CN110105336B - Viologen derivative electrochromic material and preparation method thereof - Google Patents
Viologen derivative electrochromic material and preparation method thereof Download PDFInfo
- Publication number
- CN110105336B CN110105336B CN201910460297.2A CN201910460297A CN110105336B CN 110105336 B CN110105336 B CN 110105336B CN 201910460297 A CN201910460297 A CN 201910460297A CN 110105336 B CN110105336 B CN 110105336B
- Authority
- CN
- China
- Prior art keywords
- electrochromic material
- pyrrole
- carbazole
- electrochromic
- precipitate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention discloses an electrochromic material of viologen derivatives and a preparation method thereof; the preparation method takes 4,4' -bipyridyl as a raw material to react with 1-chloro-2, 4-dinitrobenzene through Menschutkin reaction to synthesize 1,1' -bis (2, 4-dinitro) -4,4' -bipyridyl salt; then preparing a 4-nitro compound by aromatic nucleophilic amination of the N-heterocyclic compound and p-fluoronitrobenzene, and reducing the 4-nitro compound into a 4-amino compound; and finally, carrying out a Zincke reaction on the product obtained in the second step to obtain a target product. The derivative introduces pyrrole groups and carbazole, improves the electron-deficient state on 4,4' -bipyridine of the core group of the viologen compound, and reduces the electrochromic voltage of the viologen compound; and the bipolar electrochromic device can be obtained, higher contrast is realized, multiple color changes are realized, and the problem of electrolyte leakage of the solution type electrochromic device can be solved.
Description
Technical Field
The invention relates to an electrochromic material, in particular to a viologen derivative serving as an electrochromic material and a preparation method thereof, belonging to the technical field of photoelectric materials.
Background
Electrochromism is a phenomenon in which a material undergoes a stable reversible change between a colored state and a decolored state by injecting or extracting charges (ions or electrons) under the action of an external electric field, and appears as a reversible change in color and transparency in appearance. The development and application of electrochromic technology has been changing people's lives since the 21 st century. The intelligent anti-dazzle mirror of the automobile enables people to drive more safely, the intelligent light-adjusting porthole of the airplane enables people to travel more comfortably, and the intelligent light-adjusting and heat-adjusting building window enables people to live more energy-saving. The electrochromic technology is an emerging industrialized technology, and has great potential application value due to wide application field.
In 1932, 1 '-dimethyl-4, 4' -bipyridinium salts were first found to be purple in color in the reduced state by Michaelis et al (Michaelis L, Hill E S.the virology indicators [ J ]. JGen Physiol,1933, 16: 859-.
Viologen compound (V)2+) Under the action of light excitation or applied electric field, electrons are driven from anions (such as Cl)-、Br-、I-、BF3-、PF6-) Transfer to bipyridine ring to generate viologen radical univalent cation (V)+That is, delocalization of photocharges on the bipyridyl ring results in radical cations having a high molar absorption coefficient in the visible region and exhibiting a deep color (Barna GG, Fish J. an enhanced electrochromism displaying using an asymmetrical vidogen [ J]J Electrochem Soc,1981,128: 1290-1292.). In neutral state (V)0) The viologen compound has no absorption in a visible light area of 400-800 nm and is colorless and transparent.
Chinese invention patent 2014101660916 discloses an electrochromic device comprising a first electrode and a second electrode opposite to the first electrode; an electrochromic layer on either the first or second electrode; and a dielectric layer disposed between the first and second electrodes; wherein the electrochromic layer on the first electrode comprises an electrochromic material; the electrochromic material is a viologen compound electrochromic material, in particular to a compound 1- (carbazole-N-hexyl) -1 '- (phosphonic acid-2-ethyl) -4,4' bipyridine dichloride; the second electrode includes a triphenylamine species. The novel electrochromic material synthesized by the technology utilizes a novel matching method and is prepared into electrochromic electrodes matched with each other, and the assembled electrochromic device is short in color changing time and high in transmittance difference. However, the electrolyte of the electrochromic device provided by the technology is liquid electrolyte, and the problem of leakage of the liquid electrolyte exists.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a novel viologen derivative which can be used as an electrochromic material and can obtain a bipolar electrochromic device and realize higher contrast, wherein pyrrole and carbazole are simultaneously introduced into the viologen derivative, so that the electron-deficient state of a viologen compound core group 4,4' -bipyridyl is improved, and the electrochromic voltage of the viologen compound is reduced; and the problem of electrolyte leakage of the solution type electrochromic device can be solved.
The reaction equation of the viologen derivative electrochromic material is as follows:
as can be seen from the reaction equation, the preparation method of the invention takes 4,4' -bipyridyl as a raw material to react with 1-chloro-2, 4-dinitrobenzene to synthesize 1,1' -bis (2, 4-dinitro) -4,4' -bipyridyl salt through Menschutkin reaction; then preparing a 4-nitro compound by aromatic nucleophilic amination of the N-heterocyclic compound and p-fluoronitrobenzene, and reducing the 4-nitro compound into a 4-amino compound; and finally, carrying out a Zincke reaction on the product obtained in the second step to obtain a target product.
The color of the viologen monocationic is related to the substituent, the design is good, and the electrochromic materials with different colors can be obtained by changing the structure of the substituent.
The viologen of the invention has good ability of accepting electrons, and the pyrrole and the carbazole have good ability of supplying electrons, and the interaction of the two can effectively improve the electrochromic performance of the electrochromic device after the two are connected together.
