CN107011318A - Uniformpoly thiophene derivative electrochromic material and preparation method thereof - Google Patents

Abstract

The invention discloses Uniformpoly thiophene derivative electrochromic material and preparation method thereof；Uniformpoly thiophene derivative electrochromic material has following molecular structure：

Description

Oligothiophene derivative electrochromic material and preparation method thereof

technical field

The invention relates to the technical field of photoelectric materials, in particular to an oligomerized trithiophene derivative as an electrochromic material and a preparation method thereof.

Background technique

Since 1977, Japanese scientist Hideki Shirakawa, American scientists A.J.Heeger, and A.G.MacDirmid made polyethylene conductive by doping, which completely broke the traditional view that organic materials can only be used as insulating materials, making organic conductive materials a new research. field. Thus, various materials with optoelectronic properties have been derived. Electrochromism refers to the phenomenon that the optical properties (transmittance, absorptivity, etc.) of materials undergo stable and reversible changes through the injection or extraction of charges under the action of an external electric field.

Garnier, Druy and Seymour et al. (BeaujugePM, Reynolds J R.Color Control in π-Congjugated Organic Polymers for Use in Electrochromic Devices[J].ChemicalReviews.2010,110(1):268-320; Garnier F, Tourillon G.organic conducting polymers derived from substituted thiophenes as electrochromic material[J].J.Electroanal.Chem.1983,148(2):299-303.) prepared polythiophene and its derivatives, and polythiophene, poly-(3,4 The electrochromic properties of -dimethyl)thiophene, poly-(3-methyl)thiophene and poly-(2,2')dithiophene were tested. The structure of preparing the liquid electrochromic device is: ITO glass/electrochromic material/electrolyte/ITO glass. The specific device preparation method is as follows: the prepared polythiophene and its derivatives are respectively formed on the ITO glass by the method of spin coating film formation. The ITO glass is one electrode, and the other ITO glass is the other electrode. The glue bonds the two pieces of ITO glass, and the gap between them is about 0.5mm, and then the electrolyte is injected into the gap between the two pieces of ITO glass. The electrochromic device prepared according to the above literature has two characteristics: one is that the electrochromic material must be formed into a film, and the other is that there is a liquid part in the device. But there are two problems brought about by this. One is that the material must be formed into a film. This undoubtedly increases the difficulty and cost of preparing the device. Second, if the device package is not good enough or the sealant is damaged during use, there will be a risk of leakage and affect the performance of the device.

Contents of the invention

The purpose of the present invention is to provide a new oligothiophene derivative that can be used as an electrochromic material; the molecular structure of the oligothiophene derivative designed by the present invention contains a thiophene structural unit, has good conjugation, and has an amide group at its end , easy to generate interactions between molecules; at the same time, the oligothiophene derivatives prepared by the present invention can form a gel, and the device prepared by using the gel as an electrochromic material does not require a film-forming process, and may also solve the problem of Due to the use of liquid electrolyte, the device is prone to leakage problems.

Another object of the present invention is to provide a preparation method of oligothiophene derivatives that can be used as electrochromic materials.

Conjugated organic molecules have a unique structure in which single and double bonds are spaced apart. By modifying its molecular structure, its energy band structure can be adjusted, thereby changing its light absorption characteristics. Thiophene is a five-membered ring structure, which conforms to Schucker's rule. It shows good environmental and thermal stability and structural diversity in the process of doping and dedoping. The molecular structure designed in the present invention contains thiophene structural unit, has good conjugation, and has cyanoamide at the end, which is easy to generate interaction between molecules.

The reaction process of the oligothiophene derivative electrochromic material of the present invention is as follows:

The object of the invention is achieved through the following technical solutions:

The electrochromic material of oligothiophene derivatives has the following molecular structure:

The preparation method of the oligothiophene derivative electrochromic material comprises the following steps:

1) Mix cyanoacetic acid, ethanol and thionyl chloride, and reflux for 3-5h; after the reaction is completed, cool the mixture to room temperature, add NaHCO ₃ solution; add petroleum ether to extract organic matter, and wash the organic layer with saturated NaCl solution and water , then dried and filtered; the obtained crude product was separated and purified by column chromatography, eluted with petroleum ether and ethyl acetate as the eluent to obtain a light yellow liquid; added alkylamine, refluxed for 10-12h; filtered, precipitated The thing is recrystallized with ethanol again to obtain 2-cyanoacetyloctylamine;

2) Mix N,N-dimethylformamide (DMF) and dichloroethane and place in an ice-water bath at 0-5°C; then, add the catalyst POCl ₃ dropwise and stir for 1-2h; remove the mixture from the ice bath Remove from the medium and gradually raise the temperature to 35-40°C until the solution turns light yellow; dissolve the thiophene oligomer in dichloroethane, then add it to the light yellow solution, and react at room temperature for 10-12h; adjust the pH to 8-9, then stirred at 85-90°C for 1-2h; extracted with CH ₂ Cl ₂ , washed with water, dried, filtered; then separated by column chromatography, the eluents were n-hexane and dichloromethane, and evaporated to dryness Solvent, obtains solid product dialdehyde group thiophene oligomer;

3) Dissolve the 2-cyanoacetyloctylamine obtained in step 1) and the dialdehydethiophene oligomer obtained in step 2) in chloroform, add triethylamine, heat at 80-85°C, and reflux for 12-15h ; The organic layer was washed with brine, dried, and separated by column chromatography. The eluent was n-hexane and dichloromethane, and rotary evaporated to obtain oligothiophene derivatives.

To further realize the object of the present invention, preferably, in step 1), the mass ratio of cyanoacetic acid and sulfur oxychloride is 15-70:1; 100-600ml of ethanol and _{50-400mlNaHCO} are added per gram of thionyl chloride solution; the concentration of NaHCO ₃ solution is 0.2-0.6M.

Preferably, in step 1), the drying is done with anhydrous MgSO Drying; the organic layer is washed with saturated NaCl solution and water for _2-4 times; the volume ratio of petroleum ether to ethyl acetate is 3- 4:1-2.

Preferably, in step 1), 6-15 mmol of alkylamine is added per gram of light yellow liquid.

Preferably, in step 2), the volume ratio of the N,N-dimethylformamide, dichloroethane mixture and catalyst _POCl3 is 1:2-10:0.8-3; every ml N,N-di Methylformamide is added to 2-10 mmol thiophene oligomers; the thiophene oligomers are trithiophene 3T-DCNC _m , hexathiophene 6T-DCNC _m or nonathiophene 9T-DCNC _m , wherein m=5-18.

Preferably, in step 2), 1-3ml dichloroethane is added to every mmol of thiophene oligomer; the volume ratio of the n-hexane to dichloromethane is 1-3:1-2; MgSO ₄ is dried; the pH value is adjusted to 8-9 through NaOH solution, and the concentration of NaOH solution is 1-2M.

Preferably, in step 3), the molar ratio of dialdehyde thiophene oligomer to 2-cyanoacetyloctylamine is 1:3-10; 0.06-0.2 mmol of catalyst is added per mmol of dialdehyde thiophene oligomer triethylamine.

Preferably, in step 3), the drying is done with anhydrous MgSO ₄ ; the volume ratio of n-hexane to dichloromethane= is 1-2:2-4.

Compared with the prior art, the present invention has the following advantages:

1) The molecular structure of the oligomerized thiophene derivatives designed in the present invention contains thiophene structural units, has good conjugation, and has an amide group at the end, which is easy to generate interaction between molecules.

2) The oligothiophene derivative prepared by the present invention can form a gel, and the device prepared by using the gel as an electrochromic material does not need a film-forming process, and it is also possible to solve the problem of easy leakage of the device due to the use of a liquid electrolyte The problem.

detailed description

In order to better understand the present invention, the present invention will be further described below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1 A preparation method of oligothiophene derivative electrochromic material 3T-DCNC ₈ , comprising the following steps:

1) Add 5g of cyanoacetic acid, 40ml of ethanol, and 0.1g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 20ml of 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 2g of the above product and 5ml of octylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 2.34 g of needle-like white solid 2-cyanoacetyloctylamine, with a yield of 48.4%.

MS: m/z=195.3

¹ H NMR (400MHz, CDCl ₃ , δ) 8.03(br, 1H), 3.36(s, 2H), 3.29(qr, 2H), 1.53(q, 2H), 1.28(m, 10H), 0.87(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, place of manufacture Germany Bruker Company; proton spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of manufacture Germany Bruker Company.

2) Add 0.5 ml of N,N-dimethylformamide (DMF) and 3 ml of dichloroethane into a 250 ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.2 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 1 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 3mmol of trithiophene in 4ml of dichloroethane, then add to the above light yellow solution, and react at room temperature for 12h. Add 20ml of 1M NaOH solution to adjust pH=8-9, then stir at 85°C for 2h. Extract with 20ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then separated by column chromatography, the eluent is n-hexane:dichloromethane=3:1 (volume ratio), and the solvent is evaporated to dryness to obtain the solid product 5,5-dialdehyde-2,2':5',2 "-trithiophene 0.876g, productive rate 87%.

MS: m/z=304.1

¹ H NMR (DMSO-d6, ppm): 9.90 (s, 2H), 8.02 (d, 2H, J = 3.9 Hz), 7.66 (s, 2H), 7.63 (d, 2H, J = 3.9 Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 10 mmol of the product of 1) reaction and 2 mmol of the product of 2) reaction in 5 ml of chloroform, add 0.2 mmol of catalyst triethylamine (TEA), heat at 80 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=1; 4 (volume ratio) to obtain 1.184 g of the final product 3T-DCNC ₈ with a yield of 91%.

MS: m/z=658.4

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.20(s, 2H), 7.60(s, 2H), 7.59(s, 2H) 7.30(d, 2H), 7.13(m, 4H), 7.01(s, 2H), 0.89-0.78 (m, 30H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, place of manufacture Germany Bruker Company; proton spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of manufacture Germany Bruker Company.

The molecular structure of the product in this example contains a thiophene structural unit, which has good conjugation, and has cyanoamide at its end, which is easy to generate interaction between molecules, and can form a gel at room temperature. The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:40, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from yellow to light green; when a negative voltage is applied, the color changes from light green to yellow, which is reversible.

Example 2 Oligothiophene derivative electrochromic material 3T-DCNC ₈ and its preparation method:

1) Add 10g of cyanoacetic acid, 40ml of ethanol, and 0.3g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 40ml of 0.5M NaHCO ₃ solution. Then, 35ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 3.7g of the above product and 12ml of octylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 4.13 g of needle-like white solid 2-cyanoacetyloctylamine, with a yield of 45.1%.

MS: m/z=195.6

¹ H NMR (400MHz, CDCl ₃ , δ) 8.12(br, 1H), 3.31(s, 2H), 3.26(qr, 2H), 1.59(q, 2H), 1.31(m, 10H), 0.81(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 1 ml of N, N-dimethylformamide (DMF) and 10 ml of dichloroethane into a 250 ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 2.5 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 1 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 5.5 mmol of trithiophene in 10 ml of dichloroethane, then add it to the above light yellow solution, and react at room temperature for 12 h. Add 40ml of 1M NaOH solution to adjust pH=8-9, then stir at 85°C for 2h. Extract with 30ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then separate by column chromatography, the eluent is n-hexane:dichloromethane=3:1 (volume ratio), and the solvent is evaporated to dryness to obtain the solid product 5,5-dialdehyde-2,2':5',2 "-trithiophene 1.714g, productive rate 84.3%.

MS: m/z=304.1

¹ H NMR (DMSO-d6, ppm): 9.87(s, 2H), 8.06(d, 2H, J=3.9Hz), 7.661(s, 2H), 7.73(d, 2H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 20 mmol of the product of 1) reaction and 4 mmol of the product of 2) reaction in 10 ml of chloroform, add 0.2 mmol of catalyst triethylamine (TEA), heat at 80 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried, separated by column chromatography, and the eluent was n-hexane:dichloromethane=1; 3 (volume ratio), and 2.144 g of the final product 3T-DCNC ₈ was obtained, with a yield of 88.7%.

MS: m/z=658.4

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.16(s, 2H), 7.62(s, 2H), 7.51(s, 2H), 7.34(d, 2H), 7.23(m, 4H), 7.09(s, 2H), 0.89-0.78(m, 30H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:43, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant.

The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from yellow to light green; when a negative voltage is applied, the color changes from light green to yellow, which is reversible.

