CN109053531B - Asymmetric squarylium cyanine material and preparation method and application thereof - Google Patents

Asymmetric squarylium cyanine material and preparation method and application thereof Download PDF

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CN109053531B
CN109053531B CN201810924884.8A CN201810924884A CN109053531B CN 109053531 B CN109053531 B CN 109053531B CN 201810924884 A CN201810924884 A CN 201810924884A CN 109053531 B CN109053531 B CN 109053531B
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asymmetric squaraine
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董桂芳
郭航
席婵娟
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Tsinghua University
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Abstract

The invention belongs to the technical field of preparation of squaraine materials, and particularly relates to an asymmetric squaraine material and a preparation method and application thereof. The invention passes through the pair C1And C2The design and selection of the substituent enable the spectral absorption peak to be positioned in a blue-green light absorption area, so that the organic blue-green light sensitive device can be prepared, and the application requirements in the fields of blue-green light sensing and multichannel optical communication can be met; meanwhile, the absorption half-peak width of the asymmetric squaraine material solution and the absorption half-peak width of the asymmetric squaraine material in a film form are both smaller than 110nm, and the asymmetric squaraine material has very important application in the aspect of preparing a photosensitive diode. In addition, the material provided by the invention has strong stability, and can meet various processes such as evaporation, spin coating, ink-jet printing and the like.

Description

Asymmetric squarylium cyanine material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of squaraine materials, and particularly relates to an asymmetric squaraine material and a preparation method and application thereof.
Background
Squaraine is a class of functional organic dyes, highly delocalized conjugated molecules with a cyanine-like structure. It features sharp and strong absorption in long-wave region, high solubility in low-polarity solvent and high photo-thermal stability. The squarylium has the advantages of good absorption and emission properties, larger molecular rigidity, low excited state recombination energy, easy structure modification and the like, has attracted more and more attention, and is widely researched and applied to the fields of organic solar cells, organic photodetectors, photosensitive diodes and the like in recent years.
The squarylium cyanine compound is formed by condensing squaric acid and an electron-rich aromatic ring or heterocycle, can form 1, 3-substitution (the structure is shown in the following formula),
Figure BDA0001765117630000011
according to X, Y, the compounds can be classified into symmetrical and asymmetrical squaraine types. In general, asymmetric squaraines have better solubility, most importantly, richer structure adjustability, and have more excellent performance than symmetric squaraine compounds in photosensitive applications such as dye-sensitized solar cells, xerography, near-infrared sensitization and the like. However, most of the spectrum absorption peaks of the asymmetric squaraine materials disclosed in the prior art are located in red and orange light absorption areas, and the application requirements in the fields of blue-green light sensing and multichannel optical communication cannot be met, so that the design and synthesis of novel asymmetric squaraine materials are of great significance for constructing novel efficient squaraine materials and expanding the application range of the novel efficient squaraine materials.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that most of the spectrum absorption peaks of the asymmetric squaraine material in the prior art are located in red and green light absorption areas, so that the asymmetric squaraine material with the spectrum absorption peak located in a blue and green light absorption area, and the preparation method and the application thereof are provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
an asymmetric squaraine material has a structure shown in a general formula (I):
Figure BDA0001765117630000021
wherein, X1And X2Each independently selected from oxygen atom, halogen, cyano or alkanyl, C1Is a diphenylamine group or a substituted diphenylamine derivative group; c2Is one of pyrrole group, indole group, thiophene group, pyrrole group containing substituent or heteroatom, indole group containing substituent or heteroatom, and thiophene group containing substituent or heteroatom.
Preferably, X is1And X2Each represents an oxygen atom, C1Is a diphenylamine group.
Preferably, the heteroatom is at least one of S, O or N.
Preferably, the asymmetric squaraine material has the following structure:
Figure BDA0001765117630000031
the asymmetric squarylium material is applied to a blue-green light sensing device or a multi-channel optical communication device.
Further, at least one of the conductive substrate layer, the electron transport layer or the hole transport layer in the device contains the asymmetric squaraine material. The devices have a conventional structure and may include, but are not limited to, ITO anodes, hole injection layers, hole transport layers, electron injection layers, cathodes, and the like.
The preparation method of the asymmetric squaraine material comprises the following steps:
and (3) synthesis of an intermediate: the synthetic route is shown as a formula (II),
Figure BDA0001765117630000041
dissolving 3, 4-diisopropoxy-3-cyclobutene-1, 2-diketone and diphenylamine or diphenylamine derivative (reaction substrate A) in a solvent, adding concentrated hydrochloric acid, heating for reflux reaction, separating, performing hydrolysis reaction, and purifying to obtain an intermediate;
and (3) synthesis of a target product: the synthetic route is shown as a formula (III),
Figure BDA0001765117630000042
dissolving the intermediate and a reaction substrate C in a solvent, heating for reflux reaction, separating and purifying to obtain a target product; wherein the reaction substrate C is C2The substituent corresponds to the compound.
Further, the air conditioner is provided with a fan,
in the step of synthesizing the intermediate, the molar ratio of the 3, 4-diisopropoxy-3-cyclobutene-1, 2-diketone to the diphenylamine or diphenylamine derivative is 1: 1-1: 2, and the solvent is isopropanol;
in the step of synthesizing the target product, the molar ratio of the intermediate to the reaction substrate C is (5: 1-1: 1); the solvent is a mixture of toluene and n-butanol, and preferably, the volume ratio of the toluene to the n-butanol is 1: 1.
Further, in the step of synthesizing the intermediate, the reflux reaction temperature is 85-95 ℃; in the step of synthesizing the target product, the temperature of the reflux reaction is 110-120 ℃.
Further, the hydrolysis reaction in the step of synthesizing the intermediate is that the separated product is dissolved in a solvent, concentrated hydrochloric acid is added, and the mixture is heated and refluxed for 3 to 5 hours at the temperature of 65 to 75 ℃.
The technical scheme of the invention has the following advantages:
1. the asymmetric squaraine material provided by the invention is prepared by reacting C1And C2The design and selection of the substituent enable the spectral absorption peak to be positioned in a blue-green light absorption area, so that the organic blue-green light sensitive device can be prepared, and the application requirements in the fields of green light sensing and multi-channel optical communication can be met; meanwhile, the absorption half-peak width of the asymmetric squaraine material solution and the absorption half-peak width of the asymmetric squaraine material in a film form are both smaller than 110nm, and the asymmetric squaraine material has very important application in the aspect of preparing a photosensitive diode. In addition, the material provided by the invention is strong in stability, and can meet various process requirements such as an evaporation process, spin coating, ink-jet printing and the like.
2. The preparation method of the asymmetric squaraine material provided by the invention obtains the asymmetric squaraine material with a spectrum absorption peak positioned in a blue-green light absorption area through the design and synthesis of a series of squaraine materials with different absorption peaks. The preparation method is simple, the reaction sites are obvious, and the reaction process is easy to control.
3. The application of the asymmetric squaraine material provided by the invention has good hole and electron transmission characteristics, so that a hole and electron transmission layer and the like are not required to be added when a device is prepared, and the preparation process is greatly simplified.
Drawings
FIG. 1 is an absorption spectrum of an asymmetric squaraine material provided in example 1 of the present invention;
fig. 2 shows the dark current response of an asymmetric squaraine-based photodiode provided in embodiment 1 of the present invention;
fig. 3 illustrates the external quantum efficiency of an asymmetric squaraine-based photodiode provided in example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of an asymmetric squaraine material, which has the following structure:
Figure BDA0001765117630000061
the specific preparation method of the asymmetric squaraine material with the structure comprises the following steps:
step one, synthesis of an intermediate:
1.4 g of diphenylamine and 3.8g of 3, 4-diisopropoxy-3-cyclobutene-1, 2-dione are dissolved in 160mL of isopropanol, dissolved for 5 minutes with stirring, 0.8mL of concentrated hydrochloric acid is added, and the mixture is refluxed at 90 ℃ for 3 hours to give a bright yellow solution.
2. The reaction mixture was filtered to remove excess reaction substrate, the filtrate was removed by rotary evaporation, and 200mL of CHCl was used3Dissolving and then carrying out rotary evaporation to obtain a dried solid.
3. The dried solid was dissolved in 120mL of acetone and 120mL of 6M hydrochloric acid, and the solution was refluxed at 70 ℃ for 4 hours to give a deep red color.
4. The reaction was concentrated to 50mL by rotary evaporation and concentrated with CHCl3Extracting for three times (50 mL each time), collecting extractive solution, rotary steaming to obtain reddish brown residue, dissolving the residue with 500mL hot water, heating and stirring for 1 hr until the solution appears pale yellow, filtering, rotary steaming the filtrate to obtain pale yellow crystals, and drying at 100 deg.C for 8 hr to obtain intermediate
Figure BDA0001765117630000071
The second step is that: synthesis of target product
1. 1.1g of the intermediate purified in the last step is added with 0.3g of 2, 4-dimethylpyrrole, dissolved in 80mL of toluene and 80mL of n-butanol, and after complete dissolution, the solution starts to reflux at 115 ℃ for 4h, and the solution is black red.
2. Excess solvent was removed by rotary evaporation, column run, previous run with dichloromethane: enabling the mixed solution of methanol 500:3 to pass through a column, and separating a target product; the mixture ratio was changed, using dichloromethane: the mixture of methanol 1000:1 was further separated until the desired product (photoluminescence orange) was finally obtained.
And (3) performance testing: the obtained product is tested, and the absorption spectra of the solution and the film are shown in figure 1, wherein the absorption peak position of the solution absorption spectrum of the material is 480nm, the material is a blue-green light absorption material, and the absorption half-peak width under the solution and the absorption half-peak width under the film form are both less than 110 nm.
The basic photodiode device includes:
the ITO electrode comprises a flexible substrate, an ITO electrode, an asymmetric squarylium cyanine material (photosensitive layer), an aluminum electrode and the like. The asymmetric squarylium material has good hole and electron transmission characteristics, so that a hole and electron transmission layer and the like are not required to be added when the device is prepared, and the preparation process is greatly simplified.
The asymmetric squaraine material provided by the invention can be prepared by a spin coating method, an evaporation method or an ink-jet printing method. In the embodiment, the asymmetric squaraine material is prepared by an evaporation method, and the evaporation rate is 0.1 nm/s. The thickness of the vapor deposition was kept at about 50 nm. And then placing the prepared film into a vacuum chamber to finish the preparation of the aluminum electrode to obtain the photosensitive diode.
The photodiode device dark current is shown in fig. 2: as can be seen from the figure, under dark conditions and under light conditions (6 mW/cm)2) The device has good photoelectric response characteristics and has good prospects in practical application.
The external quantum efficiency of the device is shown in fig. 3: it can be seen from the figure that the external quantum efficiency can reflect the absorption of different lights by one device, the external quantum efficiency of the device exceeds 15% at 500nm (blue-green light), and the device has almost no absorption to red light, and shows good light selection characteristics.
ESI-MS (electrospray ionization Mass Spectrometry [ M/z ]]):343[M+H]+。
Elemental analysis (C)22H18N2O2): calal.calcd (theoretical value): c, 77.17; h, 5.30; n, 8.18; o, 9.35; found (measured value): c, 77.37; h, 5.20; n, 8.38; and O, 9.05.
The photoelectric response characteristics and external quantum efficiency of the device prepared from the asymmetric squaraine material provided by the embodiments 2-5 of the invention by the method are similar to those of the device prepared by the embodiment 1, and the details are not repeated.
Example 2
The embodiment provides an asymmetric squaraine material, which has the following structure:
Figure BDA0001765117630000081
the specific preparation method of the asymmetric squaraine material with the structure comprises the following steps:
step one, synthesis of an intermediate:
1.4 g of diphenylamine and 3.8g of 3, 4-diisopropoxy-3-cyclobutene-1, 2-dione are dissolved in 160mL of isopropanol, dissolved for 5 minutes with stirring, 0.8mL of concentrated hydrochloric acid is added, and the mixture is refluxed at 85 ℃ for 3 hours to give a bright yellow solution.
2. The reaction mixture was filtered to remove excess reaction substrate, the filtrate was removed by rotary evaporation, and 200mL of CHCl was used3Dissolving and then carrying out rotary evaporation to obtain a dried solid.
3. The dried solid was dissolved in 120mL of acetone and 120mL of 6M hydrochloric acid, and the solution was refluxed at 70 ℃ for 4 hours to give a deep red color.
4. The reaction was concentrated to 50mL by rotary evaporation and concentrated with CHCl3Extracting for three times (50 mL each time), collecting extractive solution, rotary steaming to obtain reddish brown residue, dissolving the residue with 500mL hot water, heating and stirring for 1 hr until the solution appears pale yellow, filtering, rotary steaming the filtrate to obtain pale yellow crystals, and drying at 100 deg.C for 8 hr to obtain intermediate
Figure BDA0001765117630000091
The second step is that: synthesis of target product
1. 1.1g of the intermediate purified last time is added with 0.5g of 2, 4-dimethylthiophene, dissolved in 80mL of toluene and 80mL of n-butanol, and after complete dissolution, the solution starts to reflux at 110 ℃ for 4h, and the solution is black red.
2. Excess solvent was removed by rotary evaporation and the column was prepared (as in example 1) to obtain the desired product.
And (3) performance testing: and testing the obtained product, wherein the position of the spectral absorption peak of the solution is 470nm, the solution is a blue light absorption material, and the absorption half-peak width under the solution and the absorption half-peak width under the film form are both less than 110 nm.
ESI-MS (electrospray ionization Mass Spectrometry [ M/z ]]):360[M+H]+。
Elemental analysis (C)22H17NO2S): calal.calcd (theoretical value): c, 73.51; h, 4.77; n, 3.90; o, 8.90; s, 8.92; found (measured value): c, 73.37; h, 4.91; n, 3.92; o, 8.92; and S, 8.88.
Example 3
The embodiment provides an asymmetric squaraine material, which has the following structure:
Figure BDA0001765117630000101
the specific preparation method of the asymmetric squaraine material with the structure comprises the following steps:
step one, synthesis of an intermediate:
1.4 g of diphenylamine and 3.8g of 3, 4-diisopropoxy-3-cyclobutene-1, 2-dione are dissolved in 160mL of isopropanol, dissolved for 5 minutes with stirring, 0.8mL of concentrated hydrochloric acid is added, and the mixture is refluxed at 95 ℃ for 3 hours to give a bright yellow solution.
2. The reaction mixture was filtered to remove excess reaction substrate, the filtrate was removed by rotary evaporation, and 200mL of CHCl was used3Dissolving and then carrying out rotary evaporation to obtain a dried solid.
3. The dried solid was dissolved in 120mL of acetone and 120mL of 6M hydrochloric acid, and the solution was refluxed at 65 ℃ for 5 hours to give a deep red color.
4. The reaction was concentrated to 50mL by rotary evaporation and concentrated with CHCl3Extracting for three times (50 mL each time), collecting extractive solution, rotary steaming to obtain reddish brown residue, dissolving the residue with 500mL hot water, heating and stirring for 1 hr until the solution appears pale yellow, filtering, rotary steaming the filtrate to obtain pale yellow crystals, and drying at 100 deg.C for 8 hr to obtain intermediate
Figure BDA0001765117630000111
The second step is that: synthesis of target product
1. 1.1g of the intermediate purified last time is added with 0.45g of 2, 4-dimethyl-3-methoxy pyrrole, dissolved in 80mL of toluene and 80mL of n-butanol, and after complete dissolution, the solution starts to reflux at 120 ℃ for 3.5h, and the solution is black red.
2. The excess solvent was removed by rotary evaporation to prepare a column, which was the same as in example 1 to obtain the desired product.
And (3) performance testing: and testing the obtained product, wherein the absorption peak positions of the obtained solution and film are 470nm, the obtained product is a blue-green light absorption material, and the absorption half-peak width under the solution and the absorption half-peak width under the film form are both less than 110 nm.
ESI-MS (electrospray ionization Mass Spectrometry [ M/z ]]):373[M+H]+。
Elemental analysis (C)23H20N2O3): calal.calcd (theoretical value): c, 74.18; h, 5.41; n, 7.52; o, 12.89; found (measured value): c, 74.37; h, 5.22; n, 7.50; o, 12.91.
Example 4
The embodiment provides an asymmetric squaraine material, which has the following structure:
Figure BDA0001765117630000121
the specific preparation method of the asymmetric squaraine material with the structure comprises the following steps:
step one, synthesis of an intermediate:
1.4 g of diphenylamine and 3.8g of 3, 4-diisopropoxy-3-cyclobutene-1, 2-dione are dissolved in 160mL of isopropanol, dissolved for 5 minutes with stirring, 0.8mL of concentrated hydrochloric acid is added, and the mixture is refluxed at 90 ℃ for 3 hours to give a bright yellow solution.
2. The reaction mixture was filtered to remove excess reaction substrate, the filtrate was removed by rotary evaporation, and 200mL of CHCl was used3Dissolving and then carrying out rotary evaporation to obtain a dried solid.
3. The dried solid was dissolved in 120mL of acetone and 120mL of 6M hydrochloric acid, and the solution was refluxed at 70 ℃ for 4 hours to give a deep red color.
4. The reaction was concentrated to 50mL by rotary evaporation and concentrated with CHCl3Extracting for three times (50 mL each time), collecting extractive solution, rotary steaming to obtain reddish brown residue, dissolving the residue with 500mL hot water, heating and stirring for 1 hr until the solution appears pale yellow, filtering, rotary steaming the filtrate to obtain pale yellow crystals, and drying at 100 deg.C for 8 hr to obtain intermediate
Figure BDA0001765117630000122
The second step is that: synthesis of target product
1. 1.1g of the intermediate purified last time is added with 0.35g of 3-methylindole, dissolved in 80mL of toluene and 80mL of n-butanol, and after complete dissolution, the solution starts to reflux at 115 ℃ for 4h, and the solution is black red.
2. The excess solvent was removed by rotary evaporation to prepare a column, which was the same as in example 1 to obtain the desired product.
And (3) performance testing: and testing the obtained product, wherein the spectral absorption peak positions of the solution and the film are 495nm, the obtained product is a blue-green light absorption material, and the absorption half-peak width under the solution and the absorption half-peak width under the film form are both less than 110 nm.
ESI-MS (electrospray ionization Mass Spectrometry [ M/z ]]):379[M+H]+。
Elemental analysis (C)25H18N2O2): calal.calcd (theoretical value): c, 79.35; h, 4.79; n, 7.40; o, 8.46; found (measured value): c, 79.36; h, 4.80; n, 7.48; and O, 8.38.
Example 5
The embodiment provides an asymmetric squaraine material, which has the following structure:
Figure BDA0001765117630000131
the specific preparation method of the asymmetric squaraine material with the structure comprises the following steps:
the first step is as follows: and (3) synthesis of an intermediate:
1. 5g of 1,1' -dinaphthylamine and 3.8g of 3, 4-diisopropoxy-3-cyclobutene-1, 2-dione are dissolved in 160mL of isopropanol, and after stirring for 5min, 0.8mL of concentrated hydrochloric acid is added and the mixture is refluxed at 90 ℃ for 3h, the solution appears bright yellow.
2. The reaction mixture was filtered to remove excess reaction substrate, the filtrate was removed by rotary evaporation, and 200mL of CHCl was used3Dissolving and then carrying out rotary evaporation to obtain a dried solid.
3. The dried solid was dissolved in 120mL of acetone and 120mL of 6M hydrochloric acid, and the solution was refluxed at 70 ℃ for 4 hours to give a deep red color.
4. The reaction was concentrated to 50mL by rotary evaporation and concentrated with CHCl3Extracting three times (50 mL each time), collecting extractive solution, rotary evaporating to obtain reddish brown residue, dissolving the residue with 500mL hot water, heating and stirring for 1 hr until the solution appears pale yellow, filtering, and rotary evaporating the filtrateTo obtain light yellow crystals, and drying at 100 ℃ for 8h to obtain an intermediate
Figure BDA0001765117630000141
The second step is that: synthesis of target product
1. 2g of the intermediate purified last time is added with 0.5g of 2, 4-dimethylpyrrole, dissolved in 80mL of toluene and 80mL of n-butanol, and after complete dissolution, reflux is started at 115 ℃ for 4h, and the solution is black red.
2. The excess solvent was removed by rotary evaporation to prepare a column, which was the same as in example 1 to obtain the desired product.
And (3) performance testing: and testing the obtained product, wherein the spectral absorption peak positions of the obtained solution and the obtained film are 485nm, the obtained product is a blue-green light absorption material, and the absorption half-peak width under the solution and the absorption half-peak width under the film form are both less than 110 nm.
ESI-MS (electrospray ionization Mass Spectrometry [ M/z ]]):443[M+H]+。
Elemental analysis (C)30H22N2O2): calal.calcd (theoretical value): c, 81.43; h, 5.01; n, 6.33; o, 7.23; found (measured value): c, 81.01; h, 5.43; n, 6.23; o, 7.33.
Comparative example 1
The comparative example provides a symmetrical squaraine material, which has the structure:
Figure BDA0001765117630000151
and (3) performance testing: and testing the obtained product, and determining that the position of the spectral absorption peak of the film is 680nm, the film is a red light absorption material, and the absorption half-peak width under the solution and the absorption half-peak width under the film form are both less than 110 nm.
Comparative example 2
The comparative example provides an asymmetric squaraine material, which has the structure:
Figure BDA0001765117630000152
and (3) performance testing: and testing the obtained product, and determining that the spectral absorption peak position of the film is 540nm, the film is a green light absorption material, and the absorption half-peak width of the film is more than 120 nm. Meanwhile, the material contains hydroxyl and long-chain alkyl groups, so that a thin film cannot be prepared in an evaporation mode, and the hydroxyl and the like are damaged at high temperature, so that the performance of the device is greatly reduced.
By comparing the data of the examples and the comparative examples, it can be seen that the comparison of C1And C2The design and selection of the substituent enable the spectral absorption peak to be positioned in a blue-green light absorption area, and the application requirements in the fields of green light sensing and multi-channel optical communication are met; meanwhile, the absorption half-peak width of the squaraine material solution and the absorption half-peak width of the film form are both less than 110nm, so that the squaraine material has very important application in the aspect of preparing a photosensitive diode; in addition, the material is more stable, and meets various process requirements such as evaporation process, spin coating, ink-jet printing and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. An asymmetric squaraine material, characterized by having a structure represented by general formula (I):
Figure FDA0002630970670000011
wherein, X1And X2Each independently selected from oxygen atom, halogen, cyano or alkanyl, C1Is a diphenylamine group or a substituted diphenylamine group; c2Is pyrrole group, indole group and thiophene group.
2. The asymmetric squaraine material of claim 1 wherein X is1And X2Each represents an oxygen atom, C1Is a diphenylamine group.
3. The asymmetric squaraine material of claim 1, wherein the asymmetric squaraine material has a structure as follows:
Figure FDA0002630970670000012
4. use of the asymmetric squaraine material of any one of claims 1-3 in a blue-green light sensing device or a multichannel optical communication device.
5. The use of the asymmetric squaraine material of claim 4 in a green sensor device or a multichannel optical communication device, wherein the asymmetric squaraine material is contained in at least one of a conductive substrate layer, an electron transport layer or a hole transport layer in the device.
6. A method of preparing an asymmetric squaraine material according to any one of claims 1-3, comprising the steps of:
and (3) synthesis of an intermediate: the synthetic route is shown as a formula (II),
Figure FDA0002630970670000021
dissolving 3, 4-diisopropoxy-3-cyclobutene-1, 2-diketone and a reaction substrate A in a solvent, adding concentrated hydrochloric acid, heating for reflux reaction, separating, performing hydrolysis reaction, and purifying to obtain an intermediate; wherein the reaction substrate A is C1Compounds corresponding to the substituents;
and (3) synthesis of a target product: the synthetic route is shown as a formula (III),
Figure FDA0002630970670000022
dissolving the intermediate and a reaction substrate C in a solvent, heating for reflux reaction, separating and purifying to obtain a target product; wherein the reaction substrate C is C2The substituent corresponds to the compound.
7. The method of claim 6, wherein the asymmetric squaraine material is selected from the group consisting of,
in the synthesis step of the intermediate, the molar ratio of the 3, 4-diisopropoxy-3-cyclobutene-1, 2-diketone to the reaction substrate A is 1: 1-1: 2, and the solvent is isopropanol;
in the step of synthesizing the target product, the molar ratio of the intermediate to the reaction substrate C is (5: 1-1: 1); the solvent is a mixture of toluene and n-butanol.
8. The method of claim 7, wherein the volume ratio of toluene to n-butanol is 1: 1.
9. The method for preparing the asymmetric squaraine material as claimed in claim 7, wherein in the step of synthesizing the intermediate, the reflux reaction temperature is 85-95 ℃;
in the step of synthesizing the target product, the temperature of the reflux reaction is 110-120 ℃.
10. The method for preparing asymmetric squaraine material according to any one of claims 7-9, wherein the hydrolysis reaction in the step of synthesizing the intermediate comprises dissolving the separated product in a solvent, adding concentrated hydrochloric acid, and heating and refluxing at 65-75 ℃ for 3-5 h.
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