CN109053531A - A kind of asymmetric side's acid cyanines material and its preparation method and application - Google Patents

A kind of asymmetric side's acid cyanines material and its preparation method and application Download PDF

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CN109053531A
CN109053531A CN201810924884.8A CN201810924884A CN109053531A CN 109053531 A CN109053531 A CN 109053531A CN 201810924884 A CN201810924884 A CN 201810924884A CN 109053531 A CN109053531 A CN 109053531A
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asymmetric side
acid cyanines
acid
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preparation
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CN109053531B (en
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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 sour cyanines technical field of material in side, and in particular to a kind of asymmetric side's acid cyanines material and its preparation method and application.The present invention passes through to C1And C2The design and selection of substituent group, so that its spectral absorption peak, which is located at bluish-green photo-absorption region, meets the application demand of bluish-green light sensing, multichannel optical communication field to prepare organic blue green light Sensitive Apparatus；Meanwhile the absorption half-peak breadth under the absorption half-peak breadth and film morphology under asymmetric side's acid cyanines material solution provided by the invention is respectively less than 110nm, there is highly important application in terms of preparing photodiode.In addition, stability of material provided by the invention is strong, it can satisfy the kinds of processes such as vapor deposition, spin coating, inkjet printing.

Description

A kind of asymmetric side's acid cyanines material and its preparation method and application
Technical field
The invention belongs to the sour cyanines technical field of material in side, and in particular to a kind of asymmetric side's acid cyanines material and its preparation Methods and applications.
Background technique
Side's acid cyanines are a kind of functional organic dyestuff, the conjugated molecule of the height delocalization with class cyanine structure.It Most significant feature is that have sharp and strong absorption in Long wavelength region, solubility is got well and had very in low polar solvent Good photo and thermal stability.Since the sour cyanines in side have good absorption and emission characteristic, biggish molecular rigidity and low excited state weight The advantages that group energy and structure are easy modification, receive more and more attention, being widely studied to apply in recent years is having The fields such as machine solar battery, organic photodetector and photodiode.
Side's acid cyanine compound is to be formed by side's acid with electron rich aromatic ring or heterocyclic condensation, and can forming 1,3- substitution, (structure is shown In following formula),
It is identical or not identical according to X, Y, and it is divided into symmetric and unsymmetric side's acid cyanines two types.In general, asymmetric Side's acid cyanines have better dissolubility, it is most important that have richer adjustability of structure, in dye sensitization sun electricity Pond, xerography, near-infrared increase the photosensitive application aspects such as sense and show compared with the more excellent performance of symmetric form side's acid compound.But It is that asymmetric side's acid cyanines material, most of spectral absorption peak disclosed in the prior art are located at blood orange photo-absorption region, it cannot Meet the application demand of bluish-green light sensing, multichannel optical communication field, thus design, the asymmetric side's acid cyanines material of synthesizing new, It is of great significance to constructing new and effective side's acid cyanines material, extending its application range.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that asymmetric side's acid cyanines material spectrum in the prior art is overcome to inhale Receiving most of peak is the defect positioned at red-green glow absorption region, so that providing a kind of spectral absorption peak is located at bluish-green photo-absorption region Asymmetric side's acid cyanines material and its preparation method and application.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of asymmetric side's acid cyanines material has structure shown in logical formula (I):
Wherein, X1And X2It is independently selected from oxygen atom, halogen, one of cyano or alkyl group, C1For hexichol amido Group or the diphenylamine derivatives group replaced；C2For pyrrole group, indolyl radical, thienyl group contains substituent group or hetero atom Pyrrole group contain one of substituent group or heteroatomic thienyl group containing substituent group or heteroatomic indolyl radical.
Preferably, the X1And X2Respectively represent oxygen atom, C1For diphenylamino group.
Preferably, the hetero atom is S, at least one of O or N.
Preferably, asymmetric side's acid cyanines material has structure as follows:
A kind of application of above-mentioned asymmetric side's acid cyanines material in bluish-green photo-sensing device or multichannel optic communication device.
Further, the conductive basal layer in the device, in at least one layer in electron transfer layer or hole transmission layer Contain asymmetric side's acid cyanines material.The device has conventional structure, can be, but not limited to include ito anode, hole note Enter layer, hole transmission layer, electron transfer layer, electron injecting layer, cathode etc..
A kind of preparation method of above-mentioned asymmetric side's acid cyanines material, comprising the following steps:
The synthesis of intermediate: shown in synthetic route such as formula (II),
3,4- diisopropoxy -3- cyclobutane -1,2- diketone and diphenylamines or diphenylamine derivatives (reaction substrate A) is molten In solvent, concentrated hydrochloric acid is added, heating carries out back flow reaction, and reaction is hydrolyzed in separation, purifies, obtains intermediate；
The synthesis of target product: shown in synthetic route such as formula (III),
Intermediate and reaction substrate C are dissolved in solvent, heating carries out back flow reaction, separates, purification, obtains target production Object；Wherein, reaction substrate C is C2Compound corresponding to substituent group.
Further,
In the synthesis step of the intermediate, 3,4- diisopropoxy -3- cyclobutane -1,2- diketone and diphenylamines or The molar ratio of diphenylamine derivatives is 1:1-1:2, and the solvent is isopropanol；
In the synthesis step of the target product, the molar ratio of intermediate and reaction substrate C are (5:1-1:1)；It is described molten Agent is the mixture of toluene and n-butanol, it is preferred that the volume ratio of toluene and n-butanol is 1:1.
Further, in the synthesis step of the intermediate, back flow reaction temperature is 85-95 DEG C；The target product In synthesis step, the temperature of back flow reaction is 110-120 DEG C.
Further, the hydrolysis in the synthesis step of the intermediate is that the product after separation is dissolved in solvent, Concentrated hydrochloric acid is added, is heated to reflux 3-5h at 65-75 DEG C.
Technical solution of the present invention has the advantages that
1. asymmetric side's acid cyanines material provided by the invention, by C1And C2The design and selection of substituent group, so that its light Spectrum absorption peak is located at bluish-green photo-absorption region, and to prepare organic blue green light Sensitive Apparatus, it is logical to meet green light sensing, multichannel light The application demand in letter field；Meanwhile absorption half-peak breadth and film shape under asymmetric side's acid cyanines material solution provided by the invention Absorption half-peak breadth under state is respectively less than 110nm, there is highly important application in terms of preparing photodiode.In addition, this hair The material settling out of bright offer is strong, can satisfy the kinds of processes such as evaporation process, spin coating, inkjet printing and wants.
2. the preparation method of asymmetric side's acid cyanines material provided by the invention passes through a series of side's acid to different absorption peaks The design and synthesis of cyanines material have obtained asymmetric side's acid cyanines material that spectral absorption peak is located at bluish-green photo-absorption region.The system Preparation Method is simple, and reaction site is obvious, easily controllable reaction process.
3. the application of asymmetric side's acid cyanines material provided by the invention, since asymmetric side's acid cyanines material has good sky Cave and electron transport property may not need additional hole, electron transfer layer etc., greatly simplify preparation process when preparing device.
Detailed description of the invention
The abosrption spectrogram for asymmetric side's acid cyanines material that Fig. 1 embodiment of the present invention 1 provides；
The brightness current-responsive based on asymmetric side's acid cyanines photodiode that Fig. 2 embodiment of the present invention 1 provides；
The external quantum efficiency based on asymmetric side's acid cyanines photodiode that Fig. 3 embodiment of the present invention 1 provides.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition Conventional reagent product.
Embodiment 1
The present embodiment provides a kind of preparations of asymmetric side's acid cyanines material, have the following structure:
Asymmetric side's acid cyanines material with above structure specific the preparation method comprises the following steps:
The first step, the synthesis of intermediate:
1, by 3,4- diisopropoxy -3- cyclobutane -1,2 of 4g diphenylamines and 3.8g,-diketone is dissolved into 160mL isopropyl 0.8mL concentrated hydrochloric acid is added after stirring and dissolving 5min for alcohol, in 90 DEG C of reflux 3h, solution presentation glassy yellow.
2, filtering reacting liquid removes extra reaction substrate, filtered fluid is removed by revolving method, with the CHCl of 200mL3Dissolution After rotate, the solid after must drying.
3, the solid after above-mentioned drying is dissolved with 120mL acetone and 6M hydrochloric acid 120mL, flow back 4h at 70 DEG C, and solution is in Existing peony.
4, by revolving method concentration of reaction solution until 50mL, uses CHCl3(each 50mL) is extracted in three times, collects extraction Liquid, revolving obtain rufous residue, and with 500mL hot water dissolving's residue, light yellow, filtering, rotation is presented in heating stirring 1h to solution Steaming filtration liquid, obtains pale yellow crystals, and dry 8h, obtains intermediate at 100 DEG C
Step 2: the synthesis of target product
1,0.3g 2 is added in the 1.1g intermediate by previous step purification, and 4- dimethyl pyrrole is dissolved in 80mL toluene and 80mL In n-butanol, start after dissolving completely in 115 DEG C of reflux 4h, dark red is presented in solution.
2, excess of solvent is removed with revolving method, prepared column, use methylene chloride: the mixed liquor mistake of methanol 500:3 early period Column, after target product separation；Change mixing liquid proportional, use methylene chloride: the mixed liquor of methanol 1000:1 continues to separate, directly To finally obtaining target product (luminescence generated by light be orange).
Performance test: products therefrom is tested, and measures solution and film absorption spectrum as shown in Figure 1, can from figure To find out, it is bluish-green light absorbing material that it is 480nm which, which absorbs peak position, the absorption half-peak under solution Absorption half-peak breadth under wide and film morphology is respectively less than 110nm.
Basic photodiode device includes:
Including flexible substrates, ITO electrode, asymmetric side's acid cyanines material (photosensitive layer), aluminium electrode etc..Due to asymmetric side's acid Cyanines material has good hole and electron transport property, may not need additional hole, electron transfer layer etc. when preparing device, greatly It is big to simplify preparation process.
Wherein, asymmetric side's acid cyanines material provided by the invention can pass through the side of spin-coating method, vapour deposition method or inkjet printing Method preparation.In embodiment, we use vapour deposition method, method preparation of the asymmetric side's acid cyanines material by vapor deposition, evaporation rate In 0.1nm/s.Keep evaporation thickness in 50nm or so.The film prepared is put into the system that aluminium electrode is completed in vacuum chamber again It is standby, obtain photodiode.
Photodiode device brightness electric current is as shown in Figure 2: it can be seen from the figure that under dark condition and illumination condition Under (6mW/cm2), the good photoelectric response characteristic that device exhibits go out has good prospect in practical applications.
Device external quantum efficiency is as shown in Figure 3: it can be seen that external quantum efficiency can reflect a device to not sharing the same light Absorbing state, device external quantum efficiency at 500nm (blue green light) is more than 15%, and is showed to feux rouges almost without absorption Good light selection characteristic is gone out.
ESI-MS (LC-MS spectrometry [M/z]): 343 [M+H]+。
Elemental analysis (C22H18N2O2): Anal.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；O,9.05.
The device that asymmetric side's acid cyanines material is prepared according to the method described above provided by 2-5 of the embodiment of the present invention, Photoelectric response characteristic and external quantum efficiency are similar to Example 1, hereafter repeat no more.
Embodiment 2
The present embodiment provides a kind of asymmetric side's acid cyanines materials, have the following structure:
Asymmetric side's acid cyanines material with above structure specific the preparation method comprises the following steps:
The first step, the synthesis of intermediate:
1, by 3,4- diisopropoxy -3- cyclobutane -1,2 of 4g diphenylamines and 3.8g,-diketone is dissolved into 160mL isopropyl 0.8mL concentrated hydrochloric acid is added after stirring and dissolving 5min for alcohol, in 85 DEG C of reflux 3h, solution presentation glassy yellow.
2, filtering reacting liquid removes extra reaction substrate, filtered fluid is removed by revolving method, with the CHCl of 200mL3Dissolution After rotate, the solid after must drying.
3, the solid after above-mentioned drying is dissolved with 120mL acetone and 6M hydrochloric acid 120mL, flow back 4h at 70 DEG C, and solution is in Existing peony.
4, by revolving method concentration of reaction solution until 50mL, uses CHCl3(each 50mL) is extracted in three times, collects extraction Liquid, revolving obtain rufous residue, and with 500mL hot water dissolving's residue, light yellow, filtering, rotation is presented in heating stirring 1h to solution Steaming filtration liquid, obtains pale yellow crystals, and dry 8h, obtains intermediate at 100 DEG C
Step 2: the synthesis of target product
1,2,4 thioxene of 0.5g is added in the 1.1g intermediate by last time purification, is dissolved in 80mL toluene and the positive fourth of 80mL In alcohol, start after dissolving completely in 110 DEG C of reflux 4h, dark red is presented in solution.
2, excess of solvent is removed with revolving method, prepared column (method is with embodiment 1), and obtained target product.
Performance test: products therefrom is tested, and it is blue light absorption that measuring solution spectrum to absorb peak position, which is 470nm, Material, the absorption half-peak breadth under absorption half-peak breadth and film morphology under solution are respectively less than 110nm.
ESI-MS (LC-MS spectrometry [M/z]): 360 [M+H]+。
Elemental analysis (C22H17NO2S): Anal.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；S,8.88.
Embodiment 3
The present embodiment provides a kind of asymmetric side's acid cyanines materials, have the following structure:
Asymmetric side's acid cyanines material with above structure specific the preparation method comprises the following steps:
The first step, the synthesis of intermediate:
1, by 3,4- diisopropoxy -3- cyclobutane -1,2 of 4g diphenylamines and 3.8g,-diketone is dissolved into 160mL isopropyl 0.8mL concentrated hydrochloric acid is added after stirring and dissolving 5min for alcohol, in 95 DEG C of reflux 3h, solution presentation glassy yellow.
2, filtering reacting liquid removes extra reaction substrate, filtered fluid is removed by revolving method, with the CHCl of 200mL3Dissolution After rotate, the solid after must drying.
3, the solid after above-mentioned drying is dissolved with 120mL acetone and 6M hydrochloric acid 120mL, flow back 5h at 65 DEG C, and solution is in Existing peony.
4, by revolving method concentration of reaction solution until 50mL, uses CHCl3(each 50mL) is extracted in three times, collects extraction Liquid, revolving obtain rufous residue, and with 500mL hot water dissolving's residue, light yellow, filtering, rotation is presented in heating stirring 1h to solution Steaming filtration liquid, obtains pale yellow crystals, and dry 8h, obtains intermediate at 100 DEG C
Step 2: the synthesis of target product
1,0.45g 2 is added in the 1.1g intermediate by last time purification, and 4- dimethyl -3- methoxypyrrole is dissolved in 80mL first In benzene and 80mL n-butanol, start after dissolving completely in 120 DEG C of reflux 3.5h, dark red is presented in solution.
2, excess of solvent is removed with revolving method, prepared column, specific method obtains target product with embodiment 1.
Performance test: products therefrom is tested, and measures solution and film spectrum absorption peak position is 470nm, be blue Green light absorbing material, the absorption half-peak breadth under absorption half-peak breadth and film morphology under solution are respectively less than 110nm.
ESI-MS (LC-MS spectrometry [M/z]): 373 [M+H]+。
Elemental analysis (C23H20N2O3): Anal.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.
Embodiment 4
The present embodiment provides a kind of asymmetric side's acid cyanines materials, have the following structure:
Asymmetric side's acid cyanines material with above structure specific the preparation method comprises the following steps:
The first step, the synthesis of intermediate:
1, by 3,4- diisopropoxy -3- cyclobutane -1,2 of 4g diphenylamines and 3.8g,-diketone is dissolved into 160mL isopropyl 0.8mL concentrated hydrochloric acid is added after stirring and dissolving 5min for alcohol, in 90 DEG C of reflux 3h, solution presentation glassy yellow.
2, filtering reacting liquid removes extra reaction substrate, filtered fluid is removed by revolving method, with the CHCl of 200mL3Dissolution After rotate, the solid after must drying.
3, the solid after above-mentioned drying is dissolved with 120mL acetone and 6M hydrochloric acid 120mL, flow back 4h at 70 DEG C, and solution is in Existing peony.
4, by revolving method concentration of reaction solution until 50mL, uses CHCl3(each 50mL) is extracted in three times, collects extraction Liquid, revolving obtain rufous residue, and with 500mL hot water dissolving's residue, light yellow, filtering, rotation is presented in heating stirring 1h to solution Steaming filtration liquid, obtains pale yellow crystals, and dry 8h, obtains intermediate at 100 DEG C
Step 2: the synthesis of target product
1, the 1.1g intermediate of last time purification is added to the 3- methyl indol of 0.35g, is dissolved in 80mL toluene and the positive fourth of 80mL In alcohol, start after dissolving completely in 115 DEG C of reflux 4h, dark red is presented in solution.
2, excess of solvent is removed with revolving method, prepared column, specific method obtains target product with embodiment 1.
Performance test: products therefrom is tested, and measures solution and film spectrum absorption peak position is 495nm, be blue Green light absorbing material, the absorption half-peak breadth under absorption half-peak breadth and film morphology under solution are respectively less than 110nm.
ESI-MS (LC-MS spectrometry [M/z]): 379 [M+H]+。
Elemental analysis (C25H18N2O2): Anal.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；O,8.38.
Embodiment 5
The present embodiment provides a kind of asymmetric side's acid cyanines materials, have the following structure:
Asymmetric side's acid cyanines material with above structure specific the preparation method comprises the following steps:
Step 1: the synthesis of intermediate:
1, by 5g 1,3,4- diisopropoxy -3- cyclobutane -1,2 of 1'- dinaphthylamine and 3.8g,-diketone is dissolved into 0.8mL concentrated hydrochloric acid is added after stirring and dissolving 5min for 160mL isopropanol, in 90 DEG C of reflux 3h, solution presentation glassy yellow.
2, filtering reacting liquid removes extra reaction substrate, filtered fluid is removed by revolving method, with the CHCl of 200mL3Dissolution After rotate, the solid after must drying.
3, the solid after above-mentioned drying is dissolved with 120mL acetone and 6M hydrochloric acid 120mL, flow back 4h at 70 DEG C, and solution is in Existing peony.
4, by revolving method concentration of reaction solution until 50mL, uses CHCl3(each 50mL) is extracted in three times, collects extraction Liquid, revolving obtain rufous residue, and with 500mL hot water dissolving's residue, light yellow, filtering, rotation is presented in heating stirring 1h to solution Steaming filtration liquid, obtains pale yellow crystals, and dry 8h, obtains intermediate at 100 DEG C
Step 2: the synthesis of target product
1, the 2g intermediate of last time purification is added to 2, the 4- dimethyl pyrrole of 0.5g, is dissolved in 80mL toluene and the positive fourth of 80mL In alcohol, start after dissolving completely in 115 DEG C of reflux 4h, dark red is presented in solution.
2, excess of solvent is removed with revolving method, prepared column, specific method obtains target product with embodiment 1.
Performance test: products therefrom is tested, and measures solution and film spectrum absorption peak position is 485nm, be blue Green light absorbing material, the absorption half-peak breadth under absorption half-peak breadth and film morphology under solution are respectively less than 110nm.
ESI-MS (LC-MS spectrometry [M/z]): 443 [M+H]+。
Elemental analysis (C30H22N2O2): Anal.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
This comparative example provides the sour cyanines material in symmetrical side, structure are as follows:
Performance test: products therefrom is tested, and it is red light absorption that measuring film spectrum absorption peak position, which is 680nm, Material, the absorption half-peak breadth under absorption half-peak breadth and film morphology under solution are respectively less than 110nm.
Comparative example 2
This comparative example provides asymmetric side's acid cyanines material, structure are as follows:
Performance test: products therefrom is tested, and measuring film spectrum absorption peak position is 540nm, is that green light absorbs Material, the absorption half-peak breadth under film morphology are all larger than 120nm.Simultaneously as the material contains hydroxyl, long chain alkyl group, The mode for not being available vapor deposition prepares film, because high temperature can destroy hydroxyl etc., device performance is greatly reduced.
By the data comparison of embodiment and comparative example it is found that by C1And C2The design and selection of substituent group, so that its Spectral absorption peak is located at bluish-green photo-absorption region, meets green light sensing, the application demand of multichannel optical communication field；This hair simultaneously The absorption half-peak breadth under absorption half-peak breadth and film morphology under the sour cyanines material solution in the side of bright offer is respectively less than 110nm, is making There is highly important application in terms of standby photodiode；In addition, material is more stable, meet evaporation process, spin coating, inkjet printing Etc. kinds of processes requirement.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or It changes still within the protection scope of the invention.

Claims (10)

1. a kind of asymmetric side's acid cyanines material, which is characterized in that have structure shown in logical formula (I):
Wherein, X1And X2Separately it is selected from oxygen atom, halogen, one of cyano or alkyl group, C1For diphenylamino group or Substituted diphenylamine derivatives group；C2For pyrrole group, indolyl radical, thienyl group contains substituent group or heteroatomic pyrrole Group is coughed up, containing substituent group or heteroatomic indolyl radical, contains one of substituent group or heteroatomic thienyl group.
2. asymmetric side's acid cyanines material according to claim 1, which is characterized in that the X1And X2Oxygen atom is respectively represented, C1For diphenylamino group.
3. asymmetric side's acid cyanines material according to claim 1 or 2, which is characterized in that the hetero atom is in S, O or N At least one.
4. asymmetric side's acid cyanines material according to claim 1, which is characterized in that asymmetric side's acid cyanines material has Structure as follows:
5. a kind of described in any item asymmetric side's acid cyanines materials of claim 1-4 are logical in bluish-green photo-sensing device or multichannel light It is applied in letter device.
6. asymmetric side's acid cyanines material according to claim 5 is in green sensor part or multichannel optic communication device Using, which is characterized in that contain in at least one layer in the conductive basal layer in the device, electron transfer layer or hole transmission layer There is asymmetric side's acid cyanines material.
7. a kind of preparation method of the described in any item asymmetric side's acid cyanines materials of claim 1-4, which is characterized in that including with Lower step:
The synthesis of intermediate: shown in synthetic route such as formula (II),
3,4- diisopropoxy -3- cyclobutane -1,2- diketone and reaction substrate A are dissolved in solvent, concentrated hydrochloric acid is added, heat into Row back flow reaction, separation, is hydrolyzed reaction, purifies, obtains intermediate；Wherein, reaction substrate A is C1Corresponding to substituent group Compound；
The synthesis of target product: shown in synthetic route such as formula (III),
Intermediate and reaction substrate C are dissolved in solvent, heating carries out back flow reaction, separates, and purification obtains target product；Its In, reaction substrate C is C2Compound corresponding to substituent group.
8. the preparation method of asymmetric side's acid cyanines material according to claim 7, which is characterized in that
In the synthesis step of the intermediate, 3,4- diisopropoxy -3- cyclobutane -1,2- diketone is with reaction substrate A's Molar ratio is 1:1-1:2, and the solvent is isopropanol；
In the synthesis step of the target product, the molar ratio of intermediate and reaction substrate C are (5:1-1:1)；The solvent is The mixture of toluene and n-butanol, it is preferred that the volume ratio of toluene and n-butanol is 1:1.
9. the preparation method of asymmetric side's acid cyanines material according to claim 7 or 8, which is characterized in that the intermediate Synthesis step in, back flow reaction temperature be 85-95 DEG C；
In the synthesis step of the target product, the temperature of back flow reaction is 110-120 DEG C.
10. according to the preparation method of the described in any item asymmetric side's acid cyanines materials of claim 7-9, which is characterized in that described Hydrolysis in the synthesis step of intermediate is that the product after separation is dissolved in solvent, concentrated hydrochloric acid is added, at 65-75 DEG C Under be heated to reflux 3-5h.
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