acid molecules to generate protons and recycle protons under the drive of low voltage, i.e. the system is opened in an acid environment and closed in a neutral environment, and induces the spiral structure of the liquid crystal molecules to change, and the generation and disappearance of CD and CPL signals are realized by depending on the switch ring of the acid response chiral molecules, thereby having the advantages of low voltage, high contrast and high chiral signals.
2. The invention adjusts the key substituent on the molecules of the formulas (1) to (3), greatly improves the sensitivity to light, enhances the chiral signal, greatly improves the compatibility with liquid crystal molecules by grafting the substituent-long alkyl chain with the structure similar to that of liquid crystal, and is beneficial to forming a stable electrochromic system.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a diagram of a test of the turn-on voltage of an electrically controlled chiral liquid crystal system in the prior art;
FIG. 2 is a graph showing the results of the cycling stability of an electrically controlled chiral liquid crystal system in the prior art;
FIG. 3 is a diagram of the acid response mechanism of an acid-responsive chiral molecule according to an embodiment of the present invention;
FIG. 4 is a schematic diagram illustrating an amplification mechanism of a chiral signal after doping of acid-responsive chiral molecules and liquid crystal according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a switching mechanism of a chiral signal of an electrochromic device with adjustable optical chiral signals under the induction of an electrochromic molecule according to an embodiment of the present invention;
FIG. 6 is a schematic diagram of the change of the optical performance of the electrochromic device with adjustable optical chiral signals before and after being powered on according to the embodiment of the present invention;
FIG. 7 is a structural formula diagram of the acid-responsive chiral molecules M1-M5 of example 1 of the present invention;
FIG. 8 is a structural diagram of the electroluminescent molecules M6-M10 according to example 1 of the present invention;
FIG. 9 is a spectrum of M1 molecules in the visible region of example 1, wherein (a) is the spectrum of PL intensity and (b) is the spectrum of CPL signal;
FIG. 10 is a flowchart of the preparation of the electrochromic device with adjustable optical chiral signal according to embodiment 1 of the present invention;
FIG. 11 is a visible region spectrum of an optically chiral signal tunable electrochromic device according to embodiment 1 of the present invention, in which (a) is a visible region spectrum of a CD signal, (b) is a visible region spectrum of a CPL signal, and (c) is a visible region spectrum of PL intensity;
FIG. 12 is a structural formula diagram of the acid-responsive chiral molecules M11-M15 of example 2 of the present invention;
FIG. 13 is a graph showing the results of in-situ CV-fluorescence measurements of an electrochromic device with tunable optical chiral signals according to example 2 of the present invention;
FIG. 14 is a structural formula diagram of the acid responsive chiral molecule M11-M15 of example 3 of the present invention;
fig. 15 is a graph showing the measurement results of the cycle stability of the electrochromic device with adjustable optical chiral signals in example 3 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. In addition, the terms "comprising," "including," and "having" are intended to be non-limiting, i.e., other steps and other ingredients can be added that do not affect the results. Materials, equipment and reagents were all commercially available unless otherwise specified.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, volume fractions, and other numerical values used in the present invention are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
At present, a chiral liquid crystal system-based electrically-controlled Circularly Polarized Luminescence (CPL) material is widely concerned about due to the advantage of strong CPL signal, but the CPL material has the disadvantages of high starting voltage, high energy consumption, poor cycle performance and the like, fig. 1-2 respectively show the starting voltage and cycle performance of the electrically-controlled circularly-polarized luminescence material in the prior art, the starting voltage of the material usually needs dozens of volts (such as 60V), and the CPL signal can be significantly reduced after the cycle number exceeds 3.
Based on this, the laboratory in previous research attempted to solve many problems of liquid crystal molecules by introducing electrochromic materials. Electrochromism refers to a phenomenon in which a material undergoes an electrochemical redox reaction under an applied electrical stimulus to change its energy level state, and changes optical properties such as color, transmittance, reflectance, and the like. The corresponding material is called electrochromic material. At present, organic micromolecular electrochromic materials mainly comprise viologen, organic dyes, isophthalate, aniline, an electroacid-base and acid-base response dye composite system and the like. However, researches show that the CPL signal of the existing electrochromic system is low, the application requirements are not met, and the electrochromic material has the problem of poor compatibility with liquid crystal molecules, so that a device which stably emits light is difficult to obtain.