Example 3 Oligothiophene derivative electrochromic material 6T-DCNC ₈ and its preparation method:

1) Add 5g of cyanoacetic acid, 40ml of ethanol, and 0.1g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 20ml of 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 2g of the above product and 5ml of octylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 2.11 g of needle-like white solid 2-cyanoacetyloctylamine, with a yield of 46.7%.

MS: m/z=195.4

¹ H NMR (400MHz, CDCl ₃ , δ) 8.01(br, 1H), 3.34(s, 2H), 3.31(qr, 2H), 1.54(q, 2H), 1.22(m, 10H), 0.871(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 0.7ml of N,N-dimethylformamide (DMF) and 5ml of dichloroethane into a 250ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.5 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 2 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 3 mmol of hexathiophene in 6 ml of dichloroethane, then add it to the above light yellow solution, and react at room temperature for 12 h. Add 30ml of 1M NaOH solution to adjust pH=8-9, then stir at 90°C for 2h. Extract with 20ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then it was separated by column chromatography, the eluent was n-hexane:dichloromethane=3:1 (volume ratio), and the solvent was evaporated to dryness to obtain 1.475 g of solid product with a yield of 84.1%.

MS:m/z=550.1

¹ H NMR (DMSO-d6, ppm): 9.71(s, 2H), 7.12(d, 2H, J=3.9Hz), 7.76(s, 2H), 6.91(d, 8H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 10 mmol of the product of 1) reaction and 2 mmol of the product of 2) reaction in 5 ml of chloroform, add 0.3 mmol of catalyst triethylamine (TEA), heat at 85 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=1;5 (volume ratio), and 2.392 g of the final product 6T-DCNC ₈ was obtained with a yield of 88%.

MS: m/z=906.2

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.17(s, 2H) 8.0(s, 2H), 7.61(s, 2H), 7.3(s, 2H), 6.91(d, 8H), 2.91(t, 2H), 1.55(m, 4H), 1.29-1.33(m, 20H), 0.97(t, 6H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, the electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and electrochromic compound at a mass ratio of 3:11:45, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from red to blue; when a negative voltage is applied, the color changes from blue to red, which is reversible.

Example 4 Oligothiophene derivative electrochromic material 6T-DCNC ₈ and its preparation method:

1) Add 10g cyanoethyl, 50ml ethanol, 0.3g thionyl chloride to a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 40ml, 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 3.6g of the above product and 10ml of octylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 4.08 g of needle-like white solid 2-cyanoacetyloctylamine, with a yield of 47.1%.

MS: m/z=195.6

¹ H NMR (400MHz, CDCl ₃ , δ) 8.11(br, 1H), 3.40(s, 2H), 3.26(qr, 2H), 1.54(q, 2H), 1.1(m, 10H), 0.81(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 1.2ml of N,N-dimethylformamide (DMF) and 10ml of dichloroethane into a 250ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 2.5 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 2 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. 5.7 mmol of hexathiophene was dissolved in 15 ml of dichloroethane, and then added to the above light yellow solution, and reacted at room temperature for 12 h. Add 50ml of 1M NaOH solution to adjust pH=8-9, then stir at 90°C for 2h. Extract with 30ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then it was separated by column chromatography, the eluent was n-hexane:dichloromethane=3:2 (volume ratio), and the solvent was evaporated to dryness to obtain 2.914 g of solid product with a yield of 86.3%.

MS: m/z=550.2

¹ H NMR (DMSO-d6, ppm): 9.59(s, 2H), 7.17(d, 2H, J=3.9Hz), 7.70(s, 2H), 7.10(d, 8H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 18 mmol of the product of 1) reaction and 3 mmol of the product of 2) reaction in 10 ml of chloroform, add 0.6 mmol of catalyst triethylamine (TEA), heat at 85 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=2;5 (volume ratio), and 4.11 g of the final product 6T-DCNC ₈ was obtained with a yield of 86.3%.

MS: m/z=906.8

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.15(s, 2H) 8.0(s, 2H), 7.67(s, 2H), 7.34(s, 2H), 7.04(d, 8H), 2.87(t, 2H), 1.57(m, 4H), 1.30-1.33(m, 20H), 0.91(t, 6H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:44, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from red to blue; when a negative voltage is applied, the color changes from blue to red, which is reversible.

Example 5 Oligothiophene derivative electrochromic material 9T-DCNC ₈ and its preparation method:

1) Add 5g of cyanoacetic acid, 40ml of ethanol, and 0.1g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 20ml of 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 2g of the above product and 5ml of octylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 2.11 g of needle-like white solid 2-cyanoacetyloctylamine, with a yield of 46.7%.

MS: m/z=195.7

¹ H NMR (400MHz, CDCl ₃ , δ) 8.13(br, 1H), 3.66(s, 2H), 3.33(qr, 2H), 1.51(q, 2H), 1.31(m, 10H), 0.97(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 1.0 ml of N, N-dimethylformamide (DMF) and 10 ml of dichloroethane into a 250 ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.0 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 2 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 3 mmol of nonathiophene in 10 ml of dichloroethane, then add it to the above light yellow solution, and react at room temperature for 12 h. Add 45ml of 1M NaOH solution to adjust pH=8-9, then stir at 90°C for 2h. Extract with 25ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then it was separated by column chromatography, the eluent was n-hexane:dichloromethane=3:1 (volume ratio), and the solvent was evaporated to dryness to obtain 1.815 g of solid product with a yield of 76.1%.

MS: m/z=796.3

¹ H NMR (DMSO-d6, ppm): 9.67(s, 2H), 7.21(d, 2H, J=3.9Hz), 7.76(s, 2H), 7.20(d, 14H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 15 mmol of the product of 1) reaction and 2 mmol of the product of 2) reaction in 10 ml of chloroform, add 0.5 mmol of catalyst triethylamine (TEA), heat at 85 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=1:5 (volume ratio) to obtain 1.89 g of the final product 9T-DCNC ₈ with a yield of 82%.

MS: m/z=1152.6

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.1(s, 2H) 8.10(s, 2H), 7.59(s, 2H), 7.13(s, 2H), 7.30(d, 14H), 2.96(t, 2H), 1.55(m, 4H), 1.28-1.43(m, 20H), 0.89(t, 6H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:40, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from orange to blue; when a negative voltage is applied, the color changes from blue to orange, which is reversible.

Example 6 Oligothiophene derivative electrochromic material 9T-DCNC ₈ and its preparation method:

1) Add 15g of cyanoacetic acid, 40ml of ethanol, and 0.4g of thionyl chloride into a 250ml three-neck flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 40ml of 0.5M NaHCO ₃ solution. Then, 50 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=3:2 (volume ratio), and the product was a light yellow liquid. Add 8g of the above product and 15ml of octylamine into a 250ml three-necked flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 3.41 g of needle-like white solid 2-cyanoacetyloctylamine, with a yield of 44.7%.

MS: m/z=195.8

¹ H NMR (400MHz, CDCl ₃ , δ) 8.22(br, 1H), 3.19(s, 2H), 3.42(qr, 2H), 1.61(q, 2H), 1.25(m, 10H), 0.59(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 1.8ml of N,N-dimethylformamide (DMF) and 10ml of dichloroethane into a 250ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.0 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 2 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 5 mmol of nonathiophene in 15 ml of dichloroethane, then add it to the above light yellow solution, and react at room temperature for 12 h. Add 50ml of 1M NaOH solution to adjust pH=8-9, then stir at 90°C for 2h. Extract with 20ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then it was separated by column chromatography, the eluent was n-hexane:dichloromethane=3:1 (volume ratio), and the solvent was evaporated to dryness to obtain 2.82 g of solid product with a yield of 71.4%.

MS: m/z=796.4

¹ H NMR (DMSO-d6, ppm): 9.94(s, 2H), 7.43(d, 2H, J=3.9Hz), 7.91(s, 2H), 7.40(d, 14H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 20 mmol of the product of 1) reaction and 3 mmol of the product of 2) reaction in 10 ml of chloroform, add 0.7 mmol of catalyst triethylamine (TEA), heat at 85 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=1;4 (volume ratio), and 2.36 g of the final product 9T-DCNC ₈ was obtained with a yield of 68.4%.

MS: m/z=1152.2

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.13(s, 2H) 8.0(s, 2H), 7.96(s, 2H), 7.43(s, 2H), 7.07(d, 14H), 2.91(t, 2H), 1.41(m, 4H), 1.21-1.29(m, 20H), 0.99(t, 6H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:40, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant.

The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from orange to blue; when a negative voltage is applied, the color changes from blue to orange, which is reversible.

