CN102942517A - Conjugated expanded viologen derivative as well as preparation method and application thereof - Google Patents
Conjugated expanded viologen derivative as well as preparation method and application thereof Download PDFInfo
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- CN102942517A CN102942517A CN2012104507533A CN201210450753A CN102942517A CN 102942517 A CN102942517 A CN 102942517A CN 2012104507533 A CN2012104507533 A CN 2012104507533A CN 201210450753 A CN201210450753 A CN 201210450753A CN 102942517 A CN102942517 A CN 102942517A
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Abstract
The invention discloses a conjugated expanded viologen derivative shown in a formula I, wherein X1 and X2 are any one of Cl, Br or I, and R1 and R2 are any one of a fat chain alkyl group or a mono aromatic group; and the conjugated expanded viologen derivative is prepared by reacting 1,2-bi(4-pyridyl)ethylene with halohydrocarbon in an organic solvent at a constant temperature of 30-80 DEG C during stirring. The conjugated expanded viologen derivative is similar to viologen, is an excellent cathode electrochromic material, has favorable electrochromism performance, and especially can display rare red, thereby expanding the color selection range of the electrochromic material, providing a novel red electrochromic display material for the colorful electrochromic material field, and having potential and extensive application prospect in the electrochromic field.
Description
Technical field
The invention belongs to the functional materials preparation field, relate to the preparation method of the viologen derivative (mainly being vinyl bipyridylium quaternary ammonium salt compound and derivative thereof) of a class Conjugate extended, and this analog derivative is as the application of novel electrochromic material.
Background technology
Electrochromism refers to that stable, reversible change phenomenon occurs the optical properties (reflectivity, transmitance, specific absorption etc.) of material, shows as the reversible change of color and transparency in appearance under DC Electric Field.Material with electrochromic property is called electrochromic material.The electrochromic device that utilizes electrochromic material to be made has some unique characteristics, as device for Optical Properties of Materials on a large scale in continuously adjustable, can realize optical modulation, operating voltage is low, energy consumption is low, be easy to unicircuit coupling, operating temperature range is wide, have high-reflectivity thereby do not need external light source etc., has a wide range of applications at aspects such as electronic console, vehicle dormer window photosystem, color-changing solar mirror, smart window, glareproof mirrors.
Electrochromic material commonly used mainly is divided into two classes: inorganic electrochromic material and organic electrochromic material.Inorganic electrochromic material is difficult to be made into panchromatic electrochromic device because Show Color is too dull, and range of application is subject to certain limitation.Organic electrochromic material then with its display color diversity and the multifarious characteristics of selection, is used more extensive.Wherein, cost is low owing to having, color abundant for Viologen Compounds, the advantages such as contrast gradient is high, the time of response is short, long service life, has comprised in intelligent smart windows, automobile rearview mirror, electrochromism digital display screen and the light-operated molecular device at electrochromic device and being used widely.Because the performance of electrochromic material is determining the performance of electrochromic device to a certain extent, one of the main direction of studying in electrochromism field is exactly the novel electrochromic material of developing excellent property at present, especially develop the colored electrochromic material of various color displays, with the range of choice of abundant expansion electrochromic material.
Summary of the invention
In view of this, the object of the invention is to develop a kind of novel electrochromic material of excellent property, with the range of choice of abundant expansion electrochromic material.
For achieving the above object, the invention provides following technical scheme:
1. the viologen derivative of Conjugate extended has structure shown in the formula I:
In the formula, X
1And X
2At random be Cl, Br or I; R
1And R
2At random be fat chain alkylene or mononuclear aromatics base.
Further, R
1And R
2At random for C1-C16 alkyl, C1-C16 thiazolinyl, the C1-C16 alkyl that the mononuclear aromatics base replaces or the C1-C16 thiazolinyl that has the mononuclear aromatics base to replace arranged.
Further, R
1And R
2At random for C1-C8 alkyl, C1-C8. thiazolinyl or phenyl is arranged or C1-C8 alkyl that substituted-phenyl replaces, described substituted-phenyl is the phenyl that C1-C8 alkyl or C1-C8 alkenyl substituted are arranged.
Further, R
1And R
2At random be methyl, ethyl, butyl, octyl group, allyl group, isopentene group, benzyl or 4-vinyl benzyl.
Further, the viologen derivative of described Conjugate extended is any in the following compound:
2. the preparation method of the viologen derivative of described Conjugate extended comprises following two kinds of technical schemes:
A.R
1And R
2Identical and X
1And X
2The preparation method of identical formula I compound comprises the steps:
In organic solvent, add shown in the formula II 1,2-two (4-pyridyl) ethene drips halohydrocarbon shown in the formula III, 1 again, the mol ratio of 2-two (4-pyridyl) ethene and halohydrocarbon is 1: 2-2.5, then 30～80 ℃ of constant temperature stirring reactions react and are cooled to room temperature after complete, and the ether that adds two volumes is made precipitation agent, filter, filtration cakes torrefaction gets that the 1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt is R shown in the formula IV
1And R
2Identical and X
1And X
2Identical formula I compound; Chemical equation is as follows:
B.R
1And R
2The preparation method of different formula I compounds comprises the steps:
A. in organic solvent, add shown in the formula II 1,2-two (4-pyridyl) ethene drips halohydrocarbon shown in the formula III, 1 again, the mol ratio of 2-two (4-pyridyl) ethene and halohydrocarbon is 1: 0.9-1.05, then 30～80 ℃ of constant temperature stirring reactions react and are cooled to room temperature after complete, and the ether that adds two volumes is made precipitation agent, filter, filtration cakes torrefaction gets 1,2-di(4-pyridyl)ethylene mono-quaternaries shown in the formula V; Chemical equation is as follows:
B. in organic solvent, add shown in the formula V 1,2-two (4-pyridyl) ethene mono-quaternaries drips halohydrocarbon shown in the formula VI, 1 again, the mol ratio of 2-two (4-pyridyl) ethene mono-quaternaries and halohydrocarbon is 1: 1-1.2, then 30～80 ℃ of constant temperature stirring reactions react and are cooled to room temperature after complete, and the ether that adds two volumes is made precipitation agent, filter, filtration cakes torrefaction gets that the 1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt is R shown in the formula VII
1And R
2Different formula I compounds; Chemical equation is as follows:
Further, organic solvent described in step a and the b is acetonitrile or dimethyl formamide.
3. the viologen derivative of described Conjugate extended is as the application of electrochromic material.
Beneficial effect of the present invention is: the present invention has developed the novel organic electrochromic material of a class---and the viologen derivative of Conjugate extended (mainly refers to vinyl bipyridylium quaternary ammonium salt compound, namely in the dipyridyl structure of Viologen Compounds, introduce vinyl and carry out Conjugate extended), this compounds is similar to purpurine, it is good cathode electrochromic material, has good electrochromic property, especially show rare redness, thereby expanded the Colour selection scope of organic electrochromic material, for colored electrochromic material field provides a class new red electrochromic display material, have potential in the electrochromism field, wide application prospect.In addition, the present invention also provides the preparation method of the viologen derivative of this Conjugate extended, the characteristics such as have reaction conditions gentleness, convenient post-treatment, yield is high, cost is low.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, the below is described in detail the preferred embodiments of the present invention.
Preparation Example 1
With 18.2g (0.1mol) 1,2-two (4-pyridyl) ethene adds in the 150ml acetonitrile, then slowly splashes into 35.5g (0.25mol) methyl iodide, 30 ℃ of constant temperature stirring reaction 72h, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry, namely get N, N '-dimethyl-1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt iodide 1 (orange solid), yield 82%; Product structure is in full accord through identifying with said structure formula 1.
Preparation Example 2
18.2g (0.1mol) 1,2-di(4-pyridyl)ethylene is added in the 150ml acetonitrile, then slowly splash into 27.2g (0.225mol) allyl bromide 98, be warming up to 50 ℃ of constant temperature stirring reaction 72h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry namely get N, N '-diallyl-1,2-two (4-pyridyl) ethene bi-quaternary ammonium salt bromide 2 (light yellow solids), yield 83%; Product structure is in full accord through identifying with said structure formula 2.
Preparation Example 3
18.2g (0.1mol) 1,2-di(4-pyridyl)ethylene is added in the 150ml acetonitrile, then slowly splash into 33.6g (0.225mol) bromo isopentene, be warming up to 80 ℃ of back flow reaction 60h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry namely get N, N '-diisoamyl thiazolinyl-1,2-two (4-pyridyl) ethene bi-quaternary ammonium salt bromide 3 (light yellow solids), yield 85%; Product structure is in full accord through identifying with said structure formula 3.
Preparation Example 4
18.2g (0.1mol) 1,2-di(4-pyridyl)ethylene is added in the 150ml acetonitrile, then slowly splash into 37.7g (0.22mol) cylite, be warming up to 80 ℃ of back flow reaction 60h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry namely get N, N '-dibenzyl-1,2-two (4-pyridyl) ethene bi-quaternary ammonium salt bromide 4 (light yellow solids), yield 83%; Product structure is in full accord through identifying with said structure formula 4.
Preparation Example 5
18.2g (0.1mol) 1,2-di(4-pyridyl)ethylene is added in the 150ml acetonitrile, then slowly splash into 31.5g (0.23mol) bromination of n-butane, be warming up to 80 ℃ of back flow reaction 74h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry namely get N, N '-dibutyl-1,2-two (4-pyridyl) ethene bi-quaternary ammonium salt bromide 5 (light yellow solids), yield 82%; Product structure is in full accord through identifying with said structure formula 5.
Preparation Example 6
18.2g (0.1mol) 1,2-di(4-pyridyl)ethylene is added in the 150ml acetonitrile, then slowly splash into 42.5g (0.22mol) n-octane bromide, be warming up to 80 ℃ of back flow reaction 72h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry namely get N, N '-dioctyl-1,2-two (4-pyridyl) ethene bi-quaternary ammonium salt bromide 6 (light yellow solids), yield 81%; Product structure is in full accord through identifying with said structure formula 6.
Preparation Example 7
With 18.2g (0.1mol) 1,2-two (4-pyridyl) ethene adds in the 150ml acetonitrile, then slowly splash into 14.2g (0.1mol) methyl iodide, 30 ℃ of constant temperature stirring reaction 72h, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, and 50 ℃ of oven dry namely get the N-methyl isophthalic acid, 2-two (4-pyridyl) ethene mono-quaternaries iodide (orange solid), yield 81%;
With gained N-methyl isophthalic acid, 2-two (4-pyridyl) ethene mono-quaternaries iodide are dissolved in the 150ml dimethyl formamide (DMF), then slowly splash into 18.8g (0.11mol) cylite, be warming up to 80 ℃ of constant temperature stirring reaction 60h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, and 50 ℃ of oven dry namely get iodate bromination N, N '-methyl, benzyl-1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt 7 (yellow solid), total recovery 70.2%; Product structure is in full accord through identifying with said structure formula 7.
Preparation Example 8
With 18.2g (0.1mol) 1,2-two (4-pyridyl) ethene adds in the 150ml acetonitrile, then slowly splashes into 15.6g (0.1mol) iodoethane, is warming up to 40 ℃ of constant temperature stirring reaction 60h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, and filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry, namely get N-ethyl-1,2-di(4-pyridyl)ethylene mono-quaternaries iodide (orange solid), yield 82%.
With gained N-ethyl-1,2-two (4-pyridyl) ethene mono-quaternaries iodide are dissolved among the 150ml DMF, then slowly splash into 16.4g (0.11mol) bromo isopentene, be warming up to 80 ℃ of constant temperature stirring reaction 64h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, and 50 ℃ of oven dry namely get iodate bromination N, N '-ethyl, isopentene group-1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt 8 (yellow solid), total recovery 69.7%; Product structure is in full accord through identifying with said structure formula 8.
Preparation Example 9
With 18.2g (0.1mol) 1,2-two (4-pyridyl) ethene adds in the 100ml acetonitrile, then slowly splash into the Benzyl Chloride that 12.7g (0.1mol) uses the 50mL dilution in acetonitrile, be warming up to 50 ℃ of constant temperature stirring reaction 48h, filter, filter cake washs with anhydrous diethyl ether, vacuum-drying, namely get N-benzyl-1,2-di(4-pyridyl)ethylene mono-quaternaries muriate (light yellow solid), yield 74%;
With gained N-benzyl-1,2-two (4-pyridyl) ethene mono-quaternaries muriate is dissolved among the 150ml DMF, then slowly splash into 21.2g (0.11mol) n-octane bromide, be warming up to 80 ℃ of constant temperature stirring reaction 72h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, and 50 ℃ of oven dry namely get chlorination bromination N, N '-benzyl, octyl group-1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt 9 (orange solid), total recovery 66.3%; Product structure is in full accord through identifying with said structure formula 9.
Preparation Example 10
With 18.2g (0.1mol) 1,2-two (4-pyridyl) ethene adds in the 150ml acetonitrile, then slowly splashes into 15.6g (0.1mol) iodoethane, is warming up to 40 ℃ of constant temperature stirring reaction 60h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filters, and filter cake washs with anhydrous diethyl ether, 50 ℃ of oven dry, namely get N-ethyl-1,2-di(4-pyridyl)ethylene mono-quaternaries iodide (orange solid), yield 82%;
With gained N-ethyl-1,2-two (4-pyridyl) ethene mono-quaternaries iodide are dissolved among the 150ml DMF, then slowly splash into 13.3g (0.105mol) to vinyl chlorination benzyl, be warming up to 80 ℃ of constant temperature stirring reaction 64h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, and 50 ℃ of oven dry namely get iodate chlorination N, N '-ethyl, to vinyl benzyl-1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt 10 (orange solid), total recovery 69.7%; Product structure is in full accord through identifying with said structure formula 10.
Preparation Example 11
With 18.2g (0.1mol) 1,2-two (4-pyridyl) ethene adds in the 100ml acetonitrile, then slowly splash into the Benzyl Chloride that 12.7g (0.1mol) uses the 50mL dilution in acetonitrile, be warming up to 50 ℃ of constant temperature stirring reaction 48h, filter, filter cake washs with anhydrous diethyl ether, vacuum-drying, namely get N-benzyl-1,2-di(4-pyridyl)ethylene mono-quaternaries muriate (light yellow solid), yield 74%;
With gained N-benzyl-1,2-two (4-pyridyl) ethene mono-quaternaries muriate is dissolved among the 150ml DMF, then slowly splash into 13.3g (0.11mol) allyl bromide 98, be warming up to 40 ℃ of constant temperature stirring reaction 72h, be cooled to room temperature, the ether that adds two volumes is made precipitation agent, filter, filter cake washs with anhydrous diethyl ether, and 50 ℃ of oven dry namely get chlorination bromination N, N '-benzyl, allyl group-1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt 11 (orange solid), total recovery 65.3%; Product structure is in full accord through identifying with said structure formula 11.
The structural analysis of above-mentioned product 1-11 shows, halohydrocarbon and 1, the position of 2-two (4-pyridyl) ethylene reaction is all on the nitrogen-atoms of 4-pyridyl, by adjusting the charging capacity of halohydrocarbon, what obtain is mono-quaternaries or bi-quaternary ammonium salt product, wherein can contain the bi-quaternary ammonium salt product of trace in the mono-quaternaries product, can carry out purifying by recrystallization.The structural characterization data of part of compounds are as follows:
Compound 1:
1H NMR (D
2O, 300M, δ/ppm): 8.64 (d, J=6.0Hz, 4H), 8.10 (d, J=3.0Hz, 4H), 7.74 (s, 2H), 4.24 (s, 6H).
13C NMR (75MHz, D
2O, TMS): δ
C150.49,145.35,133.72,125.72,47.91.APCI-MS (m/z): 465[M
2+I
2] .FT-IR (KBr, cm
-1): 3069 (w, Ar C-H)
s, 3014 (m ,=CH)
s, 2945 (m, CH
3)
s, 1633 (s, C=C)
s, 1594 (s, Ar C=C)
s, 1522 (m, Ar C=C)
s, 1475 (m, CH
2)
δ, 1384 (m, CH
3)
δ, 755,725.
Compound 2:
1H NMR (D
2O, 300M, δ/ppm): 8.71 (d, J=6.0Hz, 4H), 8.14 (d, J=6.0Hz, 4H), 7.78 (s, 2H), 6.09-5.96 (m, 2H), 5.45-5.34 (m, 4H), 5.09 (d, J=6.0Hz, 4H).
13C NMR (75MHz, D
2O, TMS): δ
C151.56,144.53,133.91,129.96,125.98,123.07,63.02.APCI-MS (m/z): 424[M
2+Br
2] .FT-IR (KBr, cm
-1): 3102 (w, Ar C-H)
s, 3081 (w, Ar C-H)
s, 3018 (m ,=CH)
s, 2933 (m, CH
2)
s, 2873 (m, CH)
s, 1631 (s, C=C)
s, 1517 (s, Ar C=C)
s, 1473 (m, Ar C=C)
s, 1450 (m, CH
2)
δ, 738,664.
Compound 3:
1H NMR (D
2O, 300M, δ/ppm): 8.64 (s, 4H), 8.07 (s, 4H), 7.73 (d, J=3.0Hz, 2H), 5.41 (s, 2H), 5.06 (d, J=6.0Hz, 4H), 1.73 (s, 12H).
13C NMR (75MHz, D
2O, TMS): δ
C151.17,145.66,143.97,133.67,125.69,114.87,58.51,24.96,17.53.APCI-MS (m/z): 480[M
2+Br
2] .FT-IR (KBr, cm
-1): 3036 (w, Ar C-H)
s, 3011 (m ,=CH)
s, 2931 (m, CH
2)
s, 1632 (s, C=C)
s, 1595 (s, ArC=C)
s, 1521 (m, Ar C=C)
s, 1474 (m, CH
2)
δ, 775,706.
Compound 4:
1H NMR (D
2O, 300M, δ/ppm): 8.80-8.72 (broad d, 4H), 8.14-8.06 (broad d, 4H), 7.79-7.71 (broad d, 4H), 7.42-7.34 (broad d, 6H), (5.72-5.64 broad d, 2H), 4.76 (s, 4H).
13C NMR (75MHz, D
2O, TMS): δ
C144.50,133.88,129.95,129.60,129.04,128.94,125.99,125.82,64.15.APCI-MS (m/z): 524[M
2+Br
2] .FT-IR (KBr, cm
-1): 3030 (m ,=CH)
s, 2974 (m, CH
2)
s, 1632 (s, C=C)
s, 1592 (s, Ar C=C)
s, 1521 (m, Ar C=C)
s, 1494 (m, Ar C=C)
s, 1471 (m, Ar C=C)
s1454 (m, CH
2)
δ, 818,731.
Compound 5:
1H NMR (D
2O, 300M, δ/ppm): 8.66 (d, J=6.0Hz, 4H), 8.12 (d, J=3.0Hz, 4H), (7.77 s, 2H), 5.88-5.76 (m, 2H), (4.54 t, J=7.2Hz, 4H), 2.13 (m, 4H), 1.18-1.30 (m, 4H), (0.98 t, J=6.3Hz, 6H) .APCI-MS (m/z): 456[M
2+Br
2] .FT-IR (KBr, cm
-1): 3053 (w, Ar C-H)
s, 3013 (m ,=CH)
s, 2933 (m, CH
2)
s, 1631 (s, C=C)
s, 1593 (s, Ar C=C)
s, 1521 (m, Ar C=C)
s, 1472 (m, CH
2)
δ, 1381 (m, CH
3)
δ, 801,727.
Compound 6:
1H NMR (D
2O, 300M, δ/ppm): 8.68 (d, J=6.0Hz, 4H), 8.11 (d, J=3.0Hz, 4H), (7.79 s, 2H), 5.93-5.81 (m, 2H), (4.67 t, J=7.2Hz, 4H), 2.09 (m, 4H), 1.25-1.36 (m, 20H), (0.94 t, J=6.3Hz, 6H) .APCI-MS (m/z): 568[M
2+Br
2] .FT-IR (KBr, cm
-1): 3046 (w, Ar C-H)
s, 2931 (m, CH
2)
s, 2857 (m, CH
2)
s, 1632 (s, C=C)
s, 1594 (s, Ar C=C)
s, 1518 (m, Ar C=C)
s, 1475 (m, CH
2)
δ, 1379 (m, CH
3)
δ, 816,725.
Application Example 1
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 60 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 1,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 1 that Preparation Example 1 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless pink that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 1 as stated above, its electrochromic property is similar.
Application Example 2
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 40 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 2,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 2 that Preparation Example 2 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless carmetta that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 2 as stated above, its electrochromic property is similar.
Application Example 3
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 30 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 3,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 3 that Preparation Example 3 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless carmetta that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 3 as stated above, its electrochromic property is similar.
Application Example 4
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 50 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 4,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 4 that Preparation Example 4 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless pink that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 4 as stated above, its electrochromic property is similar.
Application Example 5
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 60 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 5,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 5 that Preparation Example 5 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless pink that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 5 as stated above, its electrochromic property is similar.
Application Example 6
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 50 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 6,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 6 that Preparation Example 6 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless pink that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 6 as stated above, its electrochromic property is similar.
Application Example 7
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 50 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 7,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 7 that Preparation Example 7 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless pink that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 7 as stated above, its electrochromic property is similar.
Application Example 8
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 50 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 8,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 8 that Preparation Example 8 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless carmetta that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 8 as stated above, its electrochromic property is similar.
Application Example 9
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 60 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 9,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 9 that Preparation Example 9 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless carmetta that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 9 as stated above, its electrochromic property is similar.
Application Example 10
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 50 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 10,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 10 that Preparation Example 10 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless carmetta that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 10 as stated above, its electrochromic property is similar.
Application Example 11
Get the ITO conductive glass of 2 60 * 80mm, be bonded in aspectant mode with the ito surface of frame glue with 2 sheet glass, form the high cavity of 60 μ m, and leave a fill orifice; Pour into the carbonic allyl ester solution (be dissolved in 0.1g compound 11,0.05g ferrocene and 0.2g (vinyl acetate-methyl methacrylate) multipolymer in the 15mL propylene carbonate and get final product) of the compound 11 that Preparation Example 11 makes from fill orifice to cavity, then use UV rubber seal mouth, make electrochromic device.Be under the condition of 1.5V at driving voltage, the color of this electrochromic device is by the colourless pink that becomes, and circulates after 10000 times, and the color of electrochromic device and weight thereof are without obvious change.
The electrochromic device that makes with N-methylpyrroline ketone solution or the gamma-butyrolactone solution of compound 11 as stated above, its electrochromic property is similar.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (8)
1. the viologen derivative of Conjugate extended has structure shown in the formula I:
In the formula, X
1And X
2At random be Cl, Br or I; R
1And R
2At random be fat chain alkylene or mononuclear aromatics base.
2. the viologen derivative of Conjugate extended according to claim 1 is characterized in that, R
1And R
2At random for C1-C16 alkyl, C1-C16 thiazolinyl, the C1-C16 alkyl that the mononuclear aromatics base replaces or the C1-C16 thiazolinyl that has the mononuclear aromatics base to replace arranged.
3. the viologen derivative of Conjugate extended according to claim 2 is characterized in that, R
1And R
2At random for C1-C8 alkyl, C1-C8. thiazolinyl or phenyl is arranged or C1-C8 alkyl that substituted-phenyl replaces, described substituted-phenyl is the phenyl that C1-C8 alkyl or C1-C8 alkenyl substituted are arranged.
4. the viologen derivative of Conjugate extended according to claim 3 is characterized in that, R
1And R
2At random be methyl, ethyl, butyl, octyl group, allyl group, isopentene group, benzyl or 4-vinyl benzyl.
5. the viologen derivative of Conjugate extended according to claim 4 is characterized in that, the viologen derivative of described Conjugate extended is any in the following compound:
6. the preparation method of the viologen derivative of Conjugate extended claimed in claim 1 is characterized in that,
A.R
1And R
2Identical and X
1And X
2The preparation method of identical formula I compound comprises the steps:
In organic solvent, add shown in the formula II 1,2-two (4-pyridyl) ethene drips halohydrocarbon shown in the formula III, 1 again, the mol ratio of 2-two (4-pyridyl) ethene and halohydrocarbon is 1: 2-2.5, then 30～80 ℃ of constant temperature stirring reactions react and are cooled to room temperature after complete, and the ether that adds two volumes is made precipitation agent, filter, filtration cakes torrefaction gets that the 1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt is R shown in the formula IV
1And R
2Identical and X
1And X
2Identical formula I compound; Chemical equation is as follows:
B.R
1And R
2The preparation method of different formula I compounds comprises the steps:
A. in organic solvent, add shown in the formula II 1,2-two (4-pyridyl) ethene drips halohydrocarbon shown in the formula III, 1 again, the mol ratio of 2-two (4-pyridyl) ethene and halohydrocarbon is 1: 0.9-1.05, then 30～80 ℃ of constant temperature stirring reactions react and are cooled to room temperature after complete, and the ether that adds two volumes is made precipitation agent, filter, filtration cakes torrefaction gets 1,2-di(4-pyridyl)ethylene mono-quaternaries shown in the formula V; Chemical equation is as follows:
B. in organic solvent, add shown in the formula V 1,2-two (4-pyridyl) ethene mono-quaternaries drips halohydrocarbon shown in the formula VI, 1 again, the mol ratio of 2-two (4-pyridyl) ethene mono-quaternaries and halohydrocarbon is 1: 1-1.2, then 30～80 ℃ of constant temperature stirring reactions react and are cooled to room temperature after complete, and the ether that adds two volumes is made precipitation agent, filter, filtration cakes torrefaction gets that the 1,2-di(4-pyridyl)ethylene bi-quaternary ammonium salt is R shown in the formula VII
1And R
2Different formula I compounds; Chemical equation is as follows:
7. the preparation method of the viologen derivative of Conjugate extended according to claim 1 is characterized in that, organic solvent described in step a and the b is acetonitrile or dimethyl formamide.
8. the viologen derivative of Conjugate extended claimed in claim 1 is as the application of electrochromic material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106432061A (en) * | 2016-06-12 | 2017-02-22 | 上海大学 | High sensitivity color-changing acetophenone substituent viologen compound and synthesis method thereof |
| CN108997427A (en) * | 2018-08-01 | 2018-12-14 | 南方科技大学 | The electrochromic device and purposes of electrochromic compounds, purposes and its preparation |
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