The purpose of the invention is realized by the following technical scheme:
the viologen derivative electrochromic material has the following molecular structural formula (A) or molecular structural formula (B):
the preparation method of the viologen derivative electrochromic material comprises the following steps:
the preparation method of the viologen derivative electrochromic material with the molecular structural formula (A) comprises the following steps:
1) mixing pyrrole, DMSO and K2CO3Mixing uniformly at N2Stirring at room temperature for 20-30 min under the atmosphere, adding parafluoronitrobenzene, and refluxing for 12-15 h at 100-105 ℃; after the reaction was completed, the solution was cooledCooling to room temperature, adding cold water, precipitating, and filtering; washing the precipitate with water and petroleum ether to obtain N- (4-nitrophenyl) pyrrole;
2) uniformly mixing the N- (4-nitrophenyl) pyrrole obtained in the step 1), Pd/C and ethanol, and carrying out N mixing at the temperature of 80-85 DEG C2Refluxing for 10-20 min in the atmosphere, adding hydrazine hydrate by using an injector, continuously reacting for 10-12 h, filtering while hot, and removing the solvent by rotary evaporation; passing dichloromethane through silica gel chromatographic column to obtain N- (4-aminophenyl) pyrrole;
3) uniformly mixing 4,4' -bipyridyl, 1-chloro-2, 4-dinitrobenzene and acetonitrile, and heating and refluxing for 40-48 h; cooling to room temperature, filtering to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain a white solid 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt;
4) dissolving the N- (4-aminophenyl) pyrrole obtained in the step 2) and the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt obtained in the step 3) in a proper amount of ethanol, and dissolving N2Heating and refluxing for 6-8 h under protection; cooling to room temperature, filtering to obtain crude product, recrystallizing with acetone, adding distilled water to the recrystallized product, and adding NH4PF6Stirring for 1-2 h for precipitation, filtering, washing with water, and drying to obtain the viologen derivative electrochromic material with the molecular structural formula (A);
the preparation method of the viologen derivative electrochromic material with the molecular structural formula (B) comprises the following steps:
(1) carbazole, dry DMSO, K2CO3Mixing in N2Stirring for 10-30 min at room temperature under the atmosphere, adding parafluoronitrobenzene, heating to 100-120 ℃, and heating and refluxing for 12-15 h; after the reaction is finished, cooling the solution to room temperature to obtain a crude product, and adding methanol for precipitation to obtain yellow crystal N- (4-nitrophenyl) carbazole;
(2) mixing the N- (4-nitrophenyl) carbazole, Pd/C and ethanol, N2Heating and refluxing in the atmosphere, slowly adding hydrazine hydrate, heating and refluxing for 10-12 h at the reflux temperature, cooling to room temperature, filtering, and distilling to remove the solvent; recrystallizing in petroleum ether to obtain N- (4-aminophenyl) carbazole;
(3) mixing 4,4' -bipyridine, 1-chloro-2, 4-dinitrobenzene and acetonitrile, and heating and refluxing for 40-48 h; cooling to room temperature, filtering to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain a white solid 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt;
(4) dissolving the N- (4-aminophenyl) carbazole obtained in the step 2) and the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt obtained in the step 3) in ethanol, and heating and refluxing for 6-8 h; cooling to room temperature, filtering to obtain crude product, recrystallizing with diethyl ether, adding distilled water to the recrystallized product, and adding NH4PF6Stirring for 1-2 h for precipitation, filtering, washing with water, and drying to obtain the viologen derivative electrochromic material with the molecular structural formula (B).
To further achieve the object of the present invention, preferably, the pyrrole, p-fluoronitrobenzene and K in step 1)2CO3Is 1.0: 1.2-1.4: 1.5-2.0, adding 1200-1500 mL of DMSO per mol of pyrrole;
carbazole, parafluoronitrobenzene and K in step (1)2CO3In a molar ratio of 1: 1.2-2.0: 1.5-2.5, and adding 450-500 mL of DMSO into each mol of carbazole.
Preferably, the precipitate in the step 1) is washed by water for 3-5 times, and washed by petroleum ether for 3-5 times; the volume of methanol required for each millimole of crude product in the step (1) is 6-10 mL.
Preferably, the mass ratio of the N- (4-nitrophenyl) pyrrole to the Pd/C in the step 2) is 1: 0.02-0.04, adding 4.0-5.0 mL of hydrazine hydrate and 20-30 mL of ethanol into each gram of N- (4-nitrophenyl) pyrrole;
the mass ratio of the N- (4-nitrophenyl) carbazole to the Pd/C in the step (2) is 1: 0.02-0.04, and adding 4.0-5.0 mL of hydrazine hydrate and 20-30 mL of ethanol into each gram of N-p-nitrophenyl carbazole.
Preferably, the mass ratio of the 4,4' -bipyridyl to the 1-chloro-2, 4-dinitrobenzene in the step 3) is 1: 7.0-7.8, adding 18-25 mL of acetonitrile into each gram of bipyridyl;
the mass ratio of the 4,4' -bipyridyl to the 1-chloro-2, 4-dinitrobenzene in the step (3) is 1: 7.0-7.8, and adding 18-25 mL of acetonitrile into each gram of bipyridyl.
Preferably, the precipitate in the step 3) is washed 3-4 times with acetonitrile and acetone respectively; and (3) washing the precipitate with acetonitrile and acetone for 3-4 times respectively.
Preferably, the molar mass ratio of the N- (4-aminophenyl) pyrrole to the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridyl salt in the step 4) is 2.5-3.0: 1, adding 90-100 mL of ethanol into each millimole of N- (4-aminophenyl) pyrrole;
the molar mass ratio of the N- (4-aminophenyl) carbazole to the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridyl salt in the step (4) is 2.5-3.0: 1, adding 90-100 mL of ethanol into each millimole of N- (4-aminophenyl) carbazole.
Preferably, the volume of acetone added into each mole of the crude product in the step 4) is 20-30 mL; the added NH4PF6The molar ratio of the compound to the recrystallized substance is 15-20: 1; and washing the precipitate for 3-4 times by using water.
Preferably, in the step (4), the volume of ether added to each mole of crude product is 10-20 mL; the added NH4PF6The molar ratio of the compound to the recrystallized substance is 15-20: 1; and washing the precipitate for 3-4 times by using water.
Compared with the prior art, the invention has the following advantages:
1) the viologen derivative designed by the invention introduces a pyrrole group and carbazole, and the electron-rich effect of the two N-heteroatom groups improves the electron-deficient state of the viologen compound core group 4,4' -bipyridyl, and reduces the electrochromic voltage of the viologen compound.
2) Viologen is a cathode electrochromic material, carbazole and pyrrole are anode electrochromic materials, and a bipolar electrochromic device can be obtained by introducing carbazole and pyrrole into viologen, so that superimposed colors of two colors are obtained in an electrochromic process, and higher contrast is realized, which is difficult to realize by a single electrochromic material.
3) Compared with the prior invention, the electrochromic device made of the two electrochromic materials obtained by the invention has various color changes and higher contrast. In addition, the electrochromic active substance is contained in the gel electrolyte in the invention, so that the problem of electrolyte leakage of the solution type electrochromic device is solved.
Drawings
FIG. 1 is a drawing of Compound A of example 11H NMR spectrum.
Figure 2 is a digital photograph of the color change of the electrochromic device ECD1 prepared from compound a in example 1.
Fig. 3 is a spectroelectrochemical diagram of an electrochromic device ECD1 prepared from compound a in example 1.
FIG. 4 is a drawing of Compound A from example 21H NMR spectrum.
Figure 5 is a digital photograph of the color change of the electrochromic device ECD2 prepared from compound a in example 2.
Fig. 6 is a spectroelectrochemical diagram of an electrochromic device ECD2 prepared from compound a in example 2.
FIG. 7 is a drawing of Compound B of example 31H NMR spectrum.
Figure 8 is a digital photograph of the color change of the electrochromic device ECD3 prepared from compound B in example 3.
Fig. 9 is a spectroelectrochemical diagram of an electrochromic device ECD3 prepared from compound B in example 3.
FIG. 10 is a drawing of Compound B of example 41H NMR spectrum.
Figure 11 is a digital photograph of the color change of the electrochromic device ECD4 prepared from compound B in example 4.
Fig. 12 is a spectroelectrochemical diagram of an electrochromic device ECD4 prepared from compound B in example 4.
Detailed Description
For better understanding of the present invention, the present invention will be further described with reference to the following drawings and examples, but the present invention is not limited thereto.
Example 1
A preparation method of a viologen derivative electrochromic material (A), 1'- (4-pyrrolylphenyl) -4,4' -bipyridine comprises the following steps:
1) into a 250mL three-necked flask was added 2.1g of pyrrole, 40mL of DMF, 8.9g K2CO3At 100 ℃ N2Stirring for 30min in atmosphere, adding 5.4g p-fluoronitrobenzene, and heatingRefluxing for 5 h; after the reaction is finished, cooling the solution to room temperature, adding cold water, precipitating and filtering; washing the precipitate with water for 3 times, and drying; treating the obtained crude product with 100mL of diethyl ether to obtain N- (4-nitrophenyl) pyrrole with a yield of 66%;
MS:m/z=188.1
1H NMR(600MHz,Chloroform-d)8.24(d,2H),7.88(d,2H),7.32(d,2H),6.34(t,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
2) Into a 250mL three-necked flask was added 3.3g N- (4-nitrophenyl) pyrrole, 0.1gPd/C, 2.5mL hydrazine hydrate, 80mL ethanol, N2Heating and refluxing for 12h in the atmosphere, filtering, and distilling to remove the solvent; recrystallizing in 100mL petroleum ether to obtain N- (4-aminophenyl) pyrrole with the yield of 78.5%;
MS:m/z=158.1
1H NMR(600MHz,Chloroform-d)7.41(d,2H),7.28(d,2H),6.72(d,2H),6.30(t,2H),4.34(s,2H)。
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
3) Adding 1.8g of 4,4' -bipyridine, 8.3g of 1-chloro-2, 4-dinitrobenzene and 50mL of acetonitrile into a 250mL three-neck flask, and heating and refluxing for 72 h; cooling to room temperature, filtering, washing the precipitate with ethanol and water, and vacuum drying to obtain white solid 1,1 '-bis (2, 4-dinitro) 4,4' -bipyridine salt with yield of 83.2%;
MS:m/z=560.0
1H NMR(600MHz,Chloroform-d)9.3(d,4H),8.90(d,4H),8.83(s,2H),8.25(d,2H),8.21(d,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
4) Adding 2.0g N-p-aminophenylpyrrole, 2.5g of 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt and 80mL of ethanol into a 250mL three-necked bottle, and heating and refluxing for 80 h; cooling to room temperature, filtering, recrystallizing with 30mL acetone, adding distilled water to the recrystallized material, and adding 14.55g NH4PF6And stirring for 2h to precipitate, filtering, washing with water, and drying to obtain the target product with the yield of 65%.
As shown in FIG. 1, the compound A obtained in this example (1,1'- (4-pyrrolylphenyl) -4,4' -bipyridinedihexafluorophosphate) was purified1The H NMR spectrum shows:
MS:m/z=730.2
1H NMR(600MHz,Chloroform-d)9.75(d,4H),9.14(d,4H),8.06(dd,8H),7.64(t,4H),6.39(t,4H)。
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
The solid electrochromic device is mainly prepared from a target product 1,1'- (4-pyrrolylphenyl) -4,4' -bipyridyl dihexafluorophosphate, and has the following structure: ITO glass/gel electrochromic layer/ITO glass. The preparation process of the device comprises the following steps: the method comprises the following steps of (1) preparing an electrochromic compound by using anhydrous tetra-n-butylammonium perchlorate, acetonitrile, polymethyl methacrylate (PMMA), propylene carbonate, 1'- (4-pyrrolylphenyl) -4,4' -bipyridyl dihexafluorophosphate and ferrocene which are target products of the electrochromic compound in a mass ratio of 3: 70: 6.328: 20: 0.64: 0.032 to obtain electrochromic gel, uniformly coating the electrochromic gel on one ITO glass, covering another ITO glass, and sealing with sealant.
The performance of the device: the device does not leak in the preparation process, and the preparation process is simple and easy to implement; and when a voltage of-2.0V is applied, the color of the device is changed from yellow to cyan, the response time is 3s, the performance of the device is stable in the test process, and the color is changed uniformly.
Testing an instrument: electrochemical workstation, model CHI750A, shanghai chenhua instruments, inc; a cyclic tester for electrochromic devices, type II, and Kjeldahl of Kyoto Seika is a photoelectric technology company Limited.
Figure 2 is a digital photograph of the color change of the electrochromic device ECD1 prepared from compound a in example 1. As can be seen from fig. 2, at 0.0V, ECD1 has a high optical transmittance at about 670nm, and the electrochromic device ECD1 is yellow.
The ultraviolet-visible spectrometer and the electrochromic device cycle tester are used together, and the ultraviolet-visible spectrogram of the device is tested under different voltages, so that the spectroelectrochemical spectrogram of the device is obtained, as shown in fig. 3. When a voltage of-2.0V was applied to the device ECD1, the transmittance decreased in the 560nm-780nm range, and the electrochromic device ECD1 showed a bluish green color (fig. 2). Electrochromic devices can undergo a reversible color change between yellow and cyan when voltages of-2.0V and 1.0V (or 0.0V) are alternately applied to the device. Its optical contrast at 670nm was 63%.