Example 7 Oligothiophene derivative electrochromic material 3T-DCNC ₅ and its preparation method:

1) Add 5g of cyanoacetic acid, 40ml of ethanol, and 0.1g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 20ml of 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 2g of the above product and 26mmol pentylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol to obtain 2.09 g of needle-like white solid 2-cyanoacetylpentylamine, with a yield of 53.1%.

MS: m/z=153.4

¹ H NMR (400MHz, CDCl ₃ , δ) 8.88(br, 1H), 3.44(s, 2H), 3.71(qr, 2H), 1.61(q, 2H), 1.41(m, 4H), 0.89(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 0.5 ml of N,N-dimethylformamide (DMF) and 3 ml of dichloroethane into a 250 ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.2 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 1 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 3mmol of trithiophene in 4ml of dichloroethane, then add to the above light yellow solution, and react at room temperature for 12h. Add 20ml of 1M NaOH solution to adjust pH=8-9, then stir at 85°C for 2h. Extract with 20ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then separated by column chromatography, the eluent is n-hexane:dichloromethane=3:1 (volume ratio), and the solvent is evaporated to dryness to obtain the solid product 5,5-dialdehyde-2,2':5',2 "-trithiophene 0.876g, productive rate 87%.

MS: m/z=304.7

¹ H NMR (DMSO-d6, ppm): 9.97(s, 2H), 8.41(d, 2H, J=3.9Hz), 7.49(s, 2H), 7.71(d, 2H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 10 mmol of the product of 1) reaction and 2 mmol of the product of 2) reaction in 5 ml of chloroform, add 0.2 mmol of catalyst triethylamine (TEA), heat at 80 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=1;4 (volume ratio) to obtain 1.184 g of the final product 3T-DCNC ₅ with a yield of 91%.

MS: m/z=616.7

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.24(s, 2H), 7.67(s, 2H), 7.51(s, 2H), 7.57(d, 2H), 7.41(m, 4H), 7.16(s, 2H), 0.81-0.98(m, 18H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:40, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from yellow to blue; when a negative voltage is applied, the color changes from blue to yellow, which is reversible.

Example 8 Oligothiophene derivative electrochromic material 6T-DCNC ₁₂ and its preparation method:

1) Add 5g of cyanoacetic acid, 40ml of ethanol, and 0.1g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 20ml of 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 2g of the above product and 27mmol dodecylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol, and the obtained product was 2.86 g of needle-like white solid 2-cyanoacetyl dodecylamine, and the yield was 44.3%.

MS: m/z=251.1

¹ H NMR (400MHz, CDCl ₃ , δ) 8.41(br, 1H), 3.44(s, 2H), 3.21(qr, 2H), 1.63(q, 2H), 1.21(m, 18H), 0.90(t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 0.7ml of N,N-dimethylformamide (DMF) and 5ml of dichloroethane into a 250ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.5 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 2 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 3 mmol of hexathiophene in 6 ml of dichloroethane, then add it to the above light yellow solution, and react at room temperature for 12 h. Add 30ml of 1M NaOH solution to adjust pH=8-9, then stir at 90°C for 2h. Extract with 20ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then it was separated by column chromatography, the eluent was n-hexane:dichloromethane=3:1 (volume ratio), and the solvent was evaporated to dryness to obtain 1.475 g of solid product with a yield of 84.1%.

MS: m/z=550.4

¹ H NMR (DMSO-d6, ppm): 9.67(s, 2H), 7.13(d, 2H, J=3.9Hz), 7.64(s, 2H), 7.20(d, 8H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 10 mmol of the product of 1) reaction and 2 mmol of the product of 2) reaction in 5 ml of chloroform, add 0.3 mmol of catalyst triethylamine (TEA), heat at 85 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried, separated by column chromatography, and the eluent was n-hexane:dichloromethane=1; 5 (volume ratio), and the final product 6T-DCNC ₁₂ was 2.671g, and the yield was 81.3%.

MS: m/z=1018.1

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.14(s, 2H) 8.0(s, 2H), 7.67(s, 2H), 7.23(s, 2H), 7.40(d, 8H), 2.86(t, 2H), 1.55(m, 4H), 1.27-1.43(m, 36H), 0.86(t, 6H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: firstly, an electrochromic gel is prepared by anhydrous tetra-n-butylammonium perchlorate, ethanol and an electrochromic compound at a mass ratio of 3:11:40, and the liquid electrolyte and gel electrochromic The compound is mixed, and the gel will absorb the liquid and wrap it in it. Then the gel containing the electrolyte is evenly coated on one piece of ITO glass, covered with another piece of ITO glass, and finally sealed with a sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from red to blue; when a negative voltage is applied, the color changes from blue to red, which is reversible.

Example 9 Oligothiophene derivative electrochromic material 9T-DCNC ₁₈ and its preparation method:

1) Add 5g of cyanoacetic acid, 40ml of ethanol, and 0.1g of thionyl chloride into a 250ml three-necked flask, and reflux for 5h; after the reaction is completed, cool the mixture to room temperature, and add 20ml of 0.5M NaHCO ₃ solution. Then, 20 ml of petroleum ether was added to extract the organic matter, and the organic layer was washed 3 times with saturated NaCl solution and water, then dried with anhydrous MgSO ₄ , and filtered. The crude product obtained by the above operations was separated and purified by column chromatography, the eluent used was petroleum ether:ethyl acetate=4:1 (volume ratio), and the product was a light yellow liquid. Add 2g of the above product and 28mmol of octadecylamine into a 250ml three-neck flask, and reflux for 12h. After filtration, the precipitate was recrystallized with ethanol, and the obtained product was 3.06 g of needle-like white solid 2-cyanoacetyl octadecylamine, and the yield was 41.4%.

MS: m/z=335.7

¹ H NMR (400MHz, CDCl ₃ , δ) 8.43(br, 1H), 3.31(s, 2H), 3.21(qr, 2H), 1.57(q, 2H), 1.28-1.307(m, 30H), 0.79( t, 3H).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

2) Add 1.0 ml of N, N-dimethylformamide (DMF) and 10 ml of dichloroethane into a 250 ml three-necked flask, and place the three-necked flask in an ice-water bath at 0°C. Then, 1.0 ml of catalyst POCl ₃ was added dropwise thereto, and stirred for 2 h. The mixture was removed from the ice bath and gradually warmed to 40 °C until the solution turned pale yellow. Dissolve 3 mmol of nonathiophene in 10 ml of dichloroethane, then add it to the above light yellow solution, and react at room temperature for 12 h. Add 45ml of 1M NaOH solution to adjust pH=8-9, then stir at 90°C for 2h. Extract with 25ml CH ₂ Cl ₂ , wash with water, dry with anhydrous MgSO ₄ , and filter. Then it was separated by column chromatography, the eluent was n-hexane:dichloromethane=3:1 (volume ratio), and the solvent was evaporated to dryness to obtain 1.815 g of solid product with a yield of 76.1%.

MS: m/z=796.1

¹ H NMR (DMSO-d6, ppm): 9.67(s, 2H), 7.11(d, 2H, J=3.9Hz), 7.76(s, 2H), 7.70(d, 14H, J=3.9Hz).

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

3) Dissolve 15 mmol of the product of 1) reaction and 2 mmol of the product of 2) reaction in 10 ml of chloroform, add 0.5 mmol of catalyst triethylamine (TEA), heat at 85 ° C, and reflux for 12 h; the organic layer is washed with brine, anhydrous MgSO ₄ was dried and separated by column chromatography. The eluent was n-hexane:dichloromethane=1:5 (volume ratio), and 3.03 g of the final product 9T-DCNC ₁₈ was obtained with a yield of 74.1%.

MS: m/z=1432.7

¹ H-NMR (400MHz, CDCl ₃ , δ) 8.11(s, 2H) 8.08(s, 2H), 7.606(s, 2H), 7.35(s, 2H), 7.40(d, 14H), 2.46(t, 2H), 1.59(m, 4H), 1.19-1.43(m, 40H), 1.11-1.17(m, 20H), 0.97(t, 6H)

Instruments used: mass spectrometry (MS) liquid chromatography-mass spectrometry, specification Agilent1100, produced by Bruker, Germany; hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specified AVANCE III HD400, produced by Bruker, Germany.

The gel prepared by using the product is assembled into a solid-state electrochromic device, and the device structure is: ITO glass/gel electrochromic layer/ITO glass. Device preparation process: first mix the liquid electrolyte with the gel electrochromic compound, the gel will absorb the liquid and wrap it in it, then evenly coat the gel containing the electrolyte on a piece of ITO glass, cover another piece of ITO glass, Finally seal it with sealant. The preparation process of the device is simple and does not require spin coating to form a film. Since there is no liquid electrolyte, the device is not prone to leakage. When a positive voltage is applied, the color of the device changes from red to blue; when a negative voltage is applied, the color changes from blue to red, which is reversible.

Claims (9)

1. Uniformpoly thiophene derivative electrochromic material, it is characterised in that with following molecular structure：

N=1-3, m=5-18.

2. the preparation method of Uniformpoly thiophene derivative electrochromic material described in claim 1, it is characterised in that including following step Suddenly：

1) cyanoacetic acid, ethanol and thionyl chloride are mixed, flow back 3-5h；After the completion of reaction, mixture is cooled to room temperature, plus Enter NaHCO₃Solution；Petroleum ether extraction organic matter is added, then organic layer saturation NaCl solution and water washing are dried, filtered； Obtained crude product is purified by column chromatography for separation, using petroleum ether and ethyl acetate as elution, weak yellow liquid is obtained； Alkylamine is added, flow back 10-12h；Filtering, sediment uses ethyl alcohol recrystallization again, obtains 2- cyano-acetamide octyl amine；

2) DMF and dichloroethanes are mixed, are placed in 0-5 DEG C of ice-water bath；Then, catalyst POCl is added dropwise₃, Stir 1-2h；Mixture is removed from ice bath, 35-40 DEG C is gradually warming up to until solution is changed into faint yellow；By thiophene oligomerisation Thing is dissolved in dichloroethanes, is then added in the yellow solution, 10-12h is reacted at room temperature；Regulation pH value is 8-9, so Afterwards, 1-2h is stirred at 85-90 DEG C；Use CH₂Cl₂Extraction, washing, dry, filtering；Then use column chromatography, eluant, eluent is just Hexane and dichloromethane, solvent evaporated obtain solid product dialdehyde-based thiophene oligomers；

3) take step 1) gained 2- cyano-acetamide octyl amine and step 2) gained dialdehyde-based thiophene oligomers be dissolved in three chloromethanes In alkane, triethylamine is added, 80-85 DEG C is heated, flow back 12-15h；Organic layer is washed with salt, is dried, column chromatography for separation, eluent For n-hexane and dichloromethane, revolving obtains Uniformpoly thiophene derivative.

3. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 1) in, cyanoacetic acid and the thionyl chloride mass ratio is 15-70:1；Every gram of thionyl chloride adds ethanol 100-600ml and 50- 400mlNaHCO₃Solution；NaHCO₃The concentration of solution is 0.2-0.6M.

4. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 1) in, the anhydrous MgSO of drying₄Dry；The organic layer is washed 2-4 times respectively with saturation NaCl solution and water washing；Institute The volume ratio for stating petroleum ether and ethyl acetate is 3-4:1-2.

5. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 1) in, every gram of weak yellow liquid adds 6-15mmol alkylamines.

6. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 2) in, the DMF, dichloroethanes mixing and catalyst POCl₃Volume ratio be 1:2-10：0.8-3；Often Ml DMFs add 2-10mmol thiophene oligomers；The thiophene oligomers are three thiophene 3T-DCNC_m, six Thiophene 6T-DCNC_mOr nine thiophene 9T-DCNC_m, wherein m=5-18.

7. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 2) in, the thiophene oligomers per mmol add 1-3ml dichloroethanes；The volume ratio of the n-hexane and dichloromethane is 1-3:1- 2；The anhydrous MgSO of drying₄Dry；The regulation pH value is that 8-9 is adjusted by NaOH solution, the concentration of NaOH solution For 1-2M.

8. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 3) in, the mol ratio of dialdehyde-based thiophene oligomers and 2- cyano-acetamide octyl amine is 1：3-10；It is neat per mmol dialdehyde-based thiophene Polymers adds 0.06-0.2mmol catalyst of triethylamine.

9. the preparation method of Uniformpoly thiophene derivative electrochromic material according to claim 1, it is characterised in that step 3) in, the anhydrous MgSO of drying₄Dry；The n-hexane and dichloromethane=volume ratio be 1-2:2-4.