CN115557934A - Viologen electrochromic material from yellow to green based on viologen derivative and preparation method and application thereof - Google Patents
Viologen electrochromic material from yellow to green based on viologen derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a viologen electrochromic material from yellow to green based on viologen derivatives, a preparation method and application thereof; the preparation method comprises the steps of firstly preparing 3, 6-dibromo-9- (4-nitrophenyl) carbazole, preparing 3, 6-dibromo-9- (4-aminophenyl) carbazole by using the carbazole, further obtaining 1- (2, 4-dinitrophenyl) -4,4' -bipyridine salt and 1-benzyl-1 ' - (2, 4-dinitrophenyl) -4,4' -bipyridine salt, dissolving 3, 6-dibromo-9- (4-aminophenyl) carbazole and the obtained 1-benzyl-1 ' - (2, 4-dinitrophenyl) -4,4' -bipyridine salt, heating and refluxing under inert atmosphere, purifying to obtain a primary product, and adding ammonium hexafluorophosphate to obtain a target product. The invention realizes the conversion of yellow green by introducing benzyl bromide and 3, 6-dibromocarbazole groups. The manufactured electrochromic device has low driving voltage, short response time and good cycle stability.
Description
Technical Field
The invention relates to an electrochromic material, in particular to a viologen electrochromic material from yellow to green based on viologen derivatives, a preparation method and application thereof, belonging to the technical field of photoelectric materials.
Background
Electrochromic materials refer to a class of materials that undergo a reversible color change upon application of an externally applied voltage. These materials can be applied to electrochromic devices (e.g., energy-saving smart windows, anti-glare rear view mirrors, low power displays, military camouflage materials, etc.). The electrochromic technology is a new industrialized technology, has wide application field and has huge market application prospect.
The heart of electrochromic technology is where it is the electrochromic material that plays the role of color change. Viologen is one of a plurality of electrochromic materials, and belongs to organic electrochromic materials. The electrochromic material based on the viologen derivative has the advantages of low driving voltage, high contrast, convenient assembly of an electrochromic device and the like, so the viologen derivative is widely concerned in the electrochromic field. Achieving fast, stable and reversible switching between yellow and green is a challenge for electrochromic materials. This is mainly due to the fact that achieving electrochromic switching between yellow and green in one material requires that the electrochromic material has absorption peaks at two different wavelength positions.
Chinese patent application 201910834430.6 discloses a preparation method and application of a yellow-to-green quick-response electrochromic film. The invention utilizes the color changing effect of the tungsten oxide film or the molybdenum oxide film to compound the yellow background, and realizes the conversion of yellow and green through the compound color development principle. The yellow background is obtained by depositing the gold film, so that the cost of the electrochromic device is increased; and the electrochromic device related to the technology needs to use a propylene carbonate electrolyte, and the electrolyte leaks under the bending state, which means that the technology cannot be applied to flexible devices. This limits the application of the material in the camouflage field.
Chinese invention patent application 201910460297.2 discloses an electrochromic material of viologen derivatives and a preparation method thereof. According to the invention, through the introduction of electron-donating groups pyrrole and carbazole on the bipyridyl, the electron-deficient state of 4,4' -bipyridyl of the core group of the viologen compound is improved, the electrochromic driving voltage is reduced, and the problem that the electrolyte of a solution type electrochromic device is easy to leak is solved; however, because the electrochromic material provided by the technology has a symmetrical structure and has a single absorption peak only near 700nm, the electrochromic material provided by the technology cannot realize yellow-green color change, so that the application of the material in the camouflage field is limited, and meanwhile, the electrochromic material provided by the technology has higher driving voltage (> 1.4V).
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a viologen electrochromic material which is based on viologen derivatives and can be applied to camouflage materials, has yellow-green color change, quick response and good stability, and a preparation method thereof.
The invention also aims to provide application of the viologen electrochromic material from yellow to green based on the viologen derivative in preparing camouflage materials.
The purpose of the invention is realized by the following technical scheme:
a viologen electrochromic material from yellow to green based on viologen derivatives, characterized by the following molecular structural formula (A):
the preparation method of the viologen electrochromic material from yellow to green based on the viologen derivative comprises the following steps:
(1) Dissolving 3, 6-dibromocarbazole, parafluoronitrobenzene and potassium carbonate in DMSO, stirring at room temperature, and heating and refluxing at 120-140 ℃; after the reaction is finished, 3, 6-dibromo-9- (4-nitrophenyl) carbazole is obtained through a purification process;
(2) 3, 6-dibromo-9- (4-nitrophenyl) carbazole, stannous chloride and ethanol are uniformly mixed and refluxed for 20 to 30 hours at a temperature of between 70 and 80 ℃; after the reaction is finished, 3, 6-dibromo-9- (4-aminophenyl) carbazole is obtained through a purification process;
(3) Uniformly mixing 4,4' -bipyridyl, 1-chloro-2, 4-dinitrobenzene and acetonitrile, and heating and refluxing; cooling to room temperature after reaction, separating out a precipitate, and filtering to obtain the precipitate; washing with dichloromethane to obtain 1- (2, 4-dinitrophenyl) -4,4' -bipyridine salt;
(4) Uniformly mixing the obtained 1- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt, benzyl bromide and ethanol, and heating and refluxing; cooling to room temperature after reaction, precipitating, and filtering to obtain a precipitate; washing to obtain 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt;
(5) Dissolving the obtained 3, 6-dibromo-9- (4-aminophenyl) carbazole and the obtained 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt, and heating and refluxing under an inert atmosphere; cooling to room temperature, and filtering to obtain precipitate; washing the precipitate to obtain a crude product; dissolving the crude product, and adding ammonium hexafluorophosphate; stirring at room temperature, filtering, washing with water to obtain viologen derivative electrochromic material of the molecular structural formula (A).
To further achieve the object of the present invention, preferably, in step (1), the molar ratio of the 3, 6-dibromocarbazole to the p-fluoronitrobenzene to the potassium carbonate is 1: 1.2-1.5: 1.5, adding 10 ml-20 ml of DMSO into each gram of 3, 6-dibromocarbazole.
Preferably, in the step (1), the precipitate is washed 3 to 5 times by water and 3 to 5 times by ethanol; the time of heating reflux at 120-140 ℃ after stirring at room temperature is 24-36 hours.
Preferably, in the step (2), the molar ratio of the 3, 6-dibromo-9- (4-nitrophenyl) carbazole to the stannous chloride is 1:4 to 5; 30ml to 40ml of ethanol is added into each gram of 3, 6-dibromo-9- (4-nitrophenyl) carbazole; the purification process comprises the steps of removing a solvent by rotary evaporation after the reaction is finished, dissolving residual solids in dichloromethane, extracting the solution by using a sodium hydroxide solution and a sodium carbonate solution respectively, and removing the solvent by rotary evaporation; passing through silica gel column chromatography with ethyl acetate or petroleum ether.
Preferably, the concentration of the sodium hydroxide solution is 2M-3M, and the sodium carbonate solution is a saturated solution; the silica gel column is carried out in a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1:3.
preferably, in the step (3), the molar ratio of the 4,4' -bipyridyl to the 1-chloro-2, 4-dinitrobenzene is 1:0.5 to 1:0.8; adding 20 ml-30 ml of acetonitrile into each gram of 4,4' -bipyridyl; the heating reflux time is 20-24 h.
Preferably, in the step (4), the molar ratio of the 1- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt to the benzyl bromide is 1:1.5 to 2; adding 20ml to 30ml of ethanol into each gram of 4,4' -bipyridyl; the heating reflux time is 20-24 h; the washing is to wash the precipitate with dichloromethane.
Preferably, in the step (5), the molar ratio of the 3, 6-dibromo-9- (4-aminobenzene) carbazole to the 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt is 1: 1.5-2, adding 30-40 ml of ethanol into each gram of 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt; the molar ratio of the crude product to ammonium hexafluorophosphate is 1:10 to 20; the time of heating reflux in the inert atmosphere is 12-15 h; the stirring time at room temperature is 3-4h; the washing precipitate is washed by dichloromethane, and the crude product is dissolved in methanol; the 3, 6-dibromo-9- (4-aminophenyl) carbazole and the obtained 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt are dissolved in ethanol.
The viologen electrochromic material from yellow to green based on the viologen derivative is applied to the preparation of camouflage materials.
Compared with the prior art, the invention has the following advantages:
1) The invention forms the asymmetric disubstituted viologen derivative by introducing 3, 6-dibromo carbazole and benzyl bromide, enriches the color change of the viologen derivative and realizes the yellow-green color change in one material. Compared with the Chinese patent application 201910834430.6, the electrochromic device has the advantages that a gold film does not need to be deposited to serve as a yellow background, and the cost of the electrochromic device is reduced. And the color-changing active material exists in the form of gel, and is more suitable for flexible devices compared with propylene carbonate electrolyte in Chinese patent application 201910834430.6.
2) The viologen derivative designed by the invention can realize reversible color change of yellow and green, and can be applied to the field of camouflage materials. In the camouflage material, the viologen derivative designed by the invention can realize the conversion between yellow and green through the regulation and control of the applied voltage. In desert environments, the environment color is yellow, and the voltage can be adjusted to convert the material into yellow; in a forest environment, the environment color is green, and the voltage can be adjusted to convert the material into green, so that the purpose of camouflage is achieved.
3) According to the invention, the 3, 6-dibromocarbazole is added to form the disubstituted viologen derivative, and the 3, 6-dibromocarbazole can prevent dimerization of the disubstituted viologen derivative due to the steric hindrance effect and the electron-rich effect of the 3, 6-dibromocarbazole, so that the cycle stability of the electrochromic device is improved.
4) The invention solves the problem of easy leakage of the color-changing device by preparing the electrochromic gel, and leads the color-changing device to still keep excellent performance in a flexible device.
5) 3, 6-dibromo carbazole is introduced into the viologen derivative designed by the invention, the group has an electron-rich effect, the electron-deficient effect of 4, 4-bipyridine serving as a core group of the viologen compound can be effectively improved, the optical contrast is improved, and the driving voltage is reduced.
Drawings
FIG. 1 is a schematic diagram of the process for preparing an electrochromic device of the compound A obtained in example 1.
FIG. 2 is a schematic diagram of the color change of an electrochromic device of the compound A obtained in example 1.
FIG. 3 is the NMR spectrum of Compound A obtained in example 2.
FIG. 4 is a graph showing the response time of an electrochromic device of Compound A obtained in example 2.
FIG. 5 is the NMR spectrum of Compound A obtained in example 2.
FIG. 6 is a UV-Vis spectrum of an electrochromic device of Compound A obtained in example 3 at different voltages.
FIG. 7 is a UV-Vis spectrum of an electrochromic device of Compound A obtained in example 3 before and after bending.
Detailed Description
For better understanding of the present invention, the following examples are given for illustration, but the present invention is not limited thereto.
Test equipment used in the following examples: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, bruker, germany, origin; nuclear magnetic resonance spectrometer, specification AVANCE III HD400, bruker, germany, of origin; electrochemical workstation, model CHI750A, shanghai chenhua instruments of origin; the electrochromic device circulation tester is type II, and the Kjean of the producing area is a photoelectric technology company Limited; flexible bending tester, guangzhou Crystal Equipment Ltd of origin.
The method takes 4, 4-bipyridine as a raw material, and firstly generates 1- (2, 4-dinitrophenyl) -4,4' -bipyridine salt through a Menschutkin reaction with 1-chloro-2, 4-dinitrobenzene; 1- (2, 4-dinitrobenzene) -4,4' -bipyridyl salt reacts with benzyl bromide to generate 1-benzyl-1 ' - (2, 4-dinitrophenyl) -4,4' -bipyridyl salt; then 3, 6-dibromo-carbazole reacts with p-fluoronitrobenzene to generate 3, 6-dibromo-9- (4-nitrobenzene) carbazole, and then the 3, 6-dibromo-9- (4-nitrobenzene) carbazole is further reduced into 3, 6-dibromo-9- (4-aminobenzene) carbazole under the action of stannous chloride; finally, 3, 6-dibromo-9- (4-aminobenzene) carbazole and 1-benzyl-1 '- (2, 4-dinitrobenzene) -4,4' -bipyridyl salt are subjected to a Zincke reaction to obtain a target product, wherein the reaction equation is as follows:
the viologen derivative designed by the invention has the advantages that the color change performance is influenced by a substituent, and the viologen derivative has an active site and good designability. The viologen derivative realizes that the viologen electrochromic material is changed from yellow green through the control of the introduced group, and the introduced 3, 6-dibromocarbazole has an electron-rich effect, can effectively improve the electron-deficient effect of 4, 4-bipyridyl of the viologen compound core group, improves the optical contrast and reduces the driving voltage.
Example 1
A preparation method of viologen electrochromic material (A) from yellow to green, namely 1-benzyl-1 '- (4-dibromocarbazole) -4,4' -bipyridyl dihexafluorophosphate, comprises the following steps:
1) 3.3g of 3, 6-dibromocarbazole, 1.7g of p-fluoronitrobenzene, 2.1g of potassium carbonate and 33ml of DMSO were charged in a 100ml three-necked flask, stirred and reacted at an elevated temperature of 120 ℃ for 24 hours. After the reaction was completed, it was cooled to room temperature, poured into 200ml of deionized water and stirred, filtered and the precipitate was collected, and washed three times with deionized water and anhydrous ethanol, respectively, to obtain 3.2g of pale yellow solid with a yield of 71%.
MS：m/z＝445.91
1 H NMR(600MHz,DMSO)δ8.63(d,J＝2.0Hz,2H),8.51(d,J＝9.0Hz,2H),7.98(d,J＝9.0Hz,2H),7.65(dd,J＝8.8,2.1Hz,2H),7.50(d,J＝8.6Hz,2H).
2) 2.2g of 3, 6-dibromo-9- (4-nitrobenzene) carbazole, 3.8g of stannous chloride and 66ml of absolute ethanol are added into a 100ml three-neck flask, and the mixture is heated to 70 ℃ to react for 20 hours. After the reaction is finished, the mixture is cooled to room temperature, the organic solvent is removed by rotary evaporation of the mixed solution, then the mixture is dissolved by 50ml of dichloromethane, and the mixture is extracted by 2M sodium hydroxide solution and saturated sodium carbonate solution in sequence to obtain a crude product. Mixing petroleum ether and ethyl acetate in a volume ratio of 10:3 as eluent, the product was passed through a silica gel column to give a pale yellow solid with a yield of 61%.
MS：m/z＝415.93
1 H NMR(600MHz,DMSO)δ8.54(d,J＝2.0Hz,2H),7.56(dd,J＝8.8,2.1Hz,2H),7.20(dd,J＝13.9,8.7Hz,4H),6.81(d,J＝8.6Hz,2H),5.69(s,2H).
3) 1.6g of 4,4' -bipyridine, 1.0g of 1-chloro-2, 4-dinitrobenzene and 32ml of acetonitrile are added into a 100ml three-neck flask and heated and refluxed for 20 hours; after the reaction is finished, cooling the solution to room temperature, and filtering to obtain a precipitate; the precipitate was washed 3 times with dichloromethane to give a gray powder with 84% yield.
MS：m/z＝323.08
1 H NMR(600MHz,D 2 O)δ9.41(d,J＝2.5Hz,1H),9.27(d,J＝6.5Hz,2H),8.96(d,J＝6.2Hz,1H),8.84(s,2H),8.70(s,2H),8.31(s,1H),8.04(s,2H).
4) To a 250ml three-necked flask, 1.8g of 1- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt, 2.6g of benzyl bromide and 36ml of absolute ethanol were charged. The mixture was refluxed for 20 hours. After the reaction is finished, cooling to room temperature, and removing the organic solvent by rotary evaporation. The precipitate was washed 3 times with dichloromethane to give 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt in 85% yield.
MS：m/z＝207.07
1 H NMR(600MHz,DMSO)δ9.74–9.70(m,2H),9.65–9.61(m,2H),9.17(d,J＝2.4Hz,1H),9.09–9.05(m,2H),9.03(dd,J＝8.7,2.6Hz,1H),8.96–8.92(m,2H),8.48(d,J＝8.7Hz,1H),7.69–7.64(m,2H),7.49(dddd,J＝12.1,7.0,4.6,2.3Hz,3H),6.01(s,2H).
5) Into a 250ml three-necked flask were charged 2.6g of 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt, 3.1g of 3, 6-dibromo-9- (4-aminobenzene) carbazole and 60ml of anhydrous ethanol. The mixture was refluxed for 12 hours. After the reaction is finished, cooling to room temperature, and performing rotary evaporation to remove the organic solvent. The precipitate was washed 3 times with dichloromethane to give a precipitate, which was dissolved in an appropriate amount of methanol solvent, 15.1g ammonium hexafluorophosphate was added, stirred for 3 hours, filtered and washed three times with water to give the product as a pale red solid with a yield of 85%. Fig. 3 is a nuclear magnetic hydrogen spectrum of the electrochromic material (a), and it is apparent that the chemical shifts and the number of hydrogen atoms in the nuclear magnetic hydrogen spectrum are completely consistent with the structural formula of the electrochromic material (a), so the electrochromic material (a) is successfully obtained.
MS：m/z＝323.52
1 H NMR(600MHz,DMSO)δ9.85–9.76(m,2H),9.67–9.58(m,2H),9.04–8.99(m,2H),8.98–8.93(m,2H),8.67(d,J＝2.0Hz,2H),8.33–8.25(m,2H),8.17–8.10(m,2H),7.70(ddd,J＝9.6,8.3,1.6Hz,4H),7.52–7.47(m,3H),7.44(d,J＝8.8Hz,2H),6.03(s,2H).
13 C NMR(151MHz,DMSO)δ150.05,149.24,146.45,146.32,141.51,139.42,134.64,130.27,130.06,129.79,129.53,128.63,127.82,127.60,127.16,124.53,124.47,113.61,112.30,63.88.
Preparing a device: the gel-type flexible electrochromic device ECD1 is mainly prepared from a target product 1-benzyl-1 '- (4-dibromocarbazole) -4,4' -bipyridyl dihexafluorophosphate, and the structure of the device is PET-ITO film/electrochromic active layer/PET-ITO film. The preparation process of the device comprises the following steps:
1) Anhydrous perchloric acid tetra-n-butylamine, polymethyl methacrylate, propylene carbonate and an electrochromic compound 1-benzyl-1 '- (4-dibromocarbazole) -4,4' -bipyridine dihexafluorophosphate in a mass ratio of 3:5:95:1 and stirring for 4 hours at 45 ℃ to prepare uniform electrochromic gel.
2) Uniformly coating the electrochromic gel on a PET-ITO film, standing at 40 ℃ for 2 hours after uniform coating is ensured and no obvious bubbles exist, covering the film with another PET-ITO film, and sealing the two films by using an organic silicon sealant, wherein a manufacturing flow chart of a flexible device ECD1 is shown in figure 1.
And (3) testing the performance of the device:
1) And (3) testing the color change performance: when no voltage is applied, the electrochromic device is yellow, when-0.8V voltage is applied to the device, the electrochromic device is changed into cyan and is uniform in color change, and when-1.0V voltage is applied to the device, the electrochromic device is changed into green and is uniform in color change; when the voltage application was stopped, the electrochromic reverted to yellow, a digital photograph of the device ECD1 of figure 2 at different voltages.
2) And (3) response time testing: according to the response time of the timed transmittance test device, defining the time required by the transmittance change of 90% as the color change time, and testing the flexible device ECD1 to be colored for 0.9s; the fade time was 1.0s.
3) And (3) determining the cycling stability of the electrochromic device: the peak values of the chronoamperometry current at the time of coloring at-1.0V and at the time of fading at 0V were measured by the electrochemical workstation, and the results showed that the peak values of the chronoamperometry current of the electrochromic device did not change significantly after 2000 cycles.
4) Testing the flexibility of the electrochromic device: the transmittance curves of the electrochromic device are measured by an ultraviolet-visible spectrophotometer when the electrochromic device is colored at-1.0V and faded at 0V after being bent for multiple times, and the transmittance curve of the electrochromic device is not obviously changed after being bent for 1000 times.
Example 2
A preparation method of viologen electrochromic material (A) from yellow to green, namely 1-benzyl-1 '- (4-dibromocarbazole) -4,4' -bipyridyl dihexafluorophosphate, comprises the following steps:
1) Into a 100ml three-necked flask, 3.3g of 3, 6-dibromocarbazole, 1.9g of p-fluoronitrobenzene, 1.9g of potassium carbonate and 50ml of DMSO were charged, stirred and the temperature was raised to 130 ℃ to react for 30 hours. After the reaction was completed, it was cooled to room temperature, poured into 200ml of deionized water and stirred, filtered and the precipitate was collected, washed 4 times with deionized water and anhydrous ethanol, respectively, and vacuum-dried over a silica gel column with ethyl acetate-petroleum ether (1, 6, v/v) eluent to give a pale yellow solid in 75% yield.
MS：m/z＝445.91
1 H NMR(600MHz,DMSO)δ8.63(d,J＝2.0Hz,2H),8.51(d,J＝9.0Hz,2H),7.98(d,J＝9.0Hz,2H),7.65(dd,J＝8.8,2.1Hz,2H),7.50(d,J＝8.6Hz,2H).
2) 2.2g of 3, 6-dibromo-9- (4-nitrobenzene) carbazole, 4.2g of stannous chloride and 80ml of absolute ethanol were added into a 100ml three-necked flask, and the mixture was heated to 75 ℃ to react for 25 hours. After the reaction is finished, the mixture is cooled to room temperature, the organic solvent is removed by rotary evaporation of the mixed solution, then the mixture is dissolved by 50ml of dichloromethane, and the mixture is extracted by 3M sodium hydroxide solution and saturated sodium carbonate solution in sequence to obtain a crude product. Mixing petroleum ether and ethyl acetate at a volume ratio of 10:3 as eluent, and the product is passed through a silica gel column to obtain a light yellow solid with a yield of 70%.
