CN104987748B - Organic dye, preparation method thereof and application thereof - Google Patents
Organic dye, preparation method thereof and application thereof Download PDFInfo
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The present invention provides an organic dye with formula (I) or formula (II), wherein triple bond benzene and thiadiazol triple bond benzene formic acids are electron acceptors, triphenylamine or triