CN112094400B - Orange red-green display electrochromic material based on quinacridone-bithiophene and preparation method thereof - Google Patents
Orange red-green display electrochromic material based on quinacridone-bithiophene and preparation method thereof Download PDFInfo
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Abstract
An orange red-green display electrochromic material based on quinacridone-bithiophene and a preparation method thereof, wherein the monomer is shown as a formula (I). The quinacridone-bithiophene has a rigid planar structure, has higher electrochemical activity, and is easy to electrochemically polymerize into a film. The film can realize orange-red to green reversible color change under the step voltage of 0-1.1V, the coloring time of 467nm and 707nm is respectively 3.59s and 2.82s, the fading time is respectively 0.94s and 1.31s, the contrast of the film under 707nm can reach 40%, and the contrast is hardly attenuated after 150 cycles, so that the film has good electrochemical cycle stability, is an excellent electrochromic material, and has potential application prospect in the display fields of electronic paper, electronic labels and the like.
Description
Field of the art
The invention relates to a novel electrochromic material based on quinacridone-bithiophene and a preparation method thereof.
(II) background art
Electrochromic refers to the fact that under the action of an applied voltage, oxidation-reduction reaction occurs due to charge injection and extraction, and meanwhile, the optical absorption of electrolyte ions changes in the visible light-near infrared region, and the change is macroscopically represented by reversible changes of color and transmittance. Compared with inorganic electrochromic materials, the conductive polymer in the organic electrochromic materials is paid attention to because of the advantages of abundant structural types, higher response speed, adjustable energy band, good processability and the like. The polythiophene conductive polymer has the advantages of easy modification of structure, simple synthesis and the like, and is a widely studied electrochromic material at present. In general, tetrathiofuran can be changed from yellow to blue-green under the drive of voltage, but the color is not bright enough and pure.
The quinacridone compound as a common electron acceptor structure has the advantages of good molecular planeness, easy structure modification, good physical and chemical stability, bright color and the like, and has been widely used in the organic photoelectric field, but the research of the quinacridone compound in the electrochromic field has never been reported. According to the invention, quinacridone is taken as an electron acceptor, bithiophene is taken as an electron donor, a novel donor-acceptor-donor (D-A-D) organic molecule based on quinacridone bithiophene is designed and synthesized, and the corresponding polymer electrochromic material is prepared by electrochemical polymerization.
(III) summary of the invention
In order to overcome the defects of the prior art, the invention aims to provide an orange red-green display electrochromic material based on quinacridone-bithiophene and a preparation method thereof.
The technical scheme of the invention is as follows:
orange-red-green display electrochromic material based on quinacridone-bithiophene, as shown in formula (I):
a method for preparing a quinacridone-bithiophene-based orange red-green display electrochromic material, comprising the following steps:
(1) The quinacridone (II) is subjected to alkylation reaction to obtain a quinacridone derivative C10QA (III), wherein the structural formulas are respectively as follows:
(2) Bromination reaction of C10QA (III) and N-bromosuccinimide (NBS) is carried out to obtain a brominated product C10QA-2Br (IV), wherein the structural formula of the C10QA-2Br is as follows:
(3) The bithiophene reacts with tributyl tin chloride to generate tin-plated bithiophene (V), and the tin-plated bithiophene has the following structural formula:
(4) C10QA-2Br (IV) and tin-base dithiophene (V) are subjected to a stinlle coupling reaction to generate a target product C10QA-2DT (I);
(5) The novel electrochromic material based on quinacridone-bithiophene is prepared by electrochemical polymerization by taking C10QA-2DT (I) as a monomer.
Further, the operation process of the step (1) is as follows:
sequentially adding quinacridone, 1-bromodecane, sodium hydroxide, tetrabutylammonium bromide and dimethyl sulfoxide into a single-mouth bottle, stirring at normal temperature for 24 hours, and performing post-treatment to obtain C10QA;
the ratio of the amounts of the materials added into the quinacridone, the 1-bromodecane, the sodium hydroxide and the tetrabutylammonium bromide is 1:3.5-4:3.5-4:0.4;
the adding volume of the dimethyl sulfoxide is 8-12 mL/g based on the mass of the quinacridone;
the post-reaction treatment method comprises the following steps: extracting with water and dichloromethane for three times after the reaction is finished, concentrating the extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, dichloromethane and petroleum ether as mobile phases, collecting eluent containing target compounds, removing solvent by rotary evaporation, and drying;
the volume ratio of the methylene dichloride to the petroleum ether is 2-2.5:1.
Still further, the operation procedure of the step (2) is as follows:
under the protection of nitrogen, sequentially adding C10QA, NBS and N, N-dimethylformamide DMF into a reaction bottle, heating and refluxing, carrying out light-shielding reaction for 24 hours, and carrying out post-treatment to obtain a brominated product C10QA-2Br;
the ratio of the amounts of the materials fed into the C10QA and the NBS is 1:3.5-4;
the DMF adding volume is 10-15 mL/g based on the mass of C10QA;
the post-reaction treatment method comprises the following steps: extracting with water and dichloromethane for three times after the reaction is finished, concentrating the extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, dichloromethane and petroleum ether as mobile phases, collecting eluent containing target compounds, removing solvent by rotary evaporation, and drying;
the volume ratio of the methylene dichloride to the petroleum ether is 1-1.2:1.
Further, the operation process of the step (3) is as follows:
under the protection of nitrogen, bithiophene is dissolved in anhydrous and anaerobic Tetrahydrofuran (THF), then n-hexane solution of n-butyllithium is dripped at the temperature of minus 78 ℃, the mixture is stirred for 1 hour under heat preservation, tributyltin chloride is added, the mixture is stirred for 1 hour under heat preservation, then the mixture is naturally heated to normal temperature and stirred for 12 hours, and the reaction solution is subjected to post-treatment to obtain the tin bithiophene.
The ratio of the amounts of the materials added into the bithiophene, the n-butyllithium and the tributyl tin chloride is 1:1.05-1.1:1.3;
the addition amount of THF is 9-12 mL/g based on the mass of bithiophene;
the post-reaction treatment method comprises the following steps: after the reaction is finished, taking aluminum oxide as a stationary phase and methylene dichloride as a mobile phase, collecting eluent containing a target compound, and removing the solvent by rotary evaporation.
Specifically, the operation process of the step (4) is as follows:
under the protection of nitrogen, adding C10QA-2Br, tin-modified bithiophene, tetra (triphenylphosphine) palladium and DMF into a reaction bottle, heating and refluxing for 12 hours, and performing post-treatment to obtain a target product C10QA-2DT.
The ratio of the amounts of the materials added into the C10QA-2Br and the tin-modified bithiophene is 1:3.5-4;
the added volume of the DMF is 20-30 mL/g based on the mass of C10QA-2Br;
the post-reaction treatment method comprises the following steps: extracting with water and chloroform for three times after the reaction is finished, concentrating the extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, chloroform and petroleum ether as mobile phases, collecting eluent containing target compounds, removing solvent by rotary evaporation, and drying;
the volume ratio of chloroform to petroleum ether is 0.9-1:1.
Specifically, the operation procedure of the step (5) is as follows:
c10QA-2DT shown in the formula (I) is dissolved in a mixed solution of chloroform and acetonitrile, tetrabutylammonium hexafluorophosphate is added as a supporting electrolyte, the sweeping speed is 100mV/s, and the membrane is formed by electrochemical polymerization by a cyclic voltammetry, wherein the voltage range is 0-1.3V, and the cycle number is 4-12;
the concentration of the C10QA-2DT is 0.1-2 mmol/L;
the volume ratio of the mixed solution is that: acetonitrile=9:1;
the concentration of the tetrabutylammonium hexafluorophosphate is 0.05-0.5 mol/L.
The beneficial effects of the invention are as follows: a method for preparing novel electrochromic materials from orange red to green display by electrochemical polymerization of a donor-acceptor-donor (D-A-D) quinacridone-bithiophene derivative represented by formula (I) is provided. The quinacridone-bithiophene has a rigid planar structure, has higher electrochemical activity, and is easy to electrochemically polymerize into a film. The film can realize orange-red to green reversible color change under the step voltage of 0-1.1V, the coloring time of 467nm and 707nm is respectively 3.59s and 2.82s, the fading time is respectively 0.94s and 1.31s, the contrast of the film under 707nm can reach 40%, and the contrast is hardly attenuated after 150 cycles, so that the film has good electrochemical cycle stability, is an excellent electrochromic material, and has potential application prospect in the display fields of electronic paper, electronic labels and the like.
