CN111171010A - Cathode electro-stimulation response material and preparation method thereof - Google Patents

Cathode electro-stimulation response material and preparation method thereof Download PDF

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CN111171010A
CN111171010A CN202010032422.2A CN202010032422A CN111171010A CN 111171010 A CN111171010 A CN 111171010A CN 202010032422 A CN202010032422 A CN 202010032422A CN 111171010 A CN111171010 A CN 111171010A
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palladium catalyst
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孟鸿
孙越
施明
蒋明杰
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Peking University Shenzhen Graduate School
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Abstract

The invention discloses a cathodic electrostimulation response material, wherein the cathodic electrostimulation response material comprises a structural general formula
Figure DDA0002364824130000011
At least one of the organic substances of (a); in the formula, Ar is
Figure DDA0002364824130000012
Figure DDA0002364824130000013
The position shown by the curvilinear bond is the connection position of Ar, and R1-R4 are independently selected from H, F, CH3、CF3、OCF3、SCF3、CH2C(CH3)3And the linking position being an optionally substituted position on the ring
Figure DDA0002364824130000014
One of (1); n is the number of Ar connected with R, n is an integer larger than 0, and n is smaller than or equal to the total number of connecting positions contained in R; r is selected from H, F, CN, NO2、OCF3、SCF3And the linking position being an optionally substituted position on the ring
Figure DDA0002364824130000015
Figure DDA0002364824130000021
Figure DDA0002364824130000031
One kind of (1). According to the invention, functional groups are introduced into the traditional fluorescent molecules to develop the electrochromic performance of the traditional fluorescent molecules, and the designed electric stimulation response material has high selectivity on the electrode; and the strategy can essentially broaden the selection range of the electric control intelligent material.

Description

Cathode electro-stimulation response material and preparation method thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a cathode electric stimulation response material and a preparation method thereof.
Background
Electrochromism is a phenomenon that the color or transmittance of a material can be reversibly changed under the drive of an external voltage. Electrochromic materials can be divided into inorganic electrochromic materials and organic electrochromic materials, wherein organic electrochromic micromolecules have the characteristics of simple molecular synthesis, easily-regulated color, solution processing, realization of a completely colorless state and the like; especially, the viologen electrochromic materials are taken as a typical material, and the large-scale production is realized. However, most of the conventional electrochromic materials are in the transition from a faded state to a colored state (i.e., only a single color transition can be realized), which limits the application range and is difficult to satisfy the individual requirements of people, so that the development of novel multi-color electrochromic materials can promote the practical application of the electrochromic materials.
The electric control fluorescence refers to the phenomenon that the fluorescence intensity or color of a material changes under the condition of an external electric field, and has wide application prospects in the fields of intelligent display, biological and chemical sensing, information storage and the like. The electrochromic/electric control fluorescent material is a novel electric control intelligent material and can realize an emission mode and a reflection mode simultaneously. The reflection mode refers to that the electrochromic function is started under high brightness to realize high resolution which is difficult to achieve by active luminescence; the emission mode means that the fluorescence function can be turned on at low brightness to realize high resolution. Therefore, the development of novel electrochromic/electrically-controlled fluorescent materials is expected to be applied to the field of novel intelligent display.
At present, the development of electrochromic/electrically-controlled fluorescent materials is mainly based on the improvement of the fluorescence performance of the existing electrochromic materials. For example, an aggregation-induced emission group is introduced into an existing electrochromic polymer or a small molecule to improve the fluorescence property of the electrochromic polymer or the small molecule, or a conjugated structure of a viologen derivative is increased to improve the fluorescence quantum yield of the viologen derivative; the above method does not essentially broaden the selection range of electrochromic materials. Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a cathodal electrical stimulation response material and a preparation method thereof, and aims to solve the problems that the existing electrically-controlled fluorescent/electrochromic material is small in selection range, and the color change performance/fluorescence performance under electrical stimulation is still not high.
The technical scheme of the invention is as follows:
a cathode electrical stimulation response material comprises a structural general formula
Figure BDA0002364824020000021
At least one of the organic substances of (a); in the formula, Ar is
Figure BDA0002364824020000022
Figure BDA0002364824020000023
Or
Figure BDA0002364824020000024
The position shown by the curvilinear bond is the connection position of Ar, and R1-R4 are independently selected from H, F, CH3、CF3、OCF3、SCF3、CH2C(CH3)3And the linking position being an optionally substituted position on the ring
Figure BDA0002364824020000025
One of (1); n is the number of Ar connected with R, n is an integer larger than 0, and n is smaller than or equal to the total number of connecting positions contained in R; r is selected from H, F, CN, NO2、OCF3、SCF3And the linking position being an optionally substituted position on the ring
Figure BDA0002364824020000031
Figure BDA0002364824020000041
One kind of (1).
The preparation method of the cathode electrical stimulation responsive material comprises the following steps that R contains aromatic rings, n connecting positions of R are all positioned on the aromatic rings, and
Figure BDA0002364824020000042
the method comprises the following steps: mixing Ar-H, potassium tert-butoxide and dry first organic solvent, carrying out first reaction at 90-130 deg.C to obtain first mixed solution, adding R (F)nAdding a solution formed by dissolving the second organic solvent into the first mixed solution; carrying out a second reaction at 140-150 ℃, and purifying to obtain the product
Figure BDA0002364824020000051
Wherein R (F)nIs a compound in which n connecting positions of R are all F;
r contains aromatic ring and n connecting positions of R are all positioned on the aromatic ring,
Figure BDA0002364824020000052
or
Figure BDA0002364824020000053
The method comprises the following steps: under inert atmosphere, Ar-Br, R (Y)n、K2CO3Mixing the aqueous solution, methyl trioctyl ammonium chloride, the first palladium catalyst and a third organic solvent, carrying out a third reaction at 90-130 ℃, and purifying to obtain the palladium-palladium catalyst
Figure BDA0002364824020000054
Wherein R (Y)nIs a compound in which all of the n linking positions of R are Y, Y ═ B (OH)2Or
Figure BDA0002364824020000055
Alternatively, the first and second electrodes may be,
under an inert atmosphere, mixing
Figure BDA0002364824020000056
R(X)n、K2CO3Mixing the aqueous solution, methyl trioctyl ammonium chloride, a second palladium catalyst and a fourth organic solvent, carrying out a fourth reaction at 90-130 ℃, and purifying to obtain the catalyst
Figure BDA0002364824020000057
Wherein R (X)nThe compound is a compound in which all of the n connecting positions of R are X, and X is Cl or Br.
Has the advantages that: based on the traditional fluorescent molecules, the invention develops the electrochromic property function by introducing functional groups, thereby designing and obtaining the fluorescent material with the structural general formula as
Figure BDA0002364824020000058
A cathodically electrostimulation responsive material of at least one of the organic substances of (a); the cathode electrical stimulation response material only responds to cathode electrical stimulation, and the response selectivity is high; the neutral state of the material can realize a completely colorless state, the color is very easy to regulate, multicolor electrochromism can be realized, the material has ultrahigh contrast and the performance of electrically controlled fluorescence, and the material can be applied to the fields of electrochromism, electrically controlled fluorescence and Organic Light Emitting Diodes (OLEDs) in a multifunctional way. Meanwhile, the design strategy of the cathode electrical stimulation response material essentially realizes the widening of the selection range of the electric control intelligent material.
Drawings
FIG. 1 is a graph showing the comparison of the UV-visible absorption spectrum and the property fluorescence spectrum of compounds 1 to 3 in the example of the present invention;
FIG. 2 is a graph comparing electrochemical curves of compounds 1 to 3 in the examples of the present invention.
FIG. 3 is a graph of the electrochromic properties of Compound 1 in an example of the present invention;
FIG. 4 is an electrochromic optical contrast plot of Compound 1, in accordance with an example of the present invention.
FIG. 5 is a graph of the electrochromic properties of Compound 2 in an example of the present invention;
FIG. 6 is a graph of the electrochromic contrast of Compound 2 in an example of the present invention;
FIG. 7 is a graph of the electrically controlled fluorescence performance of Compound 2 in accordance with an embodiment of the present invention;
FIG. 8 is a graph of the contrast of electrically controlled fluorescence of Compound 2 in an example of the present invention.
FIG. 9 is a graph of the electrochromic properties of Compound 3 in an example of the present invention;
FIG. 10 is a graph of the electrochromic contrast of Compound 3 in an example of the present invention.
FIG. 11 is a graph showing the electrochromic properties of Compound 4 in example 4 of the present invention.
FIG. 12 is a graph showing the electrochromic properties of Compound 5 in example 5 of the present invention.
FIG. 13 is a graph showing the electrochromic properties of Compound 6 in example 6 of the present invention.
FIG. 14 is a fluorescence spectrum of Compound 7 in example 7 of the present invention;
FIG. 15 is a graph showing the electrochromic properties of Compound 7 in example 7 of the present invention;
FIG. 16 is an electrochromic optical contrast plot of Compound 7, inventive example 7.
Detailed Description
The invention provides a cathode electro-stimulation responsive material and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a cathode electrical stimulation response material, wherein the cathode electrical stimulation response material comprises a structural general formula
Figure BDA0002364824020000071
At least one of the organic substances of (a); in the formula, Ar is
Figure BDA0002364824020000072
Or
Figure BDA0002364824020000073
The position shown by the curvilinear bond is the connection position of Ar, and R1-R4 are independently selected from H, F, CH3、CF3、OCF3、SCF3、CH2C(CH3)3And the linking position being an optionally substituted position on the ring
Figure BDA0002364824020000074
One of (1); n is the number of Ar connected with R, n is an integer larger than 0, and n is smaller than or equal to the total number of connecting positions contained in R; r is selected from H, F, CN, NO2、OCF3、SCF3And the linking position being an optionally substituted position on the ring
Figure BDA0002364824020000075
Figure BDA0002364824020000081
Figure BDA0002364824020000091
One kind of (1).
In this embodiment, based on the conventional fluorescent molecules, the electrochromic property function is developed by introducing functional groups, so as to design and obtain a fluorescent material having a general structural formula of
Figure BDA0002364824020000092
A cathodically electrostimulation responsive material of at least one of the organic substances of (a); the cathodal electrical stimulation response material only responds to cathodal electrical stimulation, and the response selectivity is high; the neutral state of the material can realize a completely colorless state, the color is very easy to regulate, multicolor electrochromism and ultrahigh contrast can be realized, the material has the performance characteristics of electrically controlled fluorescence, and the material can be applied to the fields of electrochromism, electrically controlled fluorescence and OLED. Meanwhile, the design strategy of the cathode electro-stimulation response material of the embodiment essentially realizes the widening of the selection range of the electric control intelligent material.
In one embodiment, the cathodic electro-stimulation responsive material has both electrochromic and electrically-controlled fluorescent properties.
In one embodiment, the cathodal electrostimulation response material has a general structural formula
Figure BDA0002364824020000101
At least one of the organic substances (c).
In one embodiment, the cathodic electro-stimulation responsive material comprises
Figure BDA0002364824020000102
One of the derivatives of (1).
In one embodiment, R is an electron withdrawing group. When R is an electron-withdrawing group in the above-exemplified groups, it can be reduced
Figure BDA0002364824020000103
The turn-on voltage of the electrochromic.
In one embodiment, Ar is
Figure BDA0002364824020000104
When R is H, n is 1.
In one embodiment, R1 and R2 are not both H.
In one embodiment, R1 ═ R2, and/or R3 ═ R4.
In one embodiment, R1 ═ R2 ═ R3 ═ R4.
In one embodiment of the method of the present invention,
Figure BDA0002364824020000105
is selected from
Figure BDA0002364824020000111
Figure BDA0002364824020000121
At least one of (1).
An embodiment of the present invention provides a preparation method of the cathodic electro-stimulation responsive material, wherein R contains an aromatic ring, n connecting positions of R are located on the aromatic ring, and
Figure BDA0002364824020000122
the method comprises the following steps: mixing Ar-H, potassium tert-butoxide and a dried first organic solvent, and carrying out a first reaction at 90-130 ℃ to obtain a first mixed solution; will R (F)nAdding a solution dissolved in a second organic solvent into the first mixed solution, carrying out a second reaction at 140-150 ℃, and purifying to obtain the
Figure BDA0002364824020000123
Wherein R (F)nIs a compound in which n connecting positions of R are all F;
r contains aromatic ring and n connecting positions of R are all positioned on the aromatic ring,
Figure BDA0002364824020000124
or
Figure BDA0002364824020000125
The method comprises the following steps: under inert atmosphere, Ar-Br, R (Y)n、K2CO3Mixing the aqueous solution, methyl trioctyl ammonium chloride, the first palladium catalyst and a third organic solvent, carrying out a third reaction at 90-130 ℃, and purifying to obtain the palladium-palladium catalyst
Figure BDA0002364824020000131
Wherein R (Y)nIs a compound in which all of the n linking positions of R are Y, Y ═ B (OH)2Or
Figure BDA0002364824020000132
Alternatively, the first and second electrodes may be,
under an inert atmosphere, mixing
Figure BDA0002364824020000133
R(X)n、K2CO3Mixing the aqueous solution, methyl trioctyl ammonium chloride, a second palladium catalyst and a fourth organic solvent, carrying out a fourth reaction at 90-130 ℃, and purifying to obtain the catalyst
Figure BDA0002364824020000134
Wherein R (X)nThe compound is a compound in which all of the n connecting positions of R are X, and X is Cl or Br.
That is, R contains an aromatic ring and the n linking positions of R are all located on the aromatic ring, and
Figure BDA0002364824020000135
when, can be according to the reaction formula
Figure BDA0002364824020000136
Preparation of
Figure BDA0002364824020000137
R contains aromatic ring and n connecting positions of R are all positioned on the aromatic ring,
Figure BDA0002364824020000138
or
Figure BDA0002364824020000139
When, can be according to the reaction formula
Figure BDA00023648240200001310
Or
Figure BDA0002364824020000141
Preparation of
Figure BDA0002364824020000142
In one embodiment, the inert atmosphere may be selected from, but is not limited to, one of a nitrogen atmosphere, an argon atmosphere.
In one embodiment, the Ar-H, potassium tert-butoxide, R (F)nThe molar ratio between n and 1.2 n: n-1.2 n: 1; and/or
The R (Y)n、Ar-Br、K2CO3The molar ratio of methyl trioctyl ammonium chloride to the first palladium catalyst is 1: 0.8n to n: 3n to 10 n: 0.01 n-0.05 n: 0.02 n-0.05 n; and/or
The R (X)n、
Figure BDA0002364824020000143
K2CO3The molar ratio of methyl trioctyl ammonium chloride to the second palladium catalyst is 1: n-1.5 n: 3n to 10 n: 0.01 n-0.04 n: 0.02 n-0.05 n.
In one embodiment, the first organic solvent and the second organic solvent may be independently selected from, but not limited to, one of dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide; and/or
The third organic solvent and the fourth organic solvent can be independently selected from but not limited to one of toluene, N-dimethylformamide and 1, 4-dioxane; and/or
The first palladium-based catalyst and the second palladium-based catalyst may be independently selected from, but not limited to, one of tetrakis (triphenylphosphine) palladium and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex.
In one embodiment, the time of the first reaction is 0.5 to 12 hours; and/or
The second reaction time is 2-24 h; and/or
The third reaction time is 9-24 h; and/or
The fourth reaction time is 12-24 h.
In one embodiment, the purification process after performing the second reaction comprises: extracting, collecting and drying organic phase, concentrating, and separating by column chromatography.
In one embodiment, the purification process after performing the third reaction comprises: extracting, collecting and drying organic phase, concentrating, and separating by column chromatography.
In one embodiment, the purification process after performing the third reaction comprises: extracting, collecting and drying organic phase, concentrating, and separating by column chromatography.
The present invention will be described in detail below with reference to specific examples.
EXAMPLE 1 preparation of Compound 1
(1) According to the reaction formula
Figure BDA0002364824020000151
Compound M1 was prepared according to the following procedure: after carbazole (3.34g, 20mmol), potassium tert-butoxide (t-BuOK, 2.24g, 20mmol) and dimethyl sulfoxide (DMSO, 20mL, dried over molecular sieves) were stirred at 120 ℃ for 30min, a solution of 1-bromo-3, 5-difluorobenzene (1.93g, 10mmol in 20mL DMSO) was injected. The reaction mixture was stirred at 140 ℃ for 2 h. After cooling, the mixture is cooledThe reaction mixture was extracted with chloroform, and the organic layer was over anhydrous MgSO4Drying and purifying by column chromatography on silica gel with chloroform/n-hexane (volume ratio) 1: 8 as eluent; the product M1 was obtained as a white powder with a yield of 90%.
(2) According to the reaction formula
Figure BDA0002364824020000152
Compound 1 was prepared as follows: under a nitrogen atmosphere, compound M2(2.4mmol), compound M1(0.97g, 2mmol) were charged into a 100mL pressure flask equipped with a magnetic stir bar. Toluene (20mL) and K were added2CO3Aqueous solution (2M, 6.5mL H2O), then methyltrioctylammonium chloride (Aliquat 336, 0.040g, 0.1mmol) and tetrakis (triphenylphosphine) palladium (92.4mg, 0.08mmol) were added to the flask; stirred at 100 ℃ for 24 hours and then cooled to room temperature. The reaction solution was washed with water and ethyl acetate. The organic layer was MgSO4Dried and the solvent removed under vacuum. Purification by column chromatography gave compound 1 as a white solid in 89% yield.
EXAMPLE 2 preparation of Compound 2
According to the reaction formula
Figure BDA0002364824020000161
The preparation procedure was the same as in (2) in example 1, except that the preparation was carried out by replacing the compound M2(2.4mmol) with the compound M3(2.4mmol), to obtain the compound 2; as a white solid, yield was 92%.
EXAMPLE 3 preparation of Compound 3
According to the reaction formula
Figure BDA0002364824020000162
The preparation procedure was the same as in (2) in example 1, except that the preparation was carried out by replacing the compound M2(2.4mmol) with the compound M4(2.4mmol), to obtain the compound 3; as a white solid, yield 90%.
Properties of the compounds 1 to 3 prepared in examples 1 to 3 were characterized as follows: the comparison of the measured ultraviolet visible absorption spectra (the real curves 1 to 3 correspond to the ultraviolet visible absorption spectra of the compounds 1 to 3, respectively) and the neutral state fluorescence spectra (the dotted curves 1 'to 3' correspond to the neutral state fluorescence spectra of the compounds 1 to 3, respectively) of the compounds 1 to 3 is shown in FIG. 1; a comparison of the electrochemical curves of the compounds 1 to 3 is shown in FIG. 2. As can be seen from FIG. 1, all of the compounds 1 to 3 have blue fluorescence properties, and the absorption of the behavior thereof is only in the ultraviolet region; the neutral state of the compounds 1-3 is transparent, so that the requirement of the electrochromic material on a colorless state is better met, and the high optical contrast is favorably realized. FIG. 2 shows that the compounds 1-3 have reversible two-step electrochemical reduction processes and have the potential of cathode electrochromism.
The cathodal electrostimulation response performance of the compounds 1 to 3 prepared in examples 1 to 3 was evaluated as follows:
the electrochromic performance curve of the compound 1 is shown in figure 3; the electrochromic optical contrast curve of compound 1 was measured as shown in figure 4. As can be seen from fig. 3 and 4, compound 1 can achieve a color transition from colorless to light blue to dark blue at a given negative voltage, with a contrast as high as 98%.
The electrically controlled fluorescence property curve of compound 2 was measured as shown in figure 5; the electrically controlled fluorescence contrast curve of compound 2 was measured as shown in figure 6. As can be seen from fig. 5 and 6, compound 2 can achieve a color transition from colorless to pale yellow to rose-red with a contrast as high as 99% at a given negative voltage.
The electrically controlled fluorescence property curve of compound 2 was measured as shown in figure 7; the electrically controlled fluorescence contrast curve of compound 2 was measured as shown in figure 8. As can be seen from FIGS. 7 and 8, Compound 2 also has the property of electrically controlled fluorescence, wherein the property fluorescence is blue, the fluorescence is quenched in the ionic state, the contrast of electrically controlled fluorescence depends on the thickness of the sample cell, and when the thickness of the sample cell is 5mm, the contrast is 2.7.
The electrochromic performance curve of the compound 3 is shown in fig. 9; the electrochromic optical contrast curve of compound 3 was measured as shown in fig. 10. As can be seen from fig. 9 and 10, compound 3 can achieve a color transition from colorless to pale green to positive red with a contrast as high as 98% at a given negative voltage.
It should be noted that, the compounds 1 and 3 also have the electrically controlled fluorescence property, and the electrically controlled fluorescence property is similar to that of the compound 2, and the description is not provided in the drawings. Therefore, the compounds 1 to 3 have both multicolor electrochromism performance and electric control fluorescence performance, and are good cathode electric stimulation responsiveness materials.
EXAMPLE 4 preparation of Compound 4
(1) According to the reaction formula
Figure BDA0002364824020000181
Compound M5 was prepared according to the following procedure: a mixture of 1, 3-dibromo-5-chlorobenzene (20.00g, 73.98mmol), diphenylamine (26.29g, 155.40mmol) and sodium tert-butoxide (21.32g, 222.00mmol) was dissolved in anhydrous toluene (200.0 mL). Then, the resulting mixture was degassed with nitrogen for 15min, and bis (di-tert-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (CAS No.: 887919-35-9, 0.52g, 0.74mmol) was added. After stirring under nitrogen and heating at 90 ℃ for 3 hours, the mixture was allowed to cool naturally in air. The solvent was then removed and the residue was purified by column chromatography on silica gel, in a volume ratio of 8: hexane/Dichloromethane (DCM) of 1 as eluent gave compound M5 as a white powder, yield: 77 percent.
(2) According to the reaction formula
Figure BDA0002364824020000182
Compound M6 was prepared according to the following procedure: a mixture of compound M5(25.40g, 56.95mmol), pinacol diboron ester (15.85g, 62.64mmol) and potassium acetate (16.74g, 170.90mmol) was dissolved in anhydrous 1, 4-dioxane (200.0 mL). The resulting mixture was degassed with nitrogen for 15min, then tris (dibenzylideneacetone) dipalladium (CAS number: 51364-51-30, 52g, 0.57mmol) and 2-dicyclohexylphosphino-2 ', 4', 6' -triisopropylbiphenyl (0.54g, 1.14mmol) were added. After refluxing at 110 ℃ for 12h under nitrogen, the mixture was immediately filtered. The filtrate was cooled to 0 ℃ in a refrigerator to precipitate the product and filtered again to give compound M6 as a white powder, yield: 65 percent.
(3) According to the reaction formula
Figure BDA0002364824020000191
Compound 4 was prepared as follows: a mixture of compound M6(8.08g, 15.00mmol), 4,4' -dichlorodiphenyl sulfone (1.44g, 5.00mmol), potassium carbonate (6.91g, 50mmol) and methyltrioctylammonium chloride (Aliquat 336, 0.2mmol) was dissolved in toluene (50.0mL) and H2O (25.0 mL). The resulting mixture was then degassed with nitrogen for 15 minutes and tetrakis (triphenylphosphine) palladium (0.46g, 0.40mmol) was added. After stirring under nitrogen and heating at 130 ℃ for 12 hours, the mixture was poured into water and extracted with chloroform. The organic layer was over anhydrous MgSO4And (5) drying. The solvent was then removed and the residue was purified by column chromatography on silica gel, in a volume ratio of 2: 1 in hexane/DCM as eluent to give compound 4 as a pale yellow powder. Yield: 85 percent.
The electrochromic property curve of the compound 4 is shown in fig. 11; it is known that compound 4 has a multi-color electrochromic, the color of which can be changed from a yellowish neutral state to green and magenta; and wherein the behavior has blue fluorescence. The contrast is as high as 98%.
EXAMPLE 5 preparation of Compound 5
According to the reaction formula
Figure BDA0002364824020000192
Compound 5 was prepared as follows: a mixture of compound M6(6.46g, 12.00mmol), acaricidal sulfone (2.53g, 10.00mmol), potassium carbonate (13.82g, 100mmol) and methyltrioctylammonium chloride (0.2mmol) was dissolved in toluene (100.0mL) and H2O (50.0 mL). The resulting mixture was then degassed with nitrogen for 15min and tetrakis (triphenylphosphine) palladium (0.46g, 0.40mmol) was added. After stirring under nitrogen and heating at 130 ℃ for 12h, the mixture was poured into water and extracted with chloroform. The organic layer was over anhydrous MgSO4And (5) drying. The solvent was then removed and the residue was purified by column chromatography on silica gel, in a volume ratio of 2: 1 hexane/DCM as eluent to give compound 5 as a pale yellow powder, yield: 90 percent.
The electrochromic property curve of the compound 5 is shown in fig. 12; it is known that compound 5 has a multi-color electrochromic, the color of which can be changed from a neutral state of light yellow to green and red.
EXAMPLE 6 preparation of Compound 6
(1) According to the reaction formula
Figure BDA0002364824020000201
The preparation procedure was the same as that of compound M6 shown in step (2) of example 4; the difference lies in that: the reaction was carried out by replacing compound M5(56.95mmol) with compound M1(56.95 mmol).
(2) According to the reaction formula
Figure BDA0002364824020000202
The preparation procedure was the same as that of Compound 4 shown in step (3) of example 4; the difference lies in that: reaction with compound M7(8.01g, 15mmol) instead of compound M6(15 mmol); compound 6 was obtained as a white powder with a yield of 86%.
The electrochromic performance curve of the compound 6 is shown in fig. 13; it is known that compound 6 has a polychromatic electrochromic color, which can change its color from a colorless neutral state to green and magenta; and the neutral state has blue fluorescence. The contrast is as high as 98%.
EXAMPLE 7 preparation of Compound 7
According to the reaction formula
Figure BDA0002364824020000211
The preparation procedure was the same as that for compound 5 shown in example 5; the difference lies in that: reaction with compound M7(6.41g, 12.00mmol) instead of compound M6(12.00 mmol); compound 7 was obtained as a white powder with a yield of 89%.
The fluorescence spectrum of compound 7 was measured as shown in FIG. 14; the electrochromic property curve of the compound 7 is shown in fig. 15; the electrochromic property curve of the compound 7 is shown in fig. 16; as can be seen from FIGS. 14 to 16, compound 7 has a multi-color electrochromic property, and the color thereof can be changed from a colorless neutral state to green and magenta and yellow; and the neutral state has blue fluorescence. The contrast is as high as 98%.
It should be noted that although the electrically controlled fluorescence was not characterized for the compounds prepared in all the examples, the molecules with fluorescence can exhibit the property of electrically controlled fluorescence if they can have stable ionic state, as can be seen from the phenomenon that fluorescence of fluorescent molecules in ionic state is generally quenched. The stable ionic state can be reflected from the phenomenon of electrochromism, and when the material has reversible electrochromism performance, the stable ionic state can exist. Therefore, characterization of electrochromic properties is emphasized herein for most of the examples.
EXAMPLE 8 preparation of Compound 8
According to the reaction formula
Figure BDA0002364824020000212
Compound 8 was prepared as follows: m7(6.41g, 12.00mmol) and 2-bromoanthraquinone (3.44g, 12mmol) were charged to a 300mL pressure flask with a magnetic stir bar. Toluene (75mL) and K were added2CO3Aqueous solution (2M, 25mL H2O) and sparged with nitrogen, then Aliquat 336(0.2mmol) and tetrakis (triphenylphosphine) palladium (0.46g, 0.40mmol) were added to the flask. The reaction was stirred at 100 ℃ for 24 hours and then cooled to room temperature. The reaction was washed with water and ethyl acetate. The organic layer was MgSO4Dried and the solvent removed under vacuum. Purification by column chromatography gave compound 8 as a yellow product in 60% yield.
Compound 8 has electrochromic properties, ranging from colorless in neutral state to pink blue; has blue fluorescence, and thus has electrically controlled fluorescence properties.
EXAMPLE 9 preparation of Compound 9
According to the reaction formula
Figure BDA0002364824020000221
The preparation procedure was the same as that for compound 5 shown in example 5; the difference lies in that: replacement of the acaricidal sulfone (10.00mmol) with 2- (4-bromophenyl) -1-phenyl-1H-benzimidazole (CAS number: 2620-76-0, 10.00 mmol); compound 9 was obtained as a white powder with a yield of 89%.
Compound 9 has electrochromic properties, ranging from colorless in neutral state to blue; has blue fluorescence, so that the fluorescent material has the electric control fluorescence property at the same time.
EXAMPLE 10 preparation of Compound 10
According to the reaction formula
Figure BDA0002364824020000222
The preparation procedure was the same as that for compound 5 shown in example 5; the difference lies in that: reaction with 2- (4-bromophenyl) -1-phenyl-1H-benzimidazole (CAS number: 2620-76-0, 10.00mmol) instead of acaricidal sulfone (10.00mmol) and with compound M7(6.41g, 12.00mmol) instead of compound M6(12.00 mmol); compound 10 was obtained as a white powder in 92% yield.
Compound 10 has electrochromic properties, from a neutral state colorless to purple; has blue fluorescence, so that the fluorescent material has the electric control fluorescence property at the same time.
In summary, the present invention provides a cathode electro-stimulation responsive material and a preparation method thereof. Based on the traditional fluorescent molecules, the invention develops the electrochromic property function by introducing functional groups, thereby designing and obtaining the fluorescent material with the structural general formula as
Figure BDA0002364824020000231
A cathodically electrostimulation responsive material of at least one of the organic substances of (a); the cathode electrical stimulation response material only responds to cathode electrical stimulation, and the response selectivity is high; the neutral state of the material can realize a completely colorless state, the color is very easy to regulate, multicolor electrochromism and ultrahigh contrast can be realized, the material has the performance characteristics of electrically controlled fluorescence, and the material can be applied to the fields of electrochromism, electrically controlled fluorescence and OLED. Meanwhile, the design strategy of the cathode electrical stimulation response material essentially realizes the widening of the selection range of the electric control intelligent material.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. The cathode electrical stimulation response material is characterized by comprising a structural general formula
Figure FDA0002364823980000011
At least one of the organic substances of (a); in the formula, Ar is
Figure FDA0002364823980000012
Figure FDA0002364823980000013
The position shown by the curvilinear bond is the connection position of Ar, and R1-R4 are independently selected from H, F, CH3、CF3、OCF3、SCF3、CH2C(CH3)3And the linking position being an optionally substituted position on the ring
Figure FDA0002364823980000014
One of (1); n is the number of Ar connected with R, n is an integer larger than 0, and n is smaller than or equal to the total number of connecting positions contained in R; r is selected from H, F, CN, NO2、OCF3、SCF3And the linking position being an optionally substituted position on the ring
Figure FDA0002364823980000015
Figure FDA0002364823980000021
Figure FDA0002364823980000031
One kind of (1).
2. The cathodal electrostimulation responsive material according to claim 1, characterized in that Ar is
Figure FDA0002364823980000032
When R is H, n is 1.
3. A cathodic electro-stimulation responsive material as claimed in claim 2 wherein R1 and R2 are not both H.
4. The cathodal electrostimulation responsive material according to claim 1, characterized in that R1 ═ R2, and/or R3 ═ R4.
5. The cathodal electrostimulation responsive material according to claim 1, characterized in that R1-R2-R3-R4.
6. The cathodal electrostimulation responsive material according to claim 5,
Figure FDA0002364823980000041
is selected from
Figure FDA0002364823980000042
Figure FDA0002364823980000051
At least one of (1).
7. A method for preparing a cathodic electro-stimulation responsive material as defined in any one of claims 1 to 6, wherein R contains an aromatic ring and n connecting positions of R are all located on the aromatic ring, and
Figure FDA0002364823980000052
the method comprises the following steps: mixing Ar-H, potassium tert-butoxide and a dried first organic solvent, and carrying out a first reaction at 90-130 ℃ to obtain a first mixed solution; will R (F)nAdding a solution dissolved in a second organic solvent into the first mixed solution, carrying out a second reaction at 140-150 ℃, and purifying to obtain the
Figure FDA0002364823980000053
Wherein R (F)nIs a compound in which n connecting positions of R are all F;
r contains aromatic ring and n connecting positions of R are all positioned on the aromatic ring,
Figure FDA0002364823980000054
the method comprises the following steps: under inert atmosphere, Ar-Br, R (Y)n、K2CO3Mixing the aqueous solution, methyl trioctyl ammonium chloride, the first palladium catalyst and a third organic solvent, carrying out a third reaction at 90-130 ℃, and purifying to obtain the palladium-palladium catalyst
Figure FDA0002364823980000055
Wherein R (Y)nIs a compound in which all of the n linking positions of R are Y, Y ═ B (OH)2Or
Figure FDA0002364823980000061
Alternatively, the first and second electrodes may be,
under an inert atmosphere, mixing
Figure FDA0002364823980000062
R(X)n、K2CO3Mixing the aqueous solution, methyl trioctyl ammonium chloride, a second palladium catalyst and a fourth organic solvent, carrying out a fourth reaction at 90-130 ℃, and purifying to obtain the catalyst
Figure FDA0002364823980000063
Wherein R (X)nThe compound is a compound in which all of the n connecting positions of R are X, and X is Cl or Br.
8. The method according to claim 7, wherein Ar-H, potassium tert-butoxide, R (F)nThe molar ratio between n and 1.2 n: n-1.2 n: 1; and/or
The R (Y)n、Ar-Br、K2CO3Methyl group (II)The molar ratio of the trioctyl ammonium chloride to the first palladium catalyst is 1: 0.8n to n: 3n to 10 n: 0.01 n-0.05 n: 0.01 n-0.05 n; and/or
The R (X)n、
Figure FDA0002364823980000064
K2CO3The molar ratio of methyl trioctyl ammonium chloride to the second palladium catalyst is 1: n-1.5 n: 3n to 10 n: 0.01 n-0.04 n: 0.01 n-0.05 n.
9. The method according to claim 7, wherein the first organic solvent and the second organic solvent are independently selected from one of dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide; and/or
The third organic solvent and the fourth organic solvent are independently selected from one of toluene, N-dimethylformamide and 1, 4-dioxane; and/or
The first palladium catalyst and the second palladium catalyst are independently selected from one of tetrakis (triphenylphosphine) palladium and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex.
10. The preparation method according to claim 7, wherein the time of the first reaction is 0.5-12 h; and/or
The second reaction time is 2-24 h; and/or
The third reaction time is 9-24 h; and/or
The fourth reaction time is 12-24 h.
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