In order to solve the problems of low signal and poor compatibility between molecules of the prior electrochromic system CPL, the embodiment of the invention provides an electrochromic device with adjustable optical chiral signals, which comprises acid-responsive chiral molecules and a chiral amplification medium, wherein the chiral amplification medium comprises liquid crystal and is used for amplifying the chiral signals of the acid-responsive chiral molecules, and the acid-responsive chiral molecules are selected from one or more of formulas (1) to (3);
in the formulae (1) to (3), R 1 、R 2 、R 3 And R 4 Independently selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 3 One of (1);
R 5 one selected from the group consisting of groups represented by formulas (4) to (19), wherein m and n are greater than or equal to 0;
R 6 to R 21 Independently selected from hydrogen, hydroxy, halogen, amino, C 1 -C 24 Alkyl radical, C 1 -C 24 Substituted alkyl, C 1 -C 24 Alkoxy radical, C 1 -C 24 Alkylamino radical, C 6 -C 24 Aryl radical, C containing both aromatic rings and alkanes 7 -C 24 (iii) any one of the groups in (iii).
The preparation of the electrochromic device with adjustable optical chiral signals is realized by the coordination of the acid response chiral molecules and the liquid crystal molecules, and the optical chiral signals comprise Circular Dichroism (CD) signals and Circular Polarized Luminescence (CPL) signals. Specifically, the acid-responsive chiral molecules are doped into a chiral amplification medium containing liquid crystal to obtain an acid-responsive chiral system, and taking the structure shown in formula (1) as an example, the molecules have the common property of having a chiral site and a sensitive acid-responsive group, and the acid-responsive color change mechanism of the molecules is shown in fig. 3. Under the initial neutral environment, the acid response chiral molecules with the closed loop state have no CPL signal, after a small amount of trifluoroacetic acid is added into the system, the acid response chiral molecules can capture protons released in the environment, become an open loop mode, and the appearance shows that the color of a sample is changed from colorless to pink, the optical expression shows that a visible region CD spectrum has a peak at 500nm, and a levorotatory CPL signal (left-CPL) can be detected under the excitation of 410nm light; after a small amount of alkali is added, hydrogen atoms in the environment are neutralized, so that the molecules in the system return to the initial state, namely the color of the sample returns to be the same as the initial state, the visible light region has no CD signal, and the CPL signal disappears. After the acid-responsive chiral molecules are applied to a chiral color change system, the pH value of the system is regulated, for example, in order to facilitate repeated color change, the state of the acid-responsive chiral molecules can be reversibly controlled by adding the electrochromic acid molecules and electrically controlling the electrochromic acid molecules to generate protons or recover protons at an extremely low voltage (generally lower than 5V), so that the control voltage of the device can be remarkably reduced. Compared with the chiral molecule S-Flu-A synthesized in the early stage in the laboratory, the chiral molecule S-Flu-A has the advantages that the key substituent groups on the molecules in the formulas (1) to (3) are adjusted, the sensitivity to light is greatly improved, the chiral signal is enhanced to a certain extent, the compatibility with the liquid crystal molecule is greatly improved by grafting the substituent group-long alkyl chain with the structure similar to that of the liquid crystal, but the chiral molecule S-Flu-A generally needs acid with higher concentration to respond to in practical application.
In order to better meet the requirements of practical application, the invention further amplifies the signals of the acid response chiral molecules through the periodically arranged structure of the liquid crystal. Taking nematic liquid crystal as an example to explain the amplification mechanism of the chiral amplification medium (see fig. 4), when the acid-responsive chiral molecules of the present invention are doped into the nematic liquid crystal, the acid-responsive chiral molecules induce the nematic liquid crystal to form cholesteric liquid crystal, and the two molecules are mixed to form a helical structure through self-assembly. When a small amount of trifluoroacetic acid is added into the system, hydrogen ions can be combined with acid response chiral molecules to induce the chiral molecules to open the rings, so that the molecular conformation is changed, the Helical Twisting Power (HTP) value of the chiral molecules is changed, and the screw pitch of a liquid crystal main body is influenced, at the moment, under the same optical environment, the CD signal of a visible region of the system is 20 times that before doping, and the CPL signal under the excitation of 410nm light is 100 times that before doping; after a small amount of base is added, hydrogen atoms in the system are neutralized, so that the acid-responsive chiral molecules in the system are returned to the initial state. After the chiral amplification medium is doped, the chiral signal is greatly improved, so that the use concentration of the acid-responsive chiral molecules can be reduced.
The invention mixes the chiral amplification medium liquid crystal and the acid response chiral molecules together, changes the molecular configuration of the acid response chiral molecules by regulating and controlling the pH value of the system, realizes the generation and disappearance of CD and CPL signals by depending on the switch ring of the acid response chiral molecules, has the advantages of low voltage, high contrast and high chiral signals, and has wide application prospect in the future organic photoelectric field.
The liquid crystal is nematic liquid crystal, and can be selected from any one or more of 5CB, 7CB, 5CT, CB15, E48, 8OCB, SLC1717, E7, SLC7011-100, K15 and ZLI-1132.
In order to conveniently and repeatedly regulate a CPL signal of the device and greatly reduce the driving voltage, preferably, the electrochromic device further comprises an electrochromic molecule, wherein the electrochromic molecule is a p-phenylenediamine organic micromolecule, and the structural formula of the electrochromic molecule is shown as a formula (20);
in the formula (20), R 22 And R 23 Independently selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 3 One of (1);
R 24 to R 27 Independently selected from hydrogen, hydroxy, halogen, amino, C 1 -C 24 Alkyl radical, C 1 -C 24 Substituted alkyl, C 1 -C 24 Alkoxy radical, C 1 -C 24 Alkylamino radical, C 6 -C 24 Aryl radical, C containing both aromatic rings and alkanes 7 -C 24 (iii) any one of the groups (iii);
R 28 one selected from the group consisting of groups represented by formulas (21) to (31), wherein m and n are greater than or equal to 0;
the method for indirectly regulating the chiral organic small molecules by using an electric regulation method of the electro-acid molecules refers to that the Electron transfer is often accompanied with the synchronous migration of protons in the redox reaction (such as photosynthesis, respiration and the like) according to a Proton-Coupled Electron transfer (PCET) mechanism, and the switching characteristics of the acid response chiral molecules doped into the chiral amplification medium under the electro-redox of the electro-acid molecules are shown in fig. 5 (taking the structure shown in formula (1) as an example). Under the initial neutral environment, the electrochromic chiral molecules are in a closed loop state, no CD or CPL signal exists, when a proper positive voltage is applied to the system, one proton can be released by the oxidation of nitrogen in the electrochromic chiral molecules to generate strong acidity, meanwhile, the released proton can be captured by the surrounding acid response chiral molecules to generate an open loop mode of the acid response molecules, so that the HTP value of the liquid crystal is changed, the pitch of the liquid crystal body is influenced, an enhanced CD signal and a CPL signal are generated, and after the power supply is cut off, the acid response molecules can be maintained in the open loop mode. Then, when a proper negative voltage is applied to the system, the reduction of nitrogen in the electroluminescent acid molecules can withdraw a proton and return to a neutral environment, meanwhile, the surrounding acid-response chiral molecules can release the captured proton and return to the closed-loop mode of the acid-response molecules, the CPL signal disappears, and the screw pitch of the liquid crystal system returns to the initial state. The applied positive voltage ranges from +0.1 to +5V, the applied negative voltage ranges from-5 to-0.1V, and the turn-on voltage is significantly reduced. In addition, as the adopted chiral amplification medium is liquid crystal, in order to improve the compatibility of the electroluminescent acid molecules and the liquid crystal, the invention grafts the long alkyl chain on the structure of the electroluminescent acid molecules on the basis of p-phenylenediamine, compared with the p-phenylenediamine and the derivatives thereof existing in the prior art, the structure solves the problem of direct compatibility with the liquid crystal, thereby ensuring that the structure not only has the characteristic of proton coupling electron transfer, but also can improve the solubility of the structure. The better compatibility of the electro-acid molecules and the system can further reduce the driving voltage and improve the efficiency of the device.
Based on the principle of homogeneous phase solubility, preferably, the acid responds to R of the chiral molecule 5 Radicals and R of the electroluminescent molecules 28 M and n in the groups, namely the groups shown in formulas (4) - (19) and (21) - (31) are 1-10, so that the system stability is better realized, acid response chiral molecules and electroluminescent molecules are better compatible with liquid crystal, the coordination can be more effectively realized, the electron transfer is more efficient, and the chiral signals are more obvious.
Specifically, the structural formula of the acid-responsive chiral molecule is shown as formulas (M1) - (M5) or (M11) - (M20);
specifically, the structural formula of the electro-acid molecule is shown as formulas (M6) - (M10);
optionally, the electrochromic device further comprises an electrolyte comprising an inorganic metal salt containing a metal ion selected from one or more of Li, Na, K, Rb, Cs, Cu and Ag salts, an organic metal salt containing a metal ion, a tetraalkylammonium salt and/or an ionic liquid.
Optionally, the electrochromic device further comprises an auxiliary medium, wherein the auxiliary medium comprises a substance with a reducing property, and further comprises an electrolyte. The substance with reducing property is one or more of quinone compounds, carbonyl-containing compounds, nitro-containing compounds, metal salts or metal complexes, and specifically can be p-benzoquinone and hydroquinone. The auxiliary medium generates oxidation-reduction reaction in the charge-discharge process to play a role in balancing charges.
In the above added substance, the mass ratio of the acid-responsive chiral molecules to the chiral amplification medium is 0.001-0.5: 1, the molar ratio of the acid-responsive chiral molecules to the electro-acid molecules is 0.01-100: 1; the mass ratio of the acid-responsive chiral molecules to the electrolyte is 0.01-100: 1; the mass ratio of the acid-responsive chiral molecules to the auxiliary medium is 0.01-100: 1.
optionally, the electrochromic device further comprises a conductive substrate, such as ITO glass.
In addition, the embodiment of the invention provides a preparation method of the electrochromic device with the adjustable optical chiral signal, which comprises the following steps:
s1, adding the acid response chiral molecules and the chiral amplification medium into a solvent for dissolving, and then removing the solvent to prepare a chiral amplification solution; the mass ratio of the acid-responsive chiral molecules to the chiral amplification medium is 0.001-0.5: 1;
s2, adding an electro-acid molecule and an electrolyte into the chiral amplification solution to prepare an electrochromic solution, and then assembling the electrochromic solution and a conductive substrate to prepare an electrochromic device; the molar ratio of the acid-responsive chiral molecules to the electro-acid molecules is 0.01-100: 1; the mass ratio of the acid-responsive chiral molecules to the electrolyte is 0.01-100: 1.
the preparation method of the electrochromic device with the adjustable optical chiral signal has the same advantages as the electrochromic device with the adjustable optical chiral signal in the prior art, and the details are not repeated here.
The electrochromic device with the adjustable optical chiral signal, which is prepared by the invention, changes before and after being electrified as shown in figure 6, after a weak positive voltage (0.1V to 5V) is introduced, the electrochromic device changes from colorless to pink, strong CD and CPL signals are emitted, and after the voltage is removed, the color and the optical signals are kept unchanged. After a weak negative voltage (-5V to-0.1V) is introduced, the device returns to the original colorless state from pink, and the CD and CPL signals disappear.
Alternatively, in step S1, the solvent is usually a low boiling point solvent, such as acetonitrile, methanol, dichloromethane, chloroform, tetrahydrofuran, dimethyltetrahydrofuran, etc.
Optionally, in step S2, adding an electrogenic acid molecule, an electrolyte and an auxiliary agent to the chiral amplification solution, wherein the mass ratio of the acid-responsive chiral molecule to the auxiliary agent is 0.01-100: 1. the auxiliary medium comprises a substance with reducing property, and further can comprise electrolyte. The substance with reducing property is one or more of quinone compounds, carbonyl-containing compounds, nitro-containing compounds, metal salts or metal complexes. The auxiliary medium generates oxidation-reduction reaction in the charge-discharge process to play a role in balancing charges.
Optionally, in step S2, the conductive substrate has a thickness of 20nm to 500 μm.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer.
Example 1
In this example, the synthesized M1 to M5 molecules were used as acid-responsive chiral molecules, and the structural formulas thereof are shown in fig. 7, while the synthesized M5 to M10 molecules were used as electroluminescent molecules, and the structural formulas thereof are shown in fig. 8.
Taking M1 molecule as an example, the optical performance test is shown in FIG. 9, wherein R-Rhodol-A represents M1 molecule, R-Rhodol-A + Acid represents the addition of Acid to the system, and (a) the abscissa represents wavelength and the ordinate represents fluorescence intensity, and (b) the abscissa represents wavelength and the ordinate represents CPL signal intensity. In the Initial state (Initial), the M1 molecule has no chiral signal in the visible light band, and shows a peak at 550nm after acid stimulation (acid) (fig. 9 (a)), and the chiral signal of the M1 molecule disappears after the acid is neutralized by adding base, and returns to the Initial state. Therefore, the pH value can be electrically regulated, the state of molecules can be reversibly controlled, the CPL signal can be generated and disappeared, and the method has the advantages of low control voltage and good cycle stability. However, the CPL signal of the M1 molecule is low, according to 1 The reason for generating CPL by M1 molecules in H COSY spectrum is that efficient chiral conversion from a chiral center to a chromophore is realized through intramolecular interaction, but transition allowed by an electric dipole only can present weak anisotropic signals, so CPL signals are not high, and higher concentration is usually required in practical application, but the problem of precipitation easily occurs at high concentration. Therefore, in this embodiment, the liquid crystal display device is manufactured by mixing the liquid crystal display device with liquid crystalDoping to achieve a high CPL signal at low concentrations.
An electrochromic device with adjustable optical chiral signals is prepared on the basis of M1-M5 molecules, M6-M10 molecules and E7 liquid crystal. The specific preparation process is shown in fig. 10, and comprises the following steps:
s1, adding 2mg of acid-responsive chiral molecules and 800mg of E7 liquid crystal into 400mL of dichloromethane for dissolving, and removing the solvent by means of nitrogen blowing after complete dissolution to prepare a chiral amplification solution;
s2, adding 0.225mg of electrochromic acid molecules, 40.0mg of electrolyte and 15mg of auxiliary medium into the chiral amplification solution, wherein the electrolyte is tetrabutylammonium hexafluorophosphate, the auxiliary medium is p-benzoquinone and hydroquinone, the mass of the auxiliary medium is 5mg and 10mg respectively, so as to prepare electrochromic solution, and then taking 10 mu L of the electrochromic solution by using an injector, and injecting the 10 mu L of electrochromic solution into a commercial ITO liquid crystal cell with the thickness of 20 mu m by utilizing capillary action, so that the corresponding electrochromic device can be prepared.
Taking an electrochromic device with adjustable optical chiral signals prepared by matching M1 molecules and M6 molecules as an example, the mass ratio of the acid response chiral molecules M1 to the chiral amplification medium E7 liquid crystal is 0.0025: 1; the molar ratio of the acid response chiral molecule M1 to the electro-acid molecule M5 is 5: 1; the mass ratio of the acid response chiral molecule M1 to the electrolyte tetrabutylammonium hexafluorophosphate is 0.05: 1.
similarly, taking an electrochromic device with adjustable optical chiral signals prepared by matching M1 molecules and M6 molecules as an example, optical performance tests are performed on the device, including CD signal, CPL signal and fluorescence signal tests, and the results are shown in FIG. 11, wherein the abscissa is the wavelength, and the ordinate is the CD signal ((a) diagram), the CPL signal ((b) diagram) and the fluorescence intensity ((c) diagram) in sequence from left to right.
The operation process is illustrated by taking a CD signal test as an example: attaching conductive adhesive at two edges of an electrochromic device, connecting the electrochromic device with an electrochemical workstation by using a wire, then fixing the electrochromic device in a test slot of a circular dichroism spectrometer, carrying out a CD test (corresponding to a '0V' curve in figure 11) once when the electrochromic device is not electrified, and carrying out a CD test (corresponding to a '1.5V' curve in figure 11) for the second time after a positive voltage of 1.5V is introduced for 10S; after 1h, a reverse voltage (-1.2V) was applied to it for 30S and a third CD test was performed (corresponding to the "-1.2V" curve in FIG. 11).
As can be seen from the figure, the initial state of the device is a colorless transparent state, and there is no CD signal, CPL signal, or fluorescent signal in the visible light region. When a positive voltage (1.5V) was applied to it, the color of the device changed to pink with a distinct downward CD peak at 500nm with a shoulder at 550 nm; under the excitation of 410nm light, a CPL peak which is obvious and faces downwards is arranged at 600nm, and the light-emitting asymmetry factor g lum Can reach-0.1; under 365nm light excitation, a fluorescence emission signal is obvious at 600 nm. Meanwhile, when the applied voltage of the device is removed, the coloring state of the device can be maintained for more than 20 min. After that, a reverse voltage (-1.2V) stimulus was applied to it, the pink color faded quickly, and the spectrum also returned completely to the original state. The "color-fade" cycle can be repeated more than twenty thousand times without significant performance decay, with excellent cycle performance. Meanwhile, the device can continuously work for more than 120 days, and the service life is long.
The M2-M5 molecule has the electrochromic property with adjustable optical chiral signals similar to that of the M1 molecule, and the details are not repeated.
Example 2
In this example, synthesized molecules M11 to M15 were used as acid-responsive chiral molecules, and the structural formula thereof is shown in fig. 12.
The preparation of the electrochromic device with adjustable optical chiral signals based on M11-M15 and M6-M10 molecules and 5CB liquid crystal comprises the following steps:
s1, adding 2.5mg of acid-responsive chiral molecules and 900mg of 5CB liquid crystal into 300mL of acetonitrile for dissolving, and removing the solvent by means of nitrogen blowing after complete dissolution to prepare a chiral amplification solution;
s2, adding 44.0mg electrolyte and 18mg auxiliary media of 0.3mg of electro-acid molecules into the chiral amplification solution, wherein the electrolyte is tetrabutyl ammonium hexafluorophosphate, the auxiliary media are p-benzoquinone and hydroquinone, the mass of the electrolyte is 6mg and the mass of the auxiliary media are 12mg respectively, so as to prepare an electrochromic solution, then taking 10 mu L of the electrochromic solution by using an injector, and injecting the electrochromic solution into a commercial ITO liquid crystal cell with the thickness of 15 mu m by utilizing the capillary action, so as to prepare the corresponding electrochromic device.
Taking an electrochromic device with adjustable optical chiral signals prepared by matching M11 molecules and M9 molecules as an example, an in-situ CV-fluorescence combined test is carried out on the device, and the result is shown in FIG. 13, wherein the ordinate of the upper graph is fluorescence intensity, and the ordinate of the lower graph is current. The acid-responsive chiral molecule M11 has no electro-redox ability and no change in fluorescence intensity in the visible region, and the electroluminescent molecule M9 has reversible electro-redox ability but no change in fluorescence intensity in the visible region. When the chiral organic small molecule M11 and the electroluminescent acid molecule M9 coexist in a system, the fluorescence intensity of the system can be reversibly changed along with the oxidation-reduction of the electroluminescent acid molecule M9. Thus, M9 and M11 can cooperate to realize the switch of CPL signal. The device is tested for optical performance, and initially has no CD signal, CPL signal or fluorescent signal in the visible region. When a positive voltage (1.8V) was applied thereto, a CD signal, a CPL signal, and a fluorescence signal were observed. After that, a reverse voltage (-1.4V) stimulus was applied thereto, and the spectrum completely returned to the original state.
The M12-M15 molecule has the electrochromic property with adjustable optical chiral signals similar to that of the M11 molecule, and the details are not repeated.
Example 3
In this example, the synthesized M16-M20 molecules were used as acid-responsive chiral molecules, and the structural formula thereof is shown in fig. 14.
The electrochromic device with adjustable optical chiral signals is prepared on the basis of M16-M20 and M6-M10 molecules and SLC1717 liquid crystal, and comprises the following steps:
s1, adding 1.8mg of acid-responsive chiral molecules and 800mg of SLC1717 liquid crystal into 450mL of methanol for dissolving, and removing the solvent by means of nitrogen blowing after complete dissolution to prepare a chiral amplification solution;
s2, adding 0.25mg of electrochromic acid molecules, 40.0mg of electrolyte and 15mg of auxiliary media into the chiral amplification solution, wherein the electrolyte is tetrabutylammonium hexafluorophosphate, the auxiliary media are p-benzoquinone and hydroquinone, the mass of the auxiliary media is 5mg and 10mg respectively, so as to prepare electrochromic solution, and then taking 30 mu L of the electrochromic solution by using an injector, and injecting the electrochromic solution into a commercial ITO liquid crystal cell with the thickness of 50 mu m by utilizing capillary action, so that the corresponding electrochromic device can be prepared.
Taking an electrochromic device with adjustable optical chiral signals prepared by matching M16 molecules and M10 molecules as an example, the device is subjected to an optical performance test. The initial state of the device was a colorless transparent state, and when a positive voltage (1.4V) was applied thereto, the color of the device changed to pink; after that, a stimulus of a reverse voltage (-1.0V) was applied thereto, the pink color rapidly faded away, and the device returned to the original colorless state. After that, a reverse voltage (-1.4V) stimulus was applied thereto, and the spectrum completely returned to the original state. This "color-fade" cycle can be repeated more than two thousand times without significant performance decay (as shown in fig. 15), with excellent cycle stability.
The M17-M20 molecule has the electrochromic property with adjustable optical chiral signals similar to that of the M16 molecule, and the details are not repeated.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. An electrochromic device with adjustable optical chiral signals is characterized by comprising acid-responsive chiral molecules and a chiral amplification medium, wherein the chiral amplification medium comprises liquid crystals, and the acid-responsive chiral molecules are selected from one or more of formulas (1) to (3);
in the formulae (1) to (3), R 1 、R 2 、R 3 And R 4 Independently selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 3 One of (1);
R 5 one selected from the group consisting of the groups represented by the formulae (4) to (19), wherein m andn is greater than or equal to 0;
R 6 to R 21 Independently selected from hydrogen, hydroxy, halogen, amino, C 1 -C 24 Alkyl radical, C 1 -C 24 Substituted alkyl, C 1 -C 24 Alkoxy radical, C 1 -C 24 Alkylamino radical, C 6 -C 24 Aryl radical, C containing both aromatic rings and alkanes 7 -C 24 (iii) any one of the groups in (iii).
2. The electrochromic device according to claim 1, wherein the acid-responsive chiral molecule has a structural formula as shown in formulas (M1) - (M5) or (M11) - (M20);
3. electrochromic device according to claim 1 or 2, characterized in that the liquid crystal is a nematic liquid crystal.
4. Electrochromic device according to claim 1 or 2, characterised in that the mass ratio of the acid-responsive chiral molecules and the chiral amplifying medium is 0.001-0.5: 1.
5. the electrochromic device according to claim 1 or 2, further comprising an electrochromic acid molecule having a structural formula shown in formula (20);
in the formula (20), R 22 And R 23 Independently selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 3 One of (1);
R 24 to R 27 Independently selected from hydrogen, hydroxy, halogen, amino, C 1 -C 24 Alkyl radical, C 1 -C 24 Substituted alkyl, C 1 -C 24 Alkoxy radical, C 1 -C 24 Alkylamino radical, C 6 -C 24 Aryl radical, C containing both aromatic rings and alkanes 7 -C 24 (iii) any one of the groups (iii);
R 28 one selected from the group consisting of groups represented by formulas (21) to (31), wherein m and n are greater than or equal to 0;
6. the electrochromic device according to claim 5, wherein the structural formula of the electroactive molecule is as shown in formulas (M6) - (M10);
7. the electrochromic device according to claim 5, wherein the molar ratio of said acid-responsive chiral molecules to said electroactive molecules is from 0.01 to 100: 1.
8. electrochromic device according to claim 1 or 2, characterized in that it further comprises an electrolyte and an auxiliary medium;
the electrolyte comprises inorganic metal salts containing metal ions, organic metal salts containing metal ions, quaternary tetraalkylammonium salts and/or ionic liquid, wherein the metal ions are selected from one or more of Li, Na, K, Rb, Cs, Cu and Ag salts;
the auxiliary medium comprises a substance with reduction property, and the substance with reduction property is one or more of quinone compounds, compounds containing carbonyl groups, compounds containing nitro groups, metal salts and metal complexes.
9. The electrochromic device according to claim 8, wherein the mass ratio of the acid-responsive chiral molecule to the electrolyte is 0.01-100: 1; the mass ratio of the acid-responsive chiral molecules to the auxiliary medium is 0.01-100: 1.
10. a method for preparing an electrochromic device with adjustable optical chiral signals, which is used for preparing the electrochromic device with adjustable optical chiral signals as claimed in any one of claims 1 to 9, and comprises the following steps:
s1, adding the acid response chiral molecules and the chiral amplification medium into a solvent for dissolving, and then removing the solvent to prepare a chiral amplification solution;
and S2, adding an electro-acid molecule and an electrolyte into the chiral amplification solution to prepare an electrochromic solution, and then assembling the electrochromic solution and a conductive substrate to prepare the electrochromic device.
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