(IV) description of the drawings
FIG. 1 is a synthetic route to quinacridone-bithiophene derivatives according to the invention;
FIG. 2 is a graph of electrochemical polymerization of quinacridone-bithiophene derivatives according to the present invention;
FIG. 3 is a graph of the UV-visible absorption spectra of a polymeric film of quinacridone-bithiophene according to the present invention at various voltages;
FIG. 4 is an electrochromic property of a polymeric film of quinacridone-bithiophene according to the present invention.
(fifth) detailed description of the invention
The following describes the technical scheme of the present invention with specific examples, but the scope of the present invention is not limited thereto:
example 1: synthesis of C10QA
3.12g (0.01 mol) of quinacridone, 8.84g (0.04 mol) of 1-bromodecane, 1.6g (0.04 mol) of sodium hydroxide, 1.3g (0.004 mol) of tetrabutylammonium bromide and 30mL of dimethyl sulfoxide are sequentially added into a 100mL single-neck flask, stirring is carried out for 24 hours at normal temperature, water and dichloromethane are used for extraction three times after the reaction is finished, the extract is concentrated and dehydrated by anhydrous sodium sulfate, column chromatography purification is carried out, silica gel is used as a stationary phase, dichloromethane and petroleum ether are used as mobile phases, eluent containing a target compound is collected, solvent is removed by rotary evaporation, and drying is carried out, thus obtaining orange-red solid C10QA with the yield of 85%. The characterization structure of the validation material is as follows: 1 H NMR(500MHz，CDCl 3 )δ8.82(s，2H)，8.61(dd，2H)，7.80(td，2H)，7.56(d，2H)，7.30(t，2H)，4.55(m，4H)，2.0(m，4H)，1.64(m，4H)，1.47(m，4H)，1.42-1.20(m，20H)，0.90(t，6H)。
example 2: synthesis of C10QA-2Br
C10QA 1.19g (0.002 mol) and NBS 1.25g (0.007 mol) were added to a 100mL double-necked flask, 10mL DMF was added under nitrogen protection, the mixture was refluxed under heating, and the reaction was kept away from light for 24 hours, after the reaction was completed, the three were extracted with water and methylene chlorideConcentrating the extract, removing water with anhydrous sodium sulfate, purifying by column chromatography, collecting eluent containing target compound with silica gel as stationary phase, dichloromethane and petroleum ether as mobile phase, removing solvent by rotary evaporation, and drying to obtain orange-red solid C10QA-2Br with a yield of 80%. The characterization structure of the validation material is as follows: 1 H NMR(500MHz，CDCl 3 )δ8.78(s，2H)，8.70(s，2H)，7.85(d，2H)，7.45(d，2H)，4.55(m，4H)，2.0(m，4H)，1.64(m，4H)，1.47(m，4H),，1.42-1.20(m，20H)，0.90(t，6H)。
example 3: synthesis of tin-bonded bithiophene
2g (0.014 mol) of bithiophene was dissolved in 20mL of anhydrous and anaerobic THF under nitrogen protection, 6.16mL (0.0148 mol, 2.4M) of n-hexane solution of n-butyllithium was then added dropwise at-78℃and stirred for 1 hour under heat preservation, 5.9g (0.018 mol) of tributyltin chloride was then added and stirred for 1 hour under heat preservation, followed by natural rising to normal temperature and stirring for 12 hours. After the reaction, alumina is used as a stationary phase, methylene dichloride is used as a mobile phase, eluent containing a target compound is collected, and the solvent is distilled off to obtain liquid tin-modified bithiophene which is directly applied to the example 4.
Example 4: synthesis of C10QA-2DT
C10QA-2Br 0.6g (0.8 mmol) and a small amount of tetrakis (triphenylphosphine) palladium were added to a 100mL double-necked flask, and 1.46g (3.2 mmol) of bithiophene tin and 20mL of DMF were added under nitrogen protection, and the mixture was heated under reflux for 12 hours. After the reaction is finished, extracting with water and chloroform for three times, concentrating the extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, chloroform and petroleum ether as mobile phases, collecting eluent containing a target compound, removing the solvent by rotary evaporation, and drying to obtain red solid C10QA-2DT, wherein the yield is 65%. The characterization structure of the validation material is as follows: 1 H NMR(500MHz,CDCl 3 )δ8.77(s,2H),8.75(d,J＝2.4Hz,2H),7.97(dd,J＝8.9,2.4Hz,2H),7.55(d,J＝9.1Hz,2H),7.35(d,J＝3.7Hz,2H),7.27–7.25(m,4H),7.21(d,J＝3.7Hz,2H),7.08(dd,J＝5.0,3.6Hz,2H),4.57(s,4H),2.26–2.22(m,4H),1.61(m,4H),1.55–1.24(m,24H),0.94–0.87(m,6H)。
example 5: electrochemical polymerization of C10QA-2DT
Monomer C10QA-2DT 4.61mg (0.5 mmol/L) and electrolyte tetrabutylammonium hexafluorophosphate 0.387g (0.1 mol/L) were added into a 10mL volumetric flask, the volume was fixed with a mixture of chloroform and acetonitrile (volume ratio: 9:1), and after complete dissolution, electrochemical polymerization was carried out for 3min with the electrochemical polymerization curve shown in FIG. 2. ITO glass (0.9 x 4 cm) is used as a working electrode, a platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, and a corresponding quinacridone-bithiophene derivative polymer film is obtained through cyclic voltammetry polymerization, wherein the voltage range is 0-1.3V, and the cycle number is 10. The membrane was dedoped in a blank solution (0.387 g tetrabutylammonium hexafluorophosphate dissolved in 10mL acetonitrile) for 1min, and then the electrolyte and oligomers on the membrane surface were washed off with a mixture of chloroform and acetonitrile.
Example 6: performance testing based on quinacridone-bithiophene electrochromic materials
0.387g (0.1 mol/L) of tetrabutylammonium hexafluorophosphate is added into a 10mL volumetric flask, acetonitrile is used for constant volume, the volumetric flask is used as a blank solution, ITO glass covered with the prepared polymer film is used as a working electrode, ag/AgCl is used as a reference electrode, and electrochemical, optical and electrochromic performance tests are carried out. The result shows that: the quinacridone-bithiophene polymer film can realize orange-red to green reversible color change under the step voltage of 0-1.1V, the ultraviolet-visible absorption curve is shown in figure 3, the coloring time at 467nm and 707nm is respectively 3.59s and 2.82s, the fading time is respectively 0.94s and 1.31s, the contrast of the film at 707nm can reach 40 percent, as shown in figure 4, and the contrast hardly decays after 150 cycles, and the film has good electrochemical stability.
Claims (7)
1. Orange red-green display electrochromic material based on quinacridone-bithiophene, which is characterized in that the monomer is shown as a formula (I):
2. a method for preparing the orange-red-green display electrochromic material of quinacridone-bithiophene according to claim 1, wherein the preparation method comprises the following steps:
(1) The quinacridone (II) is subjected to alkylation reaction to obtain a quinacridone derivative C10QA (III), wherein the structural formulas are respectively as follows:
(2) Bromination reaction of C10QA (III) and N-bromosuccinimide (NBS) is carried out to obtain a brominated product C10QA-2Br (IV), wherein the structural formula of the C10QA-2Br is as follows:
(3) The bithiophene reacts with tributyl tin chloride to generate tin-plated bithiophene (V), and the tin-plated bithiophene has the following structural formula:
(4) C10QA-2Br (IV) and tin-base dithiophene (V) are subjected to a stinlle coupling reaction to generate a target product C10QA-2DT (I);
(5) The novel electrochromic material based on quinacridone-bithiophene is prepared by electrochemical polymerization by taking C10QA-2DT (I) as a monomer.
3. The method of claim 2, wherein the step (1) is performed as follows:
sequentially adding quinacridone, 1-bromodecane, sodium hydroxide, tetrabutylammonium bromide and dimethyl sulfoxide into a single-mouth bottle, stirring at normal temperature for 24 hours, and performing post-treatment to obtain C10QA; the ratio of the amounts of the materials added into the quinacridone, the 1-bromodecane, the sodium hydroxide and the tetrabutylammonium bromide is 1:3.5-4:3.5-4:0.4; the adding volume of the dimethyl sulfoxide is 8-12 mL/g based on the mass of the quinacridone; the post-reaction treatment method comprises the following steps: after the reaction is finished, extracting with water and dichloromethane for three times, concentrating the extract, removing water by using anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, taking dichloromethane and petroleum ether as mobile phases, collecting eluent containing target compounds, removing solvent by rotary evaporation, and drying.
4. The method of claim 2, wherein the step (2) is performed as follows: under the protection of nitrogen, sequentially adding C10QA, NBS and N, N-dimethylformamide DMF into a reaction bottle, heating and refluxing, carrying out light-shielding reaction for 24 hours, and carrying out post-treatment to obtain a brominated product C10QA-2Br; the ratio of the amounts of the materials fed into the C10QA and the NBS is 1:3.5-4; the DMF adding volume is 10-15 mL/g based on the mass of C10QA; the post-reaction treatment method comprises the following steps: after the reaction is finished, extracting with water and dichloromethane for three times, concentrating the extract, removing water by using anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, taking dichloromethane and petroleum ether as mobile phases, the volume ratio of the dichloromethane to the petroleum ether is 1-1.2:1, collecting eluent containing target compounds, removing the solvent by rotary evaporation, and drying.
5. The method of claim 2, wherein the step (3) is performed as follows: under the protection of nitrogen, bithiophene is dissolved in anhydrous and anaerobic tetrahydrofuran THF, then n-hexane solution of n-butyllithium is dripped at the temperature of minus 78 ℃, the heat preservation and stirring are carried out for 1 hour, tributyltin chloride is added, the heat preservation and stirring are continued for 1 hour, then the temperature is naturally raised to normal temperature, the stirring is carried out for 12 hours, and the reaction solution is subjected to post treatment to obtain tin bithiophene; the ratio of the amounts of the materials added into the bithiophene, the n-butyllithium and the tributyl tin chloride is 1:1.05-1.1:1.3; the addition amount of THF is 9-12 mL/g based on the mass of bithiophene; the post-reaction treatment method comprises the following steps: after the reaction is finished, taking aluminum oxide as a stationary phase and methylene dichloride as a mobile phase, collecting eluent containing a target compound, and evaporating the solvent.
6. The method of claim 2, wherein the step (4) is performed as follows: under the protection of nitrogen, adding a bromination product C10QA-2Br, tin-modified bithiophene, tetra (triphenylphosphine) palladium and DMF into a reaction bottle, heating and refluxing for 12 hours, and performing post-treatment to obtain a target product C10QA-2DT; the ratio of the amounts of the materials added into the C10QA-2Br and the tin-modified bithiophene is 1:3.5-4; the added volume of the DMF is 20-30 mL/g based on the mass of C10QA-2Br; the post-reaction treatment method comprises the following steps: after the reaction is finished, extracting with water and chloroform for three times, concentrating the extract, removing water by using anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase, chloroform and petroleum ether as mobile phases, wherein the volume ratio of the chloroform to the petroleum ether is 0.9-1:1, collecting eluent containing target compounds, removing the solvent by rotary evaporation, and drying.
7. The method of claim 2, wherein the step (5) is performed as follows: c10QA-2DT shown in the formula (I) is dissolved in a mixed solution of chloroform and acetonitrile, tetrabutylammonium hexafluorophosphate is added as a supporting electrolyte, the sweeping speed is 100mV/s, and the membrane is formed by electrochemical polymerization by a cyclic voltammetry, wherein the voltage range is 0-1.3V, and the cycle number is 4-12; the concentration of the C10QA-2DT is 0.1-2 mmol/L; in the mixed solution, the volume ratio of chloroform: acetonitrile=9:1; the concentration of the tetrabutylammonium hexafluorophosphate is 0.05-0.5 mol/L.
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