MS：m/z＝415.93
1 H NMR(600MHz,DMSO)δ8.54(d,J＝2.0Hz,2H),7.56(dd,J＝8.8,2.1Hz,2H),7.20(dd,J＝13.9,8.7Hz,4H),6.81(d,J＝8.6Hz,2H),5.69(s,2H).
3) 1.6g of 4,4' -bipyridine, 1.3g of 1-chloro-2, 4-dinitrobenzene and 40ml of acetonitrile are added into a 100ml three-neck flask and heated and refluxed for 24 hours; after the reaction is finished, cooling the solution to room temperature, and filtering to obtain a precipitate; the precipitate was washed 3 times with dichloromethane to give the product 1- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt as a grey powder with a yield of 85%.
MS：m/z＝323.08
1 H NMR(600MHz,D 2 O)δ9.41(d,J＝2.5Hz,1H),9.27(d,J＝6.5Hz,2H),8.96(d,J＝6.2Hz,1H),8.84(s,2H),8.70(s,2H),8.31(s,1H),8.04(s,2H).
4) Into a 250ml three-necked flask were charged 1.8g of 1- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt, 2.0g of benzyl bromide and 42ml of absolute ethanol. The mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, and performing rotary evaporation to remove the organic solvent. The precipitate was washed 3 times with dichloromethane to give 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt in 83% yield.
MS：m/z＝207.07
1 H NMR(600MHz,DMSO)δ9.74–9.70(m,2H),9.65–9.61(m,2H),9.17(d,J＝2.4Hz,1H),9.09–9.05(m,2H),9.03(dd,J＝8.7,2.6Hz,1H),8.96–8.92(m,2H),8.48(d,J＝8.7Hz,1H),7.69–7.64(m,2H),7.49(dddd,J＝12.1,7.0,4.6,2.3Hz,3H),6.01(s,2H).
5) Into a 250ml three-necked flask were charged 2.6g of 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt, 3.6g of 3, 6-dibromo-9- (4-aminobenzene) carbazole and 80ml of anhydrous ethanol. The mixture was refluxed for 15 hours. After the reaction is finished, cooling to room temperature, and removing the organic solvent by rotary evaporation. The precipitate was washed 3 times with dichloromethane to give a precipitate, which was dissolved in an appropriate amount of methanol solvent, 15.1g ammonium hexafluorophosphate was added, stirred for 3 hours, filtered and washed three times with water to give a pale red solid product with a yield of 87%. Fig. 3 is a nuclear magnetic hydrogen spectrum of the electrochromic material (a), and it is apparent that the chemical shifts and the number of hydrogen atoms in the nuclear magnetic hydrogen spectrum are completely consistent with the structural formula of the electrochromic material (a), so the electrochromic material (a) is successfully obtained.
MS：m/z＝323.52
1 H NMR (600mhz, dmso) δ 9.85-9.76 (m, 2H), 9.67-9.58 (m, 2H), 9.04-8.99 (m, 2H), 8.98-8.93 (m, 2H), 8.67 (d, J =2.0hz, 2h), 8.33-8.25 (m, 2H), 8.17-8.10 (m, 2H), 7.70 (ddd, J =9.6,8.3,1.6hz, 4h), 7.52-7.47 (m, 3H), 7.44 (d, J =8.8hz, 2h), 6.03 (s, 2H) (fig. 3).
13 C NMR(151MHz,DMSO)δ150.05,149.24,146.45,146.32,141.51,139.42,134.64,130.27,130.06,129.79,129.53,128.63,127.82,127.60,127.16,124.53,124.47,113.61,112.30,63.88。
Preparing a device: a target product 1,1'- (4-dibromocarbazole) -4,4' -bipyridyl bis-hexafluorophosphate is mainly used for preparing a gel-type flexible electrochromic device ECD1, and the device has a structure of a PET-ITO film/an electrochromic active layer/a PET-ITO film. The preparation process of the device comprises the following steps:
1) Anhydrous perchloric acid tetra-n-butylamine, polymethyl methacrylate, propylene carbonate and an electrochromic compound 1,1'- (4-dibromocarbazole) -4,4' -bipyridyl dihexafluorophosphate in a mass ratio of 3:5:95:1 and stirring for 4 hours at 45 ℃ to prepare uniform electrochromic gel.
2) Uniformly coating the electrochromic gel on a PET-ITO film, standing at 45 ℃ for 2 hours after ensuring that the electrochromic gel is uniformly coated and has no obvious bubbles, covering the electrochromic gel with another PET-ITO film, and sealing the two films by using organic silicon sealant.
And (3) testing the performance of the device:
1) And (3) testing the color change performance: when no voltage is applied, the electrochromic device is yellow, when-0.8V voltage is applied to the device, the electrochromic device is changed into cyan and is uniform in color change, and when-1.0V voltage is applied to the device, the electrochromic device is changed into green and is uniform in color change; when the voltage application is stopped, the electrochromic reverts to yellow. As can be seen from the ultraviolet-visible spectrum of the device in the operation process, the device has higher transmittance to light with the wavelength range of 450nm to 780nm when no voltage is applied. When a voltage of-0.8 v was applied to the device, the transmittance of light in the wavelength range of 450nm to 780nm was significantly reduced. When a voltage of-1.4V was applied to the device, the transmittance of light in the wavelength range of 450nm to 780nm was further decreased. At 611nm, the transmittance difference of the device when no voltage is applied and-1.4V voltage is applied, namely the optical contrast reaches 70 percent,
2) Response time test: according to the response time of the timing transmittance testing device, defining the time required by the transmittance change of 90% as the color change time, and testing the coloring time of the flexible device ECD1 to be 0.9s; the fade time was 1.0s. Fig. 4 response time test results.
3) And (3) determining the cycling stability of the electrochromic device: the peak values of the chronoamperometry current of the electrochromic device at the time of coloring at-1.0V and at the time of fading at 0V were measured by the electrochemical workstation, and the result showed that the peak value of the chronoamperometry current of the electrochromic device was not significantly changed after 3500 cycles.
4) Testing the flexibility of the electrochromic device: the transmittance curves of the electrochromic device at-1.4V coloration and 0V discoloration after multiple bending were measured by an ultraviolet-visible spectrophotometer, and the results showed that the transmittance curve of the electrochromic device did not change significantly after 2000 repeated bending.
Example 3
A preparation method of viologen electrochromic material (A) from yellow to green, namely 1-benzyl-1 '- (4-dibromocarbazole) -4,4' -bipyridyl dihexafluorophosphate, comprises the following steps:
1) Into a 100ml three-necked flask were charged 3.3g of 3, 6-dibromocarbazole, 2.1g of p-fluoronitrobenzene, 2.1g of potassium carbonate and 66ml of DMSO, stirred and the temperature was raised to 140 ℃ for reaction for 36 hours. After the reaction was completed, it was cooled to room temperature, poured into 200ml of deionized water and stirred, filtered and the precipitate was collected, washed 5 times with deionized water and anhydrous ethanol, respectively, and vacuum-dried over a silica gel column chromatography with ethyl acetate-petroleum ether (1, 6, v/v) eluent to give a pale yellow solid in a yield of 79%.
MS：m/z＝445.91
1 H NMR(600MHz,DMSO)δ8.63(d,J＝2.0Hz,2H),8.51(d,J＝9.0Hz,2H),7.98(d,J＝9.0Hz,2H),7.65(dd,J＝8.8,2.1Hz,2H),7.50(d,J＝8.6Hz,2H).
2) 2.2g of 3, 6-dibromo-9- (4-nitrobenzene) carbazole, 4.7g of stannous chloride and 88ml of absolute ethanol were added into a 100ml three-necked flask, and the mixture was heated to 80 ℃ to react for 30 hours. After the reaction is finished, the mixture is cooled to room temperature, the organic solvent is removed by rotary evaporation of the mixed solution, then the mixture is dissolved by 50ml of dichloromethane, and a crude product is obtained by extracting the mixture by using a 3M sodium hydroxide solution and a saturated sodium carbonate solution in sequence. Mixing petroleum ether and ethyl acetate in a volume ratio of 10:3 as eluent, the product was passed through a silica gel column to give a pale yellow solid with 88% yield.
MS：m/z＝415.93
1 H NMR(600MHz,DMSO)δ8.54(d,J＝2.0Hz,2H),7.56(dd,J＝8.8,2.1Hz,2H),7.20(dd,J＝13.9,8.7Hz,4H),6.81(d,J＝8.6Hz,2H),5.69(s,2H).
3) 1.6g of 4,4' -bipyridine, 1.6g of 1-chloro-2, 4-dinitrobenzene and 48ml of acetonitrile are added into a 100ml three-neck flask and heated and refluxed for 24 hours; after the reaction is finished, cooling the solution to room temperature, and filtering to obtain a precipitate; the precipitate was washed 3 times with dichloromethane to give the product 1- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt as a grey powder in 87% yield.
MS：m/z＝323.08
1 H NMR(600MHz,D 2 O)δ9.41(d,J＝2.5Hz,1H),9.27(d,J＝6.5Hz,2H),8.96(d,J＝6.2Hz,1H),8.84(s,2H),8.70(s,2H),8.31(s,1H),8.04(s,2H).
4) Into a 250ml three-necked flask were charged 1.8g of 1- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt, 1.7g of benzyl bromide and 48ml of absolute ethanol. The mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, and removing the organic solvent by rotary evaporation. The precipitate was washed 3 times with dichloromethane to give 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt in 81% yield.
MS：m/z＝207.07
1 H NMR(600MHz,DMSO)δ9.74–9.70(m,2H),9.65–9.61(m,2H),9.17(d,J＝2.4Hz,1H),9.09–9.05(m,2H),9.03(dd,J＝8.7,2.6Hz,1H),8.96–8.92(m,2H),8.48(d,J＝8.7Hz,1H),7.69–7.64(m,2H),7.49(dddd,J＝12.1,7.0,4.6,2.3Hz,3H),6.01(s,2H).
5) To a 250ml three-necked flask, 2.6g of 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridinium salt, 4.1g of 3, 6-dibromo-9- (4-aminobenzene) carbazole and 100ml of absolute ethanol were charged. The mixture was refluxed for 15 hours. After the reaction is finished, cooling to room temperature, and removing the organic solvent by rotary evaporation. The precipitate was washed 3 times with dichloromethane to give a precipitate, which was dissolved in an appropriate amount of methanol solvent, 15.1g ammonium hexafluorophosphate was added, stirred for 3 hours, filtered and washed three times with water to give the product as a pale red solid with a yield of 89%. Fig. 3 is a nuclear magnetic hydrogen spectrum of the electrochromic material (a), and it is apparent that the chemical shifts and the number of hydrogen atoms in the nuclear magnetic hydrogen spectrum are completely consistent with the structural formula of the electrochromic material (a), so that the electrochromic material (a) is successfully obtained.
MS：m/z＝323.52
1 H NMR(600MHz,DMSO)δ9.85–9.76(m,2H),9.67–9.58(m,2H),9.04–8.99(m,2H),8.98–8.93(m,2H),8.67(d,J＝2.0Hz,2H),8.33–8.25(m,2H),8.17–8.10(m,2H),7.70(ddd,J＝9.6,8.3,1.6Hz,4H),7.52–7.47(m,3H),7.44(d,J＝8.8Hz,2H),6.03(s,2H).
13 C NMR (151MHz, DMSO). Delta.150.05, 149.24,146.45,146.32,141.51,139.42,134.64,130.27,130.06,129.79,129.53,128.63,127.82,127.60,127.16,124.53,124.47,113.61,112.30,63.88 (FIG. 5).
Preparing a device: a target product 1,1'- (4-dibromocarbazole) -4,4' -bipyridyl bis-hexafluorophosphate is mainly used for preparing a gel-type flexible electrochromic device ECD1, and the device has a structure of a PET-ITO film/an electrochromic active layer/a PET-ITO film. The preparation process of the device comprises the following steps:
1) Anhydrous perchloric acid tetra-n-butylamine, polymethyl methacrylate, propylene carbonate and an electrochromic compound 1,1'- (4-dibromocarbazole) -4,4' -bipyridyl dihexafluorophosphate in a mass ratio of 3:5:95:1 and stirring the mixture at 45 ℃ for 4 hours to prepare uniform electrochromic gel.
2) Uniformly coating the electrochromic gel on a PET-ITO film, standing at 45 ℃ for 2 hours after ensuring that the electrochromic gel is uniformly coated and has no obvious bubbles, covering the electrochromic gel with another PET-ITO film, and sealing the two films by using organic silicon sealant.
And (3) testing the performance of the device:
1) And (3) testing the color change performance: when no voltage is applied, the electrochromic device is yellow, when-0.8V voltage is applied to the device, the electrochromic device is changed into light green, the color change is uniform, and when-1.0V voltage is applied to the device, the electrochromic device is changed into green, the color change is uniform; when the voltage application is stopped, the electrochromic reverts to yellow. As can be seen from the ultraviolet-visible spectrum of the device in the operation process, the device has higher transmittance to light with the wavelength range of 450nm to 780nm when no voltage is applied. When a voltage of-0.8 v was applied to the device, the transmittance of light in the wavelength range of 450nm to 780nm was significantly reduced. When a voltage of-1.0 v was applied to the device, the transmittance of light in the wavelength range of 450nm to 780nm was further decreased. At 611nm, the transmittance difference of the device under the conditions of no voltage application and-1.0V voltage application, namely the optical contrast reaches 70%, and the flexible device ECD1 in FIG. 6 has a transmittance change spectrum under different driving voltages.
2) Response time test: according to the response time of the timed transmittance test device, defining the time required by the transmittance change of 90% as the color change time, and testing the flexible device ECD1 to be colored for 0.9s; the fading time was 1.0s.
3) And (3) determining the cycling stability of the electrochromic device: the peak values of the chronoamperometry current at the time of coloring at-1.0V and at the time of fading at 0V were measured by the electrochemical workstation, and the results showed that the peak values of the chronoamperometry current of the electrochromic device did not change significantly after 5000 cycles.
4) Testing the flexibility of the electrochromic device: the transmittance curves of the electrochromic device at-1.0V coloration and 0V discoloration after multiple bending were measured by an ultraviolet-visible spectrophotometer, and the results shown in fig. 7 show that the transmittance curve of the electrochromic device did not change significantly after 3000 repeated bending.
The electrochromic material realizes yellow-green color conversion by connecting different groups on two sides of bipyridyl to regulate and control color. The flexible electrochromic device is manufactured by taking the electrochromic material as an active material, and the device is of a sandwich structure, wherein the upper layer and the lower layer are PET-ITO films, and the middle layer is electrochromic gel. The electrochromic device has simple manufacturing process and easy regulation and control of the color of the device. Compared with the Chinese patent application 201910834430.6, the electrochromic material has yellow color, a gold film does not need to be deposited to serve as a yellow background, and the manufacturing cost of the device is reduced. The electrochromic device involved in the Chinese invention patent application 201910834430.6 needs a propylene carbonate electrolyte, so that the electrochromic device cannot be applied to a flexible device. The electrochromic device has good bending resistance, and still has obvious yellow-green color conversion in a bending state, so that technical support is provided for the application of the material in the field of camouflage.
Generally, benzyl is introduced to the other side of bipyridine to obtain an asymmetric viologen derivative, and different groups are introduced to two ends of viologen to adjust the optical energy gap of the viologen derivative, so that the viologen derivative has absorption peaks at different wavelength positions, the color change of the viologen-based electrochromic material is enriched, the material has yellow-green color change, and the viologen-based electrochromic material can be applied to the camouflage field. The electrochromic material improves the electron-deficient state of the viologen compound core group 4,4 '-bipyridyl and reduces the electrochromic voltage thereof by introducing 3, 6-dibromocarbazole into the 4,4' -bipyridyl. The stability of the electrochromic material formed by the 3, 6-dibromocarbazole is greatly improved due to the steric hindrance effect of the carbazole. Meanwhile, the method for realizing color regulation by connecting different groups at two ends of bipyridyl for structural modification provides an idea for subsequent color design.
Claims (10)
1. A viologen electrochromic material from yellow to green based on viologen derivatives, characterized by the following molecular structural formula (A):
2. the method for preparing a viologen electrochromic material from yellow to green based on viologen derivatives as claimed in claim 1, characterized by comprising the steps of:
(1) Dissolving 3, 6-dibromocarbazole, parafluoronitrobenzene and potassium carbonate in DMSO, stirring at room temperature, and heating and refluxing at 120-140 ℃; after the reaction is finished, 3, 6-dibromo-9- (4-nitrophenyl) carbazole is obtained through a purification process;
(2) 3, 6-dibromo-9- (4-nitrophenyl) carbazole, stannous chloride and ethanol are uniformly mixed and refluxed for 20 to 30 hours at a temperature of between 70 and 80 ℃; after the reaction is finished, 3, 6-dibromo-9- (4-aminophenyl) carbazole is obtained through a purification process;
(3) Uniformly mixing 4,4' -bipyridyl, 1-chloro-2, 4-dinitrobenzene and acetonitrile, and heating and refluxing; cooling to room temperature after reaction, precipitating, and filtering to obtain a precipitate; washing with dichloromethane to obtain 1- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt;
(4) Uniformly mixing the obtained 1- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt, benzyl bromide and ethanol, and heating and refluxing; cooling to room temperature after reaction, separating out a precipitate, and filtering to obtain the precipitate; washing to obtain 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt;
(5) Dissolving the obtained 3, 6-dibromo-9- (4-aminophenyl) carbazole and the obtained 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt, and heating and refluxing in an inert atmosphere; cooling to room temperature, and filtering to obtain precipitate; washing the precipitate to obtain a crude product; dissolving the crude product, and adding ammonium hexafluorophosphate; stirring at room temperature, filtering, and washing with water to obtain viologen derivative electrochromic material with molecular structural formula (A).
3. The method for preparing the viologen electrochromic material from yellow to green based on the viologen derivative as claimed in claim 2, wherein in the step (1), the molar ratio of the 3, 6-dibromocarbazole to the p-fluoronitrobenzene to the potassium carbonate is 1: 1.2-1.5: 1.5, adding 10 ml-20 ml of DMSO into each gram of 3, 6-dibromocarbazole.
4. The method for preparing the viologen electrochromic material from yellow to green based on the viologen derivative as claimed in claim 2, wherein in the step (1), the precipitate is washed 3 to 5 times with water and 3 to 5 times with ethanol; the time of heating reflux at 120-140 ℃ after stirring at room temperature is 24-36 hours.
5. The method for preparing a viologen electrochromic material from yellow to green based on the viologen derivative as claimed in claim 2, wherein in the step (2), the molar ratio of the 3, 6-dibromo-9- (4-nitrophenyl) carbazole to the stannous chloride is 1:4 to 5; 30ml to 40ml of ethanol is added into each gram of 3, 6-dibromo-9- (4-nitrophenyl) carbazole; the purification process comprises the steps of removing a solvent by rotary evaporation after the reaction is finished, dissolving residual solids in dichloromethane, extracting the solution by using a sodium hydroxide solution and a sodium carbonate solution respectively, and removing the solvent by rotary evaporation; passing through silica gel column chromatography with ethyl acetate or petroleum ether.
6. The method for preparing viologen electrochromic material from yellow to green based on viologen derivatives as claimed in claim 5, wherein the concentration of the sodium hydroxide solution is 2M to 3M, and the sodium carbonate solution is a saturated solution; the silica gel column is carried out in a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1:3.
7. the method for preparing viologen electrochromic material from yellow to green based on viologen derivatives as claimed in claim 2, wherein in the step (3), the molar ratio of 4,4' -bipyridine to 1-chloro-2, 4-dinitrobenzene is 1:0.5 to 1:0.8; adding 20ml to 30ml of acetonitrile into each gram of 4,4' -bipyridyl; the heating reflux time is 20-24 h.
8. The method for preparing a viologen-based viologen electrochromic material from yellow to green according to claim 2, wherein in the step (4), the molar ratio of the 1- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt to benzyl bromide is 1:1.5 to 2; adding 20ml to 30ml of ethanol into each gram of 4,4' -bipyridyl; the heating reflux time is 20-24 h; the washing is to wash the precipitate with dichloromethane.
9. The method for preparing a viologen-based viologen electrochromic material from yellow to green according to claim 2, wherein in the step (5), the molar ratio of the 3, 6-dibromo-9- (4-aminobenzene) carbazole to the 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt is 1: 1.5-2, adding 30-40 ml of ethanol into each gram of 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridyl salt; the molar ratio of the crude product to ammonium hexafluorophosphate is 1:10 to 20; the time of heating reflux in the inert atmosphere is 12-15 h; the stirring time at room temperature is 3-4h; the washing precipitate is washed by dichloromethane, and the crude product is dissolved in methanol; the 3, 6-dibromo-9- (4-aminophenyl) carbazole and the obtained 1-benzyl-1 '- (2, 4-dinitrophenyl) -4,4' -bipyridine salt are dissolved in ethanol.
10. Use of viologen electrochromic materials from yellow to green based on viologen derivatives as claimed in claim 1 for the preparation of camouflage materials.
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| CN110105336A (en) * | 2019-05-30 | 2019-08-09 | 华南理工大学 | Viologen derivative electrochromic material and preparation method thereof |
| CN114133380A (en) * | 2021-11-08 | 2022-03-04 | 华南理工大学 | Purpurin derivative electrochromism and electroluminescent photochromic material, and preparation method and application thereof |
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| CN114133380A (en) * | 2021-11-08 | 2022-03-04 | 华南理工大学 | Purpurin derivative electrochromism and electroluminescent photochromic material, and preparation method and application thereof |
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