Compared with the electrochromic device disclosed in Chinese patent 2014101660916, the target compound A in the invention has different synthesis methods, and the structure of the electrochromic device is also different. The electrolyte of the electrochromic device disclosed in the chinese patent 2014101660916 is a liquid electrolyte, and the electrolyte of the electrochromic device in the present invention is a gel, which avoids the problem of leakage of the liquid electrolyte, and simultaneously reduces possible side reactions such as dimerization, centering reaction, etc. in the solution type electrochromic device. More importantly, the electrochromic device prepared by the target compound A can realize coloring/fading at-2.0 v/0v (1.0v), which is lower than the coloring/fading voltage (-2.3v/+2.3v) of the electrochromic device disclosed by Chinese invention patent 2014101660916, because the p-pi conjugation effect of the N-phenylpyrrole group makes the free radical stable, the N-phenylpyrrole and the derivative thereof have higher hole mobility and good electron transmission performance, the bipyridyl group has stronger electron accepting capability, and the bipyridyl group are connected to form an effective 'electron pushing-electron pulling' molecular structure, so that the compound A has good charge transfer performance, the discoloring voltage is reduced, and the contrast is higher.
Example 2
A preparation method of a viologen derivative electrochromic material 1,1'- (4-pyrrolylphenyl) -4,4' -bipyridine comprises the following steps:
1) into a 250mL three-necked flask was added 4.2g pyrrole, 80mL DMF, 17.9g K2CO3At 100 ℃ N2Stirring for 30min in the atmosphere, adding 10.8g of parafluoronitrobenzene, and heating and refluxing for 5 h; after the reaction is finished, cooling the solution to room temperature, adding cold water, precipitating and filtering; washing the precipitate with water for 3 times, and drying; treating the obtained crude product with 100mL of diethyl ether to obtain N-p-nitrophenylpyrrole with the yield of 68.9%;
MS:m/z=188.1
1H NMR(600MHz,Chloroform-d)8.24(d,2H),7.88(d,2H),7.32(d,2H),6.34(t,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
2) Into a 250mL three-necked flask was added 6.7g N-p-nitrophenylpyrrole, 0.2g Pd/C, 5.0mL hydrazine hydrate, 150mL ethanol, N2Heating and refluxing for 12h in the atmosphere, filtering and performing rotary evaporation; recrystallizing in 100mL petroleum ether to obtain N-p-aminophenyl pyrrole with the yield of 75.3%;
MS:m/z=158.1
1H NMR(600MHz,Chloroform-d)7.41(d,2H),7.28(d,2H),6.72(d,2H),6.30(t,2H),4.34(s,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
3) Adding 3.7g of 4,4' -bipyridine, 16.7g of 1-chloro-2, 4-dinitrobenzene and 100mL of acetonitrile into a 250Ml three-neck flask, and heating and refluxing for 72 h; cooling to room temperature, filtering, washing the precipitate with ethanol and water, and vacuum drying to obtain white solid 1,1 '-bis (2, 4-dinitro) 4,4' -bipyridine salt with yield of 84.2%;
MS:m/z=560.0
1H NMR(600MHz,Chloroform-d)9.3(d,4H),8.90(d,4H),8.83(s,2H),8.25(d,2H),8.21(d,2H)。
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
4) Adding 4.0g N-p-aminophenyl pyrrole, 5.0g of 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt and 150mL of ethanol into a 250mL three-necked bottle, and heating and refluxing for 80 h; cooling to room temperature, filtering, recrystallizing with 50mL acetone, adding distilled water to the recrystallized material, and adding 29.10g NH4PF6And stirring for 2h to precipitate, filtering, washing with water and drying to obtain the target product 1,1'- (4-pyrrolylphenyl) -4,4' -bipyridyl dihexafluorophosphate with the yield of 70%.
As shown in FIG. 4, the compound A obtained in this example (1,1'- (4-pyrrolylphenyl) -4,4' -bipyridinedihexafluorophosphate) was purified1The H NMR spectrum shows:
MS:m/z=730.2
1H NMR(600MHz,Chloroform-d)9.75(d,4H),9.14(d,4H),8.06(dd,8H),7.64(t,4H),6.39(t,4H)。
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
The solid electrochromic device is mainly prepared from a target product 1,1'- (4-pyrrolylphenyl) -4,4' -bipyridyl dihexafluorophosphate, and has the following structure: ITO glass/gel electrochromic layer/ITO glass. The preparation process of the device comprises the following steps: the method comprises the following steps of (1) preparing an electrochromic material by using anhydrous tetra-n-butylammonium perchlorate, acetonitrile, polymethyl methacrylate (PMMA), propylene carbonate, electrochromic compound 1,1'- (4-pyrrolylphenyl) -4,4' -bipyridyl dihexafluorophosphate and ferrocene in a mass ratio of 3: 70: 6.328: 20: 0.64: 0.032 to obtain electrochromic gel, uniformly coating the electrochromic gel on one ITO glass, covering another ITO glass, and sealing with sealant.
The performance of the device: the device does not leak in the preparation process, and the preparation process is simple and easy to implement; with the application of-2.0V, the color of the device changed from yellow to cyan, with a response time of 4 s. The device performance is stable and the color change is uniform in the test process.
Testing an instrument: electrochemical workstation, model CHI750A, shanghai chenhua instruments, inc; a cyclic tester for electrochromic devices, type II, and Kjeldahl of Kyoto Seika is a photoelectric technology company Limited.
Figure 5 is a digital photograph of the color change of the electrochromic device ECD2 prepared from compound a in example 2. As can be seen from fig. 5, the ECD2 has a high optical transmittance at about 670nm at 0.0V, and the electrochromic device ECD2 is yellow.
The ultraviolet-visible spectrometer and the electrochromic device cycle tester are used together, and the ultraviolet-visible spectrogram of the device is tested under different voltages, so that the spectroelectrochemical spectrogram of the device is obtained, as shown in fig. 6. When a voltage of-2.0V was applied to the device ECD2, the transmittance decreased in the 560nm-780nm range, and the electrochromic device ECD2 showed a bluish green color (fig. 5). Electrochromic devices can undergo a reversible color change between yellow and cyan when voltages of-2.0V and 1.0V (or 0.0V) are alternately applied to the device. Its optical contrast at 670nm was 63%.
Example 3
A preparation method of a viologen derivative electrochromic material (B)1,1'- (4-carbazolyl phenyl) -4,4' -bipyridine comprises the following steps:
1) to a 250mL three-necked flask was added 4.18g carbazole, 40mL dry DMSO, 5.18g K2CO3In N at2Stirring for 10min in the atmosphere, adding 3.6g of parafluoronitrobenzene, heating to 110 ℃, and heating and refluxing for 15 h; after the reaction is finished, cooling the solution to room temperature, adding 150mL of methanol for precipitation to obtain yellow crystalline N-p-nitrophenylcarbazole with the yield of 75.4%;
MS:m/z=288.1
1H NMR(600MHz,Chloroform-d)8.36(d,2H),8.33(d,2H),8.04(d,2H),7.90(d,2H),7.39(t,2H),7.32(t,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
2) Adding 5.2g N-p-nitrophenyl carbazole, 0.2g Pd/C and 50mL ethanol into a 250mL three-necked flask, and mixing, wherein N is2Heating and refluxing in the atmosphere, slowly adding 4ml of hydrazine hydrate, heating and refluxing for 10 hours at the reflux temperature, cooling to room temperature, filtering, and performing rotary evaporation; recrystallizing in petroleum ether to obtain N-p-aminophenylcarbazole with a yield of 78.3%;
MS:m/z=258.1
1H NMR(600MHz,Chloroform-d)8.35(d,2H),7.91(d,2H),7.57(d,2H),7.37(t,2H),7.31(t,2H),6.81(d,2H),4.43(s,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
3) Adding 3.7g of 4,4' -bipyridine, 16.7g of 1-chloro-2, 4-dinitrobenzene and 100mL of acetonitrile into a 250mL three-neck flask, and heating and refluxing for 72 h; cooling to room temperature, filtering, washing the precipitate with ethanol and water, and vacuum drying to obtain white solid 1,1 '-bis (2, 4-dinitro) 4,4' -bipyridine salt with yield of 84.2%;
MS:m/z=560.0
1H NMR(600MHz,Chloroform-d)9.3(d,4H),8.90(d,4H),8.83(s,2H),8.25(d,2H),8.21(d,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
4) Adding 3.25g N-p-aminophenylcarbazole and 2.8g of 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt into a 250mL three-neck flask, dissolving in ethanol, and heating and refluxing for 80 h; cooling to room temperature, filtering, recrystallizing with 30mL diethyl ether, adding distilled water to the recrystallized material, and adding 16.3g NH4PF6And stirring for 2h to precipitate, filtering, washing with water, and drying to obtain the target product (1,1'- (4-carbazolylphenyl) -4,4' -bipyridyl dihexafluorophosphate) with the yield of 73%.
As shown in FIG. 7, production of Compound B (1,1'- (4-carbazolylphenyl) -4,4' -bipyridinedihexafluorophosphate) obtained in this example1The H NMR spectrum shows:
MS:m/z=930.3
1H NMR(600MHz,Chloroform-d)9.74(d,4H),9.02(d,4H),8.92(t,8H),8.75(d,4H),8.32(d,4H),8.24(d,4H),8.13(d,4H)。
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
The ITO glass and the target product (1,1'- (4-carbazolyl phenyl) -4,4' -bipyridyl dihexafluorophosphate) are mainly used for preparing the solid electrochromic device, and the structure of the device is as follows: ITO glass/gel electrochromic layer/ITO glass. The preparation process of the device comprises the following steps: the method is characterized in that the electrochromic material is prepared by using anhydrous tetra-n-butylammonium perchlorate, acetonitrile, polymethyl methacrylate (PMMA), propylene carbonate, electrochromic compound 1,1'- (4-carbazolylphenyl) -4,4' -bipyridyl dihexafluorophosphate and ferrocene in a mass ratio of 3: 70: 6.158: 20: 0.81: 0.032 to obtain electrochromic gel, uniformly coating the electrochromic gel on one ITO glass, covering another ITO glass, and sealing with sealant.
The performance of the device: the device does not leak in the preparation process, and the preparation process is simple and easy to implement; the device color changed from orange-red to yellow-brown with a response time of 2s by applying a voltage of-1.0V, and the color changed from yellow-brown to dark green with a response time of 3s by applying a voltage of-1.4V. The device performance is stable and the color change is uniform in the test process.
Testing an instrument: electrochemical workstation, model CHI750A, shanghai chenhua instruments, inc; a cyclic tester for electrochromic devices, type II, and Kjeldahl of Kyoto Seika is a photoelectric technology company Limited.
The ultraviolet-visible spectrometer and the electrochromic device cycle tester are used together, and the ultraviolet-visible spectrogram of the device is tested under different voltages, so that the spectroelectrochemical spectrogram of the device is obtained, as shown in fig. 9. As can be seen from fig. 9, the electrochromic device ECD3 has a high transmittance in the range of 550nm-700nm at a voltage of 0.0V, at which the color of the device shows an orange-red color. When a voltage of-1.0V was applied to the device, the transmittance was significantly reduced, and the color of the device was yellowish brown (fig. 8, fig. 8 is a digital photograph of the color change of the electrochromic device ECD3 prepared from compound B in example 3). Electrochromic devices can undergo a reversible color change between reddish-orange and brownish-yellow when voltages of-1.0V and 0.0V are alternately applied to the device. Continuing to increase the voltage to-1.4V, the device had two distinct absorption peaks at 612nm and 713nm, at which time the device was dark green in color (FIG. 8). Electrochromic devices can undergo a reversible color change between amber and dark green when voltages of-1.0V and-1.4V are alternately applied to the device. The optical transmittances at 612nm and 713nm were 56% and 44%, respectively.
The electrochromic device prepared by the target compound B in the embodiment can realize first coloring under-1.0 v, can realize second coloring when the voltage reaches-1.4 v, and has lower coloring voltage and richer color change compared with the electrochromic device disclosed in Chinese patent 2014101660916. Because the N-phenylcarbazole group has a better electron supply effect, the bipyridine group has stronger electron accepting capability, and the bipyridine group are connected to form an effective 'electron pushing-electron pulling' molecular structure, so that the compound B has good charge transfer performance, the color change voltage is reduced, and the contrast is higher.
Example 4
A preparation method of viologen derivative electrochromic material 1,1'- (4-carbazolyl phenyl) -4,4' -bipyridine comprises the following steps:
1) to a 250mL three-necked flask was added 2.09g carbazole, 20mL dry DMSO, 6.91g K2CO3In N at2Stirring for 10min in the atmosphere, adding 1.8g of parafluoronitrobenzene, heating to 110 ℃, and heating and refluxing for 15 h; after the reaction is finished, cooling the solution to room temperature, adding 100mL of methanol for precipitation to obtain yellow crystal N-p-nitrophenylcarbazole, wherein the yield is 82.4%;
MS:m/z=288.1
1H NMR(600MHz,Chloroform-d)8.36(d,2H),8.33(d,2H),8.04(d,2H),7.90(d,2H),7.39(t,2H),7.32(t,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
2) Adding 2.6g N-p-nitrophenyl carbazole, 0.1g Pd/C and 30mL ethanol into a 250mL three-necked flask, and mixing, wherein N is2Heating and refluxing in the atmosphere, slowly adding 2ml of hydrazine hydrate, heating and refluxing for 10 hours at the reflux temperature, cooling to room temperature, filtering, and performing rotary evaporation; recrystallizing in petroleum ether to obtain N-p-aminophenylcarbazole with a yield of 75.8%;
MS:m/z=258.1
1H NMR(600MHz,Chloroform-d)8.35(d,2H),7.91(d,2H),7.57(d,2H),7.37(t,2H),7.31(t,2H),6.81(d,2H),4.43(s,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
3) 1.8g of 4,4' -bipyridine, 8.4g of 1-chloro-2, 4-dinitrobenzene and 50mL of acetonitrile are added into a 250Ml three-neck flask and heated and refluxed for 72 hours; cooling to room temperature, filtering, washing the precipitate with ethanol and water, and vacuum drying to obtain white solid 1,1 '-bis (2, 4-dinitro) 4,4' -bipyridine salt with yield of 86.2%;
MS:m/z=490.1
1H NMR(600MHz,Chloroform-d)9.3(d,4H),8.90(d,4H),8.83(s,2H),8.25(d,2H),8.21(d,2H).
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
4) 1.61g N-p-aminophenylcarbazole and 1.4g of 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridyl salt are added into a 250mL three-neck flask and dissolved in ethanol, and the mixture is heated and refluxed for 80 hours; cooling to room temperature, filtering, recrystallizing with 50mL diethyl ether, adding distilled water to the recrystallized product, and adding8.15g of NH4PF6And stirring for 2h to precipitate, filtering, washing with water, and drying to obtain the target product (1,1'- (4-carbazolylphenyl) -4,4' -bipyridyl dihexafluorophosphate) with the yield of 75%.
As shown in FIG. 10, production of Compound B (1,1'- (4-carbazolylphenyl) -4,4' -bipyridinedihexafluorophosphate) obtained in this example1The H NMR spectrum shows:
MS:m/z=930.3
1H NMR(600MHz,Chloroform-d)9.74(d,4H),9.02(d,4H),8.92(t,8H),8.75(d,4H),8.32(d,4H),8.24(d,4H),8.13(d,4H)。
the instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
The instrument used was: mass Spectrometry (MS) liquid chromatography mass spectrometer, standard Agilent1100, Bruker, germany, origin; hydrogen spectroscopy (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, Bruker, germany, origin.
The ITO glass and the target product (1,1'- (4-carbazolyl phenyl) -4,4' -bipyridyl dihexafluorophosphate) are mainly used for preparing the solid electrochromic device, and the structure of the device is as follows: ITO glass/gel electrochromic layer/ITO glass. The preparation process of the device comprises the following steps: the method is characterized in that the electrochromic material is prepared by using anhydrous tetra-n-butylammonium perchlorate, acetonitrile, polymethyl methacrylate (PMMA), propylene carbonate, electrochromic compound 1,1'- (4-carbazolylphenyl) -4,4' -bipyridyl dihexafluorophosphate and ferrocene in a mass ratio of 3: 70: 6.158: 20: 0.81: 0.032 to obtain electrochromic gel, uniformly coating the electrochromic gel on one ITO glass, covering another ITO glass, and sealing with sealant.
The performance of the device: the device does not leak in the preparation process, and the preparation process is simple and easy to implement; the device color changed from orange-red to yellow-brown with a response time of 2s by applying a voltage of-1.0V, and the color changed from yellow-brown to dark green with a response time of 3s by applying a voltage of-1.4V. The device performance is stable and the color change is uniform in the test process.
Testing an instrument: electrochemical workstation, model CHI750A, shanghai chenhua instruments, inc; a cyclic tester for electrochromic devices, type II, and Kjeldahl of Kyoto Seika is a photoelectric technology company Limited.
The ultraviolet-visible spectrometer and the electrochromic device cycle tester are used together, and the ultraviolet-visible spectrogram of the device is tested under different voltages, so that the spectroelectrochemical spectrogram of the device is obtained, as shown in fig. 12. As can be seen from fig. 12, the electrochromic device ECD3 has a high transmittance in the range of 550nm-700nm at a voltage of 0.0V, at which the color of the device shows an orange-red color. When a voltage of-1.0V was applied to the device, the transmittance was significantly reduced, and the color of the device was yellowish brown (fig. 11, fig. 11 is a digital photograph of the color change of the electrochromic device ECD4 prepared from compound B in example 4). Electrochromic devices can undergo a reversible color change between reddish-orange and brownish-yellow when voltages of-1.0V and 0.0V are alternately applied to the device. Continuing to increase the voltage to-1.4V, the device had two distinct absorption peaks at 612nm and 713nm, at which time the device was dark green in color (FIG. 11). Electrochromic devices can undergo a reversible color change between amber and dark green when voltages of-1.0V and-1.4V are alternately applied to the device. The optical transmittances at 612nm and 713nm were 56% and 44%, respectively.
The electrolyte of the electrochromic device disclosed in the Chinese patent 2014101660916 is liquid electrolyte, and the electrolyte of the electrochromic device disclosed in the invention is gel, so that the problem of leakage of the liquid electrolyte is avoided. Meanwhile, the invention also reduces the side reactions which may occur in the solution type electrochromic device, such as dimerization, neutralization reaction and the like. Compared with the electrochromic device disclosed in the Chinese patent 2014101660916, the electrochromic device prepared by the target compound B can realize first coloring at-1.0 v and can realize second coloring at-1.4 v, and the electrochromic device has the advantages that the coloring voltage is reduced, the color change is richer, the N-phenylcarbazole group has a better electron supply effect, the bipyridine group has a stronger electron accepting capability, and the bipyridine group are connected to form an effective electron pushing-pulling molecular structure, so that the compound B has a good charge transfer performance, the color change voltage is reduced, and the contrast is higher.
The structure of the compound A, B synthesized in the invention is that an aromatic compound is directly connected to bipyridine, and Chinese patent invention 2014101660916 discloses that the structure of an electrochromic material is bipyridine-alkyl chain; the electrochromic material A, B in the invention has a structure of 'push electron-draw electron', and the structure makes the electrochromic material have good charge transfer characteristics, so that the electrochromic driving voltage is reduced, which cannot be achieved by the electrochromic material with the bipyridine-alkyl chain structure synthesized in the Chinese invention patent 2014101660916.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (9)
1. The preparation method of the viologen derivative electrochromic material comprises the following steps of:
the method for preparing the viologen derivative electrochromic material with the molecular structural formula (A) is characterized by comprising the following steps:
1) mixing pyrrole, DMSO and K2CO3Mixing uniformly at N2Stirring at room temperature for 20-30 min under the atmosphere, adding parafluoronitrobenzene, and refluxing for 12-15 h at 100-105 ℃; after the reaction is finished, cooling the solution to room temperature, adding cold water, precipitating and filtering; washing the precipitate with water and petroleum ether to obtain N- (4-nitrophenyl) pyrrole;
2) uniformly mixing the N- (4-nitrophenyl) pyrrole obtained in the step 1), Pd/C and ethanol, and carrying out N mixing at the temperature of 80-85 DEG C2Refluxing for 10-20 min in the atmosphere, adding hydrazine hydrate, continuously reacting for 10-12 h, filtering while hot, and removing the solvent by rotary evaporation; passing dichloromethane through silica gel chromatographic column to obtain N- (4-aminophenyl) pyrrole;
3) uniformly mixing 4,4' -bipyridyl, 1-chloro-2, 4-dinitrobenzene and acetonitrile, and heating and refluxing for 40-48 h; cooling to room temperature, filtering to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain a white solid 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt;
4) dissolving the N- (4-aminophenyl) pyrrole obtained in the step 2) and the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt obtained in the step 3) in a proper amount of ethanol, and dissolving N2Heating and refluxing for 6-8 h under protection; cooling to room temperature, filtering to obtain crude product, recrystallizing with acetone, adding distilled water to the recrystallized product, and adding NH4PF6Stirring for 1-2 h for precipitation, filtering, washing with water, and drying to obtain the viologen derivative electrochromic material with the molecular structural formula (A);
the preparation method of the viologen derivative electrochromic material with the molecular structural formula (B) comprises the following steps:
(1) carbazole, dry DMSO, K2CO3Mixing in N2Stirring for 10-30 min at room temperature under the atmosphere, adding parafluoronitrobenzene, heating to 100-120 ℃, and heating and refluxing for 12-15 h; after the reaction is finished, cooling the solution to room temperature to obtain a crude product, and adding methanol for precipitation to obtain yellow crystal N- (4-nitrophenyl) carbazole;
(2) mixing the N- (4-nitrophenyl) carbazole, Pd/C and ethanol, N2Heating and refluxing in the atmosphere, adding hydrazine hydrate, heating and refluxing for 10-12 h at the reflux temperature, cooling to room temperature, filtering, and distilling to remove the solvent; recrystallizing in petroleum ether to obtain N- (4-aminophenyl) carbazole;
(3) mixing 4,4' -bipyridine, 1-chloro-2, 4-dinitrobenzene and acetonitrile, and heating and refluxing for 40-48 h; cooling to room temperature, filtering to obtain a precipitate, washing the precipitate, and drying in vacuum to obtain a white solid 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt;
(4) dissolving the N- (4-aminophenyl) carbazole obtained in the step 2) and the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt obtained in the step 3) in ethanol, and heating and refluxing for 6-8 h; cooling to room temperature, filtering to obtain crude product, recrystallizing with diethyl ether, adding distilled water to the recrystallized material, and filteringAddition of NH4PF6Stirring for 1-2 h for precipitation, filtering, washing with water, and drying to obtain the viologen derivative electrochromic material with the molecular structural formula (B).
2. The method for preparing the viologen derivative electrochromic material according to claim 1, wherein the pyrrole, p-fluoronitrobenzene and K in step 1) are2CO3Is 1.0: 1.2-1.4: 1.5-2.0, adding 1200-1500 mL of DMSO per mol of pyrrole;
carbazole, parafluoronitrobenzene and K in step (1)2CO3In a molar ratio of 1: 1.2-2.0: 1.5-2.5, and adding 450-500 mL of DMSO into each mol of carbazole.
3. The preparation method of the viologen derivative electrochromic material according to claim 1, wherein the precipitate in the step 1) is washed with water for 3-5 times and with petroleum ether for 3-5 times; the volume of methanol required for each millimole of crude product in the step (1) is 6-10 mL.
4. The preparation method of the viologen derivative electrochromic material according to claim 1, wherein the mass ratio of the N- (4-nitrophenyl) pyrrole to the Pd/C in the step 2) is 1: 0.02-0.04, adding 4.0-5.0 mL of hydrazine hydrate and 20-30 mL of ethanol into each gram of N- (4-nitrophenyl) pyrrole; adding hydrazine hydrate is adding bronze drum injection;
the mass ratio of the N- (4-nitrophenyl) carbazole to the Pd/C in the step (2) is 1: 0.02-0.04, adding 4.0-5.0 mL of hydrazine hydrate and 20-30 mL of ethanol into each gram of N-p-nitrophenylcarbazole; the hydrazine hydrate is added as a copper drum injection.
5. The method for preparing the viologen derivative electrochromic material according to claim 1, wherein the mass ratio of the 4,4' -bipyridine to the 1-chloro-2, 4-dinitrobenzene in the step 3) is 1: 7.0-7.8, adding 18-25 mL of acetonitrile into each gram of bipyridyl;
the mass ratio of the 4,4' -bipyridyl to the 1-chloro-2, 4-dinitrobenzene in the step (3) is 1: 7.0-7.8, and adding 18-25 mL of acetonitrile into each gram of bipyridyl.
6. The preparation method of the viologen derivative electrochromic material according to claim 1, wherein the precipitate in the step 3) is washed with acetonitrile and acetone for 3-4 times respectively; and (3) washing the precipitate with acetonitrile and acetone for 3-4 times respectively.
7. The method for preparing the viologen derivative electrochromic material according to claim 1, wherein the molar mass ratio of the N- (4-aminophenyl) pyrrole to the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridine salt in the step 4) is 2.5 to 3.0: 1, adding 90-100 mL of ethanol into each millimole of N- (4-aminophenyl) pyrrole;
the molar mass ratio of the N- (4-aminophenyl) carbazole to the 1,1 '-bis (2, 4-dinitro) -4,4' -bipyridyl salt in the step (4) is 2.5-3.0: 1, adding 90-100 mL of ethanol into each millimole of N- (4-aminophenyl) carbazole.
8. The preparation method of the viologen derivative electrochromic material according to claim 1, wherein the volume of acetone added to each mole of the crude product in the step 4) is 20-30 mL; the added NH4PF6The molar ratio of the compound to the recrystallized substance is 15-20: 1; and washing the precipitate for 3-4 times by using water.
9. The preparation method of the viologen derivative electrochromic material according to claim 1, wherein the volume of diethyl ether added to each mole of the crude product in the step (4) is 10-20 mL; the added NH4PF6The molar ratio of the compound to the recrystallized substance is 15-20: 1; and washing the precipitate for 3-4 times by using water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910460297.2A CN110105336B (en) | 2019-05-30 | 2019-05-30 | Viologen derivative electrochromic material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910460297.2A CN110105336B (en) | 2019-05-30 | 2019-05-30 | Viologen derivative electrochromic material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110105336A CN110105336A (en) | 2019-08-09 |
CN110105336B true CN110105336B (en) | 2020-09-22 |
Family
ID=67492914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910460297.2A Active CN110105336B (en) | 2019-05-30 | 2019-05-30 | Viologen derivative electrochromic material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110105336B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110642853A (en) * | 2019-10-16 | 2020-01-03 | 南方科技大学 | Electrochromic device and application thereof |
CN110845477A (en) * | 2019-11-20 | 2020-02-28 | 南京邮电大学 | Novel symmetrical viologen compound and preparation method and application thereof |
CN112794815A (en) * | 2021-02-03 | 2021-05-14 | 畅的新材料科技(上海)有限公司 | Electrochromic molecule with 4,4' -bipyridine as central structure and preparation method thereof |
CN114133380B (en) * | 2021-11-08 | 2022-12-16 | 华南理工大学 | Purpurin derivative electrochromism and electroluminescent photochromic material, and preparation method and application thereof |
CN114409591B (en) * | 2022-01-28 | 2023-08-11 | 福州大学 | Bishydrazide viologen derivative, preparation method thereof and humidity sensing application |
CN114524764B (en) * | 2022-02-18 | 2023-08-18 | 南京邮电大学 | Novel asymmetric viologen compound and preparation method and application thereof |
CN114907416B (en) * | 2022-05-17 | 2024-01-02 | 西安交通大学 | Selenium-containing purple-refined coordination metal macrocyclic supermolecule, and synthesis method and application thereof |
CN115557934A (en) * | 2022-10-12 | 2023-01-03 | 华南理工大学 | Viologen electrochromic material from yellow to green based on viologen derivative and preparation method and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3995314B2 (en) * | 1997-10-01 | 2007-10-24 | 富士フイルム株式会社 | Method for producing viologen derivative |
JP2007326783A (en) * | 2006-06-06 | 2007-12-20 | Fujifilm Corp | Oxonol compound and optical information-recording medium |
KR101458207B1 (en) * | 2007-11-20 | 2014-11-12 | 삼성전자주식회사 | Electrochromic Materials and Electrochromic Device Using The Same |
WO2010126121A1 (en) * | 2009-05-01 | 2010-11-04 | Ricoh Company, Ltd. | Electrochromic display apparatus |
CN102234505B (en) * | 2010-04-29 | 2014-01-01 | 比亚迪股份有限公司 | Electrochromic material and preparation method thereof, and anti-dazzling automobile rear-vision mirror |
CN102311729B (en) * | 2010-06-29 | 2014-04-02 | 比亚迪股份有限公司 | Electrochromic material, preparation method thereof, glare-proof rearview mirror for automobiles |
ES2661512T3 (en) * | 2013-09-17 | 2018-04-02 | Essilor International | Electrochromic composition |
KR101979007B1 (en) * | 2014-06-16 | 2019-05-16 | 엘지디스플레이 주식회사 | An electrochromic material, and an electrochromic particle and an electrochromic device comprising the same |
KR101957151B1 (en) * | 2016-12-07 | 2019-06-19 | 엘지디스플레이 주식회사 | Viologen compound, electrolyte, light-transmittance variable panel and display device having the compound |
-
2019
- 2019-05-30 CN CN201910460297.2A patent/CN110105336B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN110105336A (en) | 2019-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110105336B (en) | Viologen derivative electrochromic material and preparation method thereof | |
Huang et al. | Preparation and optoelectronic behaviours of novel electrochromic devices based on triphenylamine-containing ambipolar materials | |
CN114133380B (en) | Purpurin derivative electrochromism and electroluminescent photochromic material, and preparation method and application thereof | |
Shoji et al. | Synthesis of azulenophthalimides by phosphine-mediated annulation of 1, 2-diformylazulenes with maleimides | |
Shi et al. | Electrochromism of substituted phthalate derivatives and outstanding performance of corresponding multicolor electrochromic devices | |
Liu et al. | Yellow electrochromic polymer materials with fine tuning electrofluorescences by adjusting steric hindrance of side chains | |
Wang et al. | Syntheses and electrochromic and fluorescence properties of three double dithienylpyrroles derivatives | |
Wu et al. | Synthesis and optical properties of redox-active triphenylamine-based derivatives with methoxy protecting groups | |
Huang et al. | Synthesis and characteristics of novel TPA-containing electrochromic poly (ether sulfone) s with dimethylamino substituents | |
CN102311729B (en) | Electrochromic material, preparation method thereof, glare-proof rearview mirror for automobiles | |
Zhang et al. | Activity of N–H in phenothiazine derivatives: synthesis and applications in fluoride ions sensing and electrochromism | |
CN111793062B (en) | Novel asymmetric viologen compound and preparation method and application thereof | |
De Simone et al. | Theoretical and experimental investigation on the near-infrared and UV–vis spectral regions of a newly synthesized triarylamine electrochromic system | |
CN115557934A (en) | Viologen electrochromic material from yellow to green based on viologen derivative and preparation method and application thereof | |
Cai et al. | Multifunctional polyamides containing pyrrole unit with different triarylamine units owning electrochromic, electrofluorochromic and photoelectron conversion properties | |
KR20170047308A (en) | Device for controlling the passage of energy | |
Chen et al. | Thiophene-2, 5-diesters as electrochromic materials: The effect of ester groups on the device performance and stability | |
Song et al. | Effects of the acceptor pattern and substitution position on the properties of N-phenyl-carbazolyl based donor–acceptor–donor molecules | |
Li et al. | Multiple stimuli-responsive electropolymerized polymer based on quinacridone dye via breaking conjugated structure strategy | |
CN110759953B (en) | Ferrocene-improved triphenylamine derivative electrochromic composite material and preparation method thereof | |
CN114516864A (en) | Compound and preparation method thereof, electrochromic device and preparation method and application thereof | |
KR100965225B1 (en) | Electrochromic viologens with asymmetric structure and device therefrom | |
CN110499040A (en) | A kind of gulf area replaces π-extension class dyestuff and preparation method thereof | |
CN110698509B (en) | Triphenylamine derivative electrochromic composite material and preparation method thereof | |
CN113278035B (en) | Electrical stimulation response type iridium (III) complex and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |