CN117700457A - Electrochromic compound, preparation method and application - Google Patents

Electrochromic compound, preparation method and application Download PDF

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CN117700457A
CN117700457A CN202211084219.5A CN202211084219A CN117700457A CN 117700457 A CN117700457 A CN 117700457A CN 202211084219 A CN202211084219 A CN 202211084219A CN 117700457 A CN117700457 A CN 117700457A
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electrochromic
compound
drying
product
benzene
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孟鸿
邓斌
贺耀武
张超红
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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Abstract

The invention relates to the technical field of electrochromic materials, and provides an electrochromic compound, which takes tetrabipyridine as a basic framework, benzene rings, thiophene, pyrrole, furan and derivatives thereof can be introduced into pyridine, and the electrochemical properties of the material can be regulated and controlled by expanding a conjugated structure; in addition, an asymmetric structure containing an anchoring group is designed, the anchoring group can modify the nano electrode, and the color-changing material is fixed at the electrode end, so that the color-changing speed is not affected by the diffusion structure of the material, and meanwhile, an unsaturated hydrocarbon structure is introduced at the other side, so that the solubility of the material can be improved, and the conjugation degree of the material is further increased. The compound is used as electrochromic material and has the advantages of rich color, fast color changing speed, long service life and the like. The device based on the material composition has the advantages of rich color change, high contrast ratio, high response speed, long service life of the device and the like.

Description

Electrochromic compound, preparation method and application
Technical Field
The invention relates to the technical field of electrochromic materials, in particular to an electrochromic compound and a preparation method thereof, an electrochromic device and a preparation method and application thereof.
Background
Electrochromic material is a material which can be reversibly changed in optical absorption under the action of an applied potential, and has great prospect in applications such as displays, intelligent windows, optical camouflage and the like. The inorganic electrochromic materials and the organic electrochromic materials can be classified by material essence classification. Common inorganic electrochromic materials are tungsten trioxide (WO 3 ) The organic electrochromic material such as Prussian Blue (PB) contains viologen (MV) 2+ ) Conjugated polymers (PEDOT, P3 HT), etc. Unlike thermochromic or photochromic devices, electrochromic exhibits better user control and color adjustment capabilities, making this technology a popular research topic.
Wherein the viologen is in a faded state (MV 2+ ) And coloring state (MV) ) The contrast ratio and the low driving voltage are very excellent, and are widely used in rearview mirrors of vehicles.
However, the current viologen color change materials are to be improved for two main reasons. The first is that the stability of small molecule viologen devices is poor, and due to the strong ion-pi interactions, the viologen radical cations dimerize, resulting in an irreversible fade process. Secondly, the color switching speed is too slow, because the fading speed of the viologen is influenced by the diffusion speed, most of the viologen has larger viscosity and molecular weight, thus leading to slow response speed and being unsuitable for practical application.
Disclosure of Invention
The current commercial electrochromic material mainly comprises viologen compounds, and has slower response speed and low stability. Meanwhile, although the material is already applied to the automobile rearview mirror, for outdoor application scenes, the material is required to meet the color selectivity and high sensitivity of users, so that the material has higher requirements on the fading speed and the stability of devices, and the current electrochromic material cannot meet the requirements of an outdoor intelligent window on the performance of the electrochromic material.
Aiming at the defects, the invention provides an electrochromic compound, a preparation method and application, and a device based on the electrochromic compound has important significance for application scenes needing rich colors and quick response.
The technical scheme of the invention is realized by the following steps: an electrochromic compound is provided, which has the following structural formula:
wherein R is 1 Is a phosphate group (-PO (OH) 2 ) Silicic acid group (-Si (OH)) 3 ) And one of an acetate group (-COOH);
m is a direct bond, or M is selected from benzene, 1, 4-dibromo-2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
R 2 alkenyl or alkynyl;
m and n may be each independently an integer of 0 to 12;
X - selected from chloride, bromide, iodide, triflate anions, perchlorate anions, tetrafluoroborate anions.
Preferably, in one embodiment of the present invention, the electrochromic compound has the structures of the following formulas (a) to (F):
preferably, in one embodiment of the inventionIn embodiments, R of electrochromic compounds 2 Is an unsaturated alkenyl or alkynyl group; the alkenyl group includes a vinyl group (-ch=ch) 2 ) Allyl (-CH) 2 CH=CH 2 ) The method comprises the steps of carrying out a first treatment on the surface of the The alkynyl group includes an ethynyl group (-C≡CH), a propargyl group (-CH) 2 C.ident.CH), 1-propynyl (-C.ident.C-CH) 3 )。
Preferably, in one embodiment of the present invention, the electrochromic compound has any one of the structural formulas shown in formulas (1) to (9):
the invention also provides a preparation method of the electrochromic compound, which comprises the following steps:
reacting and refluxing the compound a with the compound b to obtain a compound c, refluxing the compound c and the compound d in an organic solvent to obtain a compound e, and finally acidifying and hydrolyzing to obtain the final electrochromic compound;
wherein M is a direct bond, or M is selected from benzene, 2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
the structural formula of the compound b is R 3 -(CH2) m -R 4 M is an integer between 0 and 12, R 3 Is any one of I, br and Cl, R 4 Is a substituted phosphate (-PO (OCH) 2 CH 3 ) 2 ) Methylsiloxane (-Si (OCH) 3 ) 3 ) Ethyl acetate (-COOCH) 2 CH 3 ) One of the following;
the structural formula of the compound d is R 2 -(CH2) n -R 5 N is an integer of 0 to 12, R 2 Is alkenyl or alkynyl, R 5 Is any one of I, br and Cl.
Preferably, in one embodiment of the invention, m is 2 or 3 and n is 2 or 3.
Preferably, in one embodiment of the present invention, the structural formula of the compound b is one of the following:
the structural formula of the compound d is one of the following:
preferably, in one embodiment of the invention, the M is at the 2 and/or 5 position from F, CF 3 、OCH 3 、OCF 3 Any one of substituted benzene;
or M is pyrrole substituted by benzene, benzyl and derivatives thereof at the N position;
alternatively, M is 2 and/or the 3 position is defined by CF 3 、OCH 3 、OCF 3 Pyrrole or thiophene of any kind.
The invention also provides an electrochromic device comprising a first conductive layer, a second conductive layer, a semiconductor layer, an electrochromic layer, and an electrolyte layer between the first conductive layer and the second conductive layer; the electrochromic layer uses the electrochromic compound or the electrochromic compound obtained by the preparation method.
Preferably, in one embodiment of the present invention, the first conductive layer and the second conductive layer comprise one of FTO, ITO conductive glass; the semiconductor layer comprises one of titanium dioxide and tin dioxide;
preferably, in one embodiment of the present invention, the semiconductor layer is titanium dioxide;
preferably, in one embodiment of the present invention, the first conductive layer and the second conductive layer are FTOs.
Preferably, in one embodiment of the present invention, the concentration of the material in the electrochromic layer may be 5mg/mL,10mg/mL,15mg/mL,20mg/mL,30mg/mL;
preferably, in one embodiment of the present invention, the electrochromic layer has a material concentration of 10mg/mL;
preferably, in one embodiment of the present invention, the electrolyte layer includes an electrolyte and a solvent. The electrolyte comprises one or more of lithium perchlorate, lithium chloride and lithium bistrifluoromethane sulfonyl imide; the solvent comprises propylene carbonate, tetrahydrofuran, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, ethyl acetate and other high boiling point solvents;
preferably, in one embodiment of the present invention, the electrolyte is lithium chloride;
preferably, in one embodiment of the present invention, the solvent is propylene carbonate;
preferably, in one embodiment of the invention, the concentration of the electrolyte is 0.1M.
Preferably, in one embodiment of the present invention, the preparation process includes: the electrochromic material solution was immersed in the semiconductor layer for grafting for 24 hours, and the electrolyte layer was filled between the semiconductor layer and the second conductive layer.
Preferably, in one embodiment of the present invention, the preparation process includes: coating a semiconductor layer on the first conductive layer, and grafting an electrochromic layer on the semiconductor layer;
preferably, in one embodiment of the present invention, the preparation process includes: the electrochromic device includes a semiconductor layer and a second conductive layer defining a fill space therebetween, the method comprising: and filling the electrolyte layer into the filling space, and sealing to obtain the electrochromic device.
The invention also provides an electrochromic device, and application of the electrochromic device in intelligent windows, rearview mirrors or electronic equipment.
The beneficial effects are as follows:
the electrochromic compound provided by the invention takes tetrabipyridine as a basic framework, benzene ring, thiophene, pyrrole, furan and derivatives thereof can be introduced into pyridine, and the electrochemical property of the material can be regulated and controlled by expanding a conjugated structure; in addition, an asymmetric structure containing an anchoring group is designed, the anchoring group can modify the nano electrode, and the color-changing material is fixed at the electrode end, so that the color-changing speed is not affected by the diffusion structure of the material, and meanwhile, an unsaturated hydrocarbon structure is introduced at the other side, so that the solubility of the material can be improved, and the conjugation degree of the material is further increased. The compound is used as electrochromic material and has the advantages of rich color, fast color changing speed, long service life and the like. The device based on the material composition has the advantages of rich color change, high contrast ratio, high response speed, long service life of the device and the like.
Drawings
FIG. 1 shows a schematic structural diagram of an electrochromic device according to one example of the present application;
FIG. 2 shows a cyclic voltammogram of one of the devices;
fig. 3 shows the optical stability diagram at 600nm of the electrochromic device of one of the devices, the voltage for color switching being-1.5 v,5s, +1.5v,5s, 1000 cycles.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention will now be described in further detail with reference to the drawings and examples.
The synthesis of the target compound comprises four steps:
the first step is to synthesize compound a by reaction with 4-pyridineboronic acid containing either a dibromo or a chloro-substituted M. Wherein M can be a direct bond or benzene ring, thiophene, pyrrole, thienothiophene, thiazole and substituted derivatives thereof,
the reaction equation is as follows:
the second step is to synthesize a viologen compound with an anchoring group on one side, and to react the compound a with at least one of halogenated phosphate, carboxylate and methylsiloxane. Wherein R is 4 Is a substituted phosphate (-PO (OCH) 2 CH 3 ) 2 ) Methylsiloxane (-Si (OCH) 3 ) 3 ) Ethyl acetate (-COOCH) 2 CH 3 ) One of the following; the reaction equation is as follows:
the third step is to obtain a bilateral substituted pyridine derivative, wherein R 2 For unsaturated alkenyl or alkynyl, alkenyl includes vinyl (-ch=ch) 2 ) Allyl (-CH) 2 CH=CH 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Alkynyl groups include ethynyl (-C.ident.CH), propargyl (-CH) 2 C.ident.CH), 1-propynyl (-C.ident.C-CH) 3 ) The reaction equation is as follows:
the fourth step is hydrolysis in an acidic environment, wherein R 1 Is a substituted phosphoric acid (-PO (OH) 2 ) Silicic acid (-Si (OH)) 3 ) And one of carboxylic acids (-COOH), the reaction equation is as follows:
example 1
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 1mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction is completed, ethyl acetate is used for precipitation, and the monosubstituted viologen derivative is obtained. The resulting first step product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a second-step product. Finally, the second step of product is placed in a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(400MHz,DMSO)δ9.08(dd,4H),8.96(dd,4H),5.29(d,2H),5.08(d,2H),4.80(s,2H),2.42(d,2H),1.55-1.48(m,5H)ppm.
example 2
1mol of 2, 5-dibromothiophene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the 2, 5-di (pyridine-4-yl) thiophene. Next, 1mol of 2, 5-di (pyridin-4-yl) thiophene was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying the acetonitrile to obtain the product,dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ for 12 hours in a vacuum drying oven to obtain the product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.91,8.78,7.79,7.60,7.40,6.00,5.93,5.25,5.22,5.21,5.19,4.95,4.93,4.86,4.83,4.63,3.39,3.36,3.31,3.28.
example 3
1mol of 2, 5-dibromo-3, 4-bis (trifluoromethyl) thiophene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (3, 4-bis (trifluoromethyl) thiophene-2, 5-diyl) bipyridine in the first step. Next, 1mol of 4,4' - (3, 4-bis (trifluoromethyl) thiophene-2, 5-diyl) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to the pear-shaped flask in equimolar ratio to propargyl bromide, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added,reflux was carried out at 100℃for 10h. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.81(s,2H),8.76(s,2H),7.80(s,2H),7.65(s,2H),5.93(s,2H),4.67(s,2H),4.63(s,2H),3.27(s,2H),2.94(s,2H),2.64(s,1H).
example 4
1mol of 2, 5-dibromo-thieno [3,2-b]Thiophene, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying with silica gel column to obtain the final product 2, 5-di (pyridin-4-yl) thieno [3,2-b ]]Thiophene. Next 1mol of 2, 5-di (pyridin-4-yl) thieno [3,2-b]Thiophene, 50mL of Acetonitrile (ACN) was poured, followed by slow addition of 0.5mol of (3-bromopropyl) trimethoxysilane. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second step product was then reacted with bromopolyl (Br-CH) 2 C≡ch) was added to the pear-shaped flask in equimolar ratio, and 50mL ACN was added thereto and stirred for 24 hours. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows:
1 H NMR(500MHz,Chloroform-d)δ8.82(s,5H),7.73(s,2H),7.56(s,3H),7.49(s,2H),6.41(s,3H),5.04(d,J=12.5Hz,1H),4.86(d,J=12.5Hz,1H),4.43(s,2H),2.89(s,1H),2.13–2.06(m,4H),2.01(d,J=12.3Hz,1H).
example 5
1mol of 1, 4-dibromobenzene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the filter residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined, poured into an erlenmeyer flask containing anhydrous Na2SO4, dried for 1h, distilled under reduced pressure, and finally purified by a silica gel column to give the first step of product 1, 4-di (pyridin-4-yl) benzene. Next, 1mol of 1, 4-di (pyridin-4-yl) benzene was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of ethyl 4-bromobutyrate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
Of chemical structureThe characterization is as follows: 1 H NMR(500MHz,Chloroform-d)δ9.01(s,2H),8.56(s,2H),7.74(d,J=7.5Hz,4H),7.66(s,4H),6.00(s,1H),5.22(s,2H),4.94(d,J=12.5Hz,1H),4.84(d,J=12.5Hz,1H),4.65(s,2H),2.50(d,J=12.5Hz,1H),2.44(d,J=12.5Hz,1H),2.26(s,2H).
example 6
1mol of 1, 4-dibromo-2, 5-bis (trifluoromethyl) benzene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (2, 5-bis (trifluoromethyl) -1, 4-phenylene) bipyridine in the first step. Next, 1mol of 4,4' - (2, 5-bis (trifluoromethyl) -1, 4-phenylene) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.81(s,2H),8.76(s,2H),7.78(s,2H),7.65(d,J=3.1Hz,4H),5.99(s,1H),5.93(s,2H),5.19(s,2H),4.94(d,J=12.5Hz,1H),4.79(d,J=12.5Hz,1H),4.63(s,2H),3.27(s,2H).
example 7
1mol of 1, 4-dibromo-2, 5-dimethoxybenzene, 3mol of 4-pyridineboronic acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under a nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (2, 5-dimethoxy-1, 4-phenylene) bipyridine in the first step. Next, 1mol of 4,4' - (2, 5-dimethoxy-1, 4-phenylene) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.78(d,J=15.0Hz,5H),7.75(s,3H),7.62(s,3H),7.04(s,2H),6.00(s,1H),5.20(s,2H),4.94(d,J=12.5Hz,1H),4.79(d,J=12.5Hz,1H),4.64(s,2H),3.87(s,6H),2.47(d,J=12.4Hz,1H),2.41(d,J=12.4Hz,1H),2.36(d,J=12.3Hz,1H),2.26(d,J=12.5Hz,1H).
example 8
1mol of 5, 7-dibromo-2, 3-dihydrothieno [3,4-b][1,4]Dioxin, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying with silica gel column to obtain the final product 5, 7-di (pyridin-4-yl) -2, 3-dihydrothieno [3,4-b ]][1,4]Dioxin. Next 1mol of 5, 7-bis (pyridin-4-yl) -2, 3-dihydrothieno [3,4-b][1,4]Dioxin, pour into 50mL of Acetonitrile (ACN), then slowly add 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.99(s,2H),8.87(s,2H),7.56(s,2H),7.51(s,2H),6.12(s,2H),6.00(s,1H),5.19(s,2H),4.94(d,J=12.5Hz,1H),4.79(d,J=12.5Hz,1H),4.63(s,2H),4.32(d,J=8.8Hz,3H),4.27(s,1H),3.43(d,J=12.5Hz,1H),3.32(d,J=12.3Hz,1H).
example 9
1mol of 2, 5-dibromo-1-phenyl-1H-pyrrole, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1H, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (1-phenyl-1H-pyrrole-2, 5-diyl) bipyridine in the first step. Next, 1mol of 4,4' - (1-phenyl-1H-pyrrole-2, 5-diyl) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.87(s,2H),8.81(s,2H),7.94(s,2H),7.77(s,2H),7.54–7.34(m,8H),6.12(s,2H),6.00(s,1H),5.19(s,2H),4.87(d,J=12.3Hz,1H),4.71(d,J=12.4Hz,1H),4.63(s,2H),3.38(d,J=12.3Hz,1H),3.27(d,J=12.5Hz,1H).
example 10
1mol of 2, 5-dibromo-1- (4- (trifluoromethoxy) benzyl) -1H-pyrrole, 3mol of 4-pyridineboronic acid, 8mThe potassium carbonate of the ol is added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1H, distilling under reduced pressure, and purifying by silica gel column to obtain the product 4,4' - (1- (4- (trifluoromethoxy) benzyl) -1H-pyrrole-2, 5-diyl) bipyridine in the first step. Next, 1mol of 4,4' - (1- (4- (trifluoromethoxy) benzyl) -1H-pyrrole-2, 5-diyl) bipyridine was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product.
The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.82(s,2H),8.76(s,2H),7.77(d,J=7.5Hz,4H),7.44(s,2H),7.27–7.18(m,5H),5.97(s,1H),5.93(s,2H),5.49(dt,J=12.3,1.0Hz,1H),5.39(dt,J=12.4,1.0Hz,1H),5.19(s,2H),4.94(d,J=12.3Hz,1H),4.79(d,J=12.5Hz,1H),4.64(s,2H),3.27(s,2H).
example 11
1mol of 2, 5-dibromofuran, 3mol of 4-pyridineboronic acid, 8mol of potassium carbonate are added to the dryThen injecting a mixed solvent of 1, 4-dioxane, ethanol and triethylamine into a reaction bottle under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10 mol% of Pd (PPh 3 ) 4 Pour into a bottle quickly and stir at 100 degrees celsius for 24 hours. After cooling to room temperature, the residue was washed with DCM, the filtrates were separated and extracted, the organic layers were combined and poured into a flask containing anhydrous Na 2 SO 4 Drying for 1h, distilling under reduced pressure, and purifying by silica gel column to obtain the 2, 5-di (pyridin-4-yl) furan as the first step product. Next, 1mol of 2, 5-di (pyridin-4-yl) furan was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ9.12(s,1H),9.00(s,1H),7.87(s,2H),7.16(s,1H),6.00(s,0H),5.93(s,1H),5.22(s,1H),4.95(s,1H),4.63(s,1H),3.46–3.34(m,1H).
example 12
1mol of 2, 5-dibromothiazolo [5,4-d ] thiazole, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10% (mol) of Pd (PPh 3) 4 was poured rapidly into a bottle and stirred at 100℃for 24h. After cooling to room temperature, the filter residue is washed with DCM, the filtrate is separated and extracted, the organic layers are combined, poured into an conical flask filled with anhydrous Na2SO4, dried for 1h, distilled under reduced pressure, and finally purified by a silica gel column to obtain the product of the first step, namely 2, 5-di (pyridine-4-yl) thiazolo [5,4-d ] thiazole. Next, 1mol of 2, 5-di (pyridin-4-yl) thiazolo [5,4-d ] thiazole was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ9.01(s,2H),8.85(s,2H),8.12(s,2H),8.01(s,2H),6.12(s,2H),6.00(s,1H),5.19(s,2H),4.94(d,J=12.5Hz,1H),4.79(d,J=12.5Hz,1H),4.63(s,2H),3.43(d,J=12.5Hz,1H),3.32(d,J=12.3Hz,1H).
example 13
1mol of 2, 5-dibromothiophene [3,2-b ] thiophene, 3mol of 4-pyridine boric acid and 8mol of potassium carbonate are added into a dry Schlenk flask, and then a mixed solvent of 1, 4-dioxane, ethanol and triethylamine is injected into the reaction flask under the nitrogen atmosphere, wherein the volume ratio of the three solvents is 1:5:1. finally 10% (mol) of Pd (PPh 3) 4 was poured rapidly into a bottle and stirred at 100℃for 24h. After cooling to room temperature, the filter residue is washed with DCM, the filtrate is separated and extracted, the organic layers are combined, poured into an conical flask filled with anhydrous Na2SO4, dried for 1h, distilled under reduced pressure, and finally purified by a silica gel column to obtain the product of the first step, namely 2, 5-di (pyridine-4-yl) thieno [3,2-b ] thiophene. Next, 1mol of 2, 5-di (pyridin-4-yl) thieno [3,2-b ] thiophene was poured into 50mL of Acetonitrile (ACN), followed by slow addition of 0.5mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After completion of the reaction, precipitation with ethyl acetate gives the monosubstituted second step product. The resulting second stage product was then added to a pear-shaped flask at an equimolar ratio to bromopropene, and 50mL of ACN was added and stirred for 24h. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a product of the third step. Finally, the product of the third step is put into a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1H NMR (500 MHz, chloroform-d) δ8.85 (s, 2H), 8.81 (s, 2H), 7.84 (s, 2H), 7.74 (s, 2H), 7.56 (s, 2H), 6.12 (s, 2H), 6.00 (s, 1H), 5.19 (s, 2H), 4.94 (d, J=12.5 Hz, 1H), 4.79 (d, J=12.5 Hz, 1H), 4.63 (s, 2H), 3.38 (d, J=12.3 Hz, 1H), 3.27 (d, J=12.5 Hz, 1H).
Comparative example 1
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 1mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction is completed, ethyl acetate is used for precipitation, and the monosubstituted viologen derivative is obtained. The resulting first step product was then added to a pear-shaped flask in equimolar ratio to bromopropane, and 50mL ACN was added and stirred for 24 hours. Spin-drying acetonitrile, dissolving with water, adding dichloromethane for extraction, spin-drying, and drying at 60 ℃ in a vacuum drying oven for 12 hours to obtain a second-step product. Finally, the second step of product is placed in a pear-shaped bottle, excessive diluted hydrochloric acid is added, and reflux is carried out for 10 hours at 100 ℃. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.79(d,J=7.8Hz,5H),7.92(s,2H),7.72(s,2H),6.04(s,2H),4.59(s,2H),4.34(s,2H),3.30(s,2H),1.97(s,2H),0.98(s,3H).
comparative example 2
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 2mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction was completed, acetonitrile was dried by spin-drying, dissolved in water, extracted by adding methylene chloride, dried by spin-drying, and dried in a vacuum oven at 60℃for 12 hours. Finally, excess dilute hydrochloric acid was added and the mixture was refluxed at 100℃for 10 hours. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows
The chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.76(s,1H),7.85(s,1H),5.93(s,1H),4.63(s,1H),3.37(s,1H).
comparative example 3
2mol of 4-4' -bipyridine were placed in a pear-shaped bottle, followed by 50mL of Acetonitrile (ACN), followed by slow addition of 2mol of diethyl 2-bromoethylphosphonate. The mixture was refluxed at 80 ℃ for 24h. After the reaction was completed, acetonitrile was dried by spin-drying, dissolved in water, extracted by adding methylene chloride, dried by spin-drying, and dried in a vacuum oven at 60℃for 12 hours. Finally, excess dilute hydrochloric acid was added and the mixture was refluxed at 100℃for 10 hours. And after the reaction is finished, adding ethanol to precipitate solid, filtering and drying a filter cake to obtain a final product. The chemical structural formula is as follows:
the chemical structure is characterized as follows: 1 H NMR(500MHz,Chloroform-d)δ8.79(s,2H),7.89(s,2H),4.33(s,2H),1.97(s,2H),0.96(s,3H).
results examples
The cathode electrochromic materials synthesized in examples 1 to 13 and comparative examples 1 to 3 described above were applied to electrochromic devices, respectively. It should be noted that the electrochromic materials of the cathodes synthesized in examples 1 to 13 and comparative examples 1 to 3 are prepared by salifying chloride ions, and the electrochromic materials prepared by salifying bromide ions, iodide ions, triflate anions, perchlorate anions and tetrafluoroborate anions have similar properties to those of chloride ions, and are not described in detail herein.
The preparation method comprises the following steps of 2 The slurry was knife coated onto FTO, heated to 120 degrees celsius at a rate of 10 degrees per minute, held for 30 minutes and then annealed. TiO is mixed with 2 immersing/FTO in the solution of viologen with different concentrations for 12h, washing with deionized water and ethanol, and drying in a vacuum drying oven at 60 ℃. Adsorbed viologen/TiO 2 The FTO is closely attached to the other ITO with the 3M double faced adhesive tape around, and electrolyte is injected; preferably, the electrolyte is 0.1M LiClO 4 PC solution, tiO of (C) 2 The thickness is 3 μm. The electrochromic device is obtained after assembly, and the specific structure of the electrochromic device is shown in fig. 1.
After the device was assembled, we performed a series of studies on electrochromic devices based on the above examples, and tested the transmittance at the characteristic peak with time, thereby obtaining the coloring time (t coloring ) And fade time (t) bleaching ) The results are shown in Table 1.
TABLE 1
As seen from table 1, the difference in M structure affects the driving voltage of the device depending on the electronegativity of the M cell, and if the M electrons have electron withdrawing ability, the HOMO-LUMO energy level can be lowered, thereby lowering the driving voltage. As in examples 1,2 and 6, which are electron withdrawing units, the voltage to drive the device to change color is relatively low; in the embodiment 7, the methoxy group contained in the benzene ring belongs to an electron donating group, so that the driving voltage can be increased, and in the embodiment 9, the electron cloud distribution is more uniform due to the conjugation of the phenylpyrrole, so that the driving voltage is increased; second, the M group can affect the final color of the device, as in examples 8-10 for pink and example 1 for blue-violet; second, the coloring and fading time of the material is affected by the molecular weight of the material, steric hindrance, and the color switching speed is the slowest as in example 9.
The electrochromic device prepared by the invention has the characteristics of high contrast ratio and rapid color switching, and the cyclic voltammogram of the device is stable and the driving voltage required by color change is low as shown in the figure 2; as can be seen from fig. 3, the color switching speed of the device is about 1s, the contrast is close to 70%, the device can be continuously switched 10000 times, and no optical attenuation occurs.
To demonstrate the characteristics of this example, a comparative example was designed and synthesized. Comparative example 1 is an anchoring structure containing a butyl structure. From the test results, the color of the material is single, blue due to the absence of the incorporated M units, and the discoloration and fading speed of the device is slower than that of the examples due to the high steric hindrance of the alkyl groups; comparative example 2 is a viologen containing a double-sided anchoring group, the material color exhibiting a blue color due to the absence of incorporated M units. In addition, the device composed of the material has a very low color-changing and fading speed because the viologen with anchoring groups on both sides is tightly adsorbed on the semiconductor layer, so that the intercalation and deintercalation of ions are difficult, and the device has lower stability than the embodiment during the test because the electron cloud of the material is highly concentrated in bipyridylium salt; comparative example 3 is a structure without anchor groups and alkynyl groups, and the rate of discoloration and fading of the device is limited by diffusion of the material itself, since there is no chemisorption with the semiconductor, and thus the rate of discoloration and fading of the device is the slowest.
According to the electrochromic material prepared by the embodiment of the invention, unsaturated alkyne, especially allyl and propargyl, is introduced, free radical polymerization cannot be performed due to the structural characteristics of the electrochromic material, and meanwhile, the conjugated structure can be effectively further expanded, the electron cloud density is reduced, and the stability of the material is improved; secondly, the short and small alkyne structure has the characteristic of small steric hindrance. The other end of the color-changing material has low steric hindrance after being subjected to chemical adsorption with the semiconductor layer, so that the intercalation and deintercalation of ions can be promoted, and the color switching speed of the electrochromic device is improved. Furthermore, the presence of the unique anchoring structure chemisorbs to the semiconductor layer, so that discoloration and fading of the device is not limited by diffusion of the material itself. The above features enable us to obtain high performance electrochromic devices beyond those based on conventional material devices.
The primers listed above are only partially representative, and other electrochromic compounds containing the same ideas are within the scope of this patent.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (10)

1. An electrochromic compound characterized by the following structural formula:
wherein R is 1 Is phosphate-PO (OH) 2 Silicic acid radical-Si (OH) 3 And one of acetate-COOH;
m is a direct bond, or M is selected from benzene, 1, 4-dibromo-2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
R 2 alkenyl or alkynyl;
m and n may be each independently an integer of 0 to 12;
X - selected from chloride, bromide, iodide, triflate anions, perchlorate anions, tetrafluoroborate anions.
2. Electrochromic compound according to claim 1, characterized in that it has the structure of formulae (a) to (F) as follows:
3. electrochromic compound according to claim 1, characterized in that R 2 Is an unsaturated alkenyl or alkynyl group; the alkenyl group includes vinyl-ch=ch 2 allyl-CH 2 CH=CH 2 The method comprises the steps of carrying out a first treatment on the surface of the The alkynyl group includes ethynyl-C.ident.CH, propargyl-CH 2 C.ident.CH, 1-propynyl-C.ident.C-CH 3
4. The electrochromic compound according to claim 1, characterized by having any one of the structural formulae shown in formulae (1) to (9):
5. electrochromic compound according to claim 1, characterized in that M is in position 2 and/or 5 by F, CF 3 、OCH 3 、OCF 3 Any one of substituted benzene;
or M is pyrrole substituted by benzene, benzyl and derivatives thereof at the N position;
alternatively, M is 2 and/or the 3 position is defined by CF 3 、OCH 3 、OCF 3 Pyrrole or thiophene of any kind.
6. A method for producing an electrochromic compound according to any one of claims 1 to 5, characterized by comprising the steps of:
reacting and refluxing the compound a with the compound b to obtain a compound c, refluxing the compound c and the compound d in an organic solvent to obtain a compound e, and finally acidifying and hydrolyzing to obtain the final electrochromic compound;
wherein M is a direct bond, or M is selected from benzene, 2, 5-bis (trifluoromethyl) benzene, thiophene, furan, phenylpyrrole, thienothiophene, 2, 3-dihydrothieno [3,4-b ] [1,4] dioxin, thiazolothiazole and substituted derivatives thereof;
the structural formula of the compound b is R 3 -(CH2) m -R 4 M is an integer between 0 and 12, R 3 Is any one of I, br and Cl, R 4 Is a substituted phosphate (-PO (OCH) 2 CH 3 ) 2 ) Methylsiloxane (-Si (OCH) 3 ) 3 ) Ethyl acetate (-COOCH) 2 CH 3 ) One of the following;
the structural formula of the compound d is R 2 -(CH2) n -R 5 N is an integer of 0 to 12, R 2 Is alkenyl or alkynyl, R 5 Is any one of I, br and Cl.
7. The method of claim 6, wherein m is 2 or 3 and n is 2 or 3.
8. The method of claim 6, wherein the compound b has one of the following structural formulas:
the structural formula of the compound d is one of the following:
9. an electrochromic device comprising a first conductive layer, a second conductive layer, a semiconductor layer, an electrochromic layer, and an electrolyte layer between the first conductive layer and the second conductive layer; the electrochromic layer uses the electrochromic compound according to any one of claims 1 to 5 or the electrochromic compound obtained by the production method according to any one of claims 6 to 8.
10. Use of the electrochromic device of claim 9 in a smart window, a rearview mirror or an electronic device.
CN202211084219.5A 2022-09-06 2022-09-06 Electrochromic compound, preparation method and application Pending CN117700457A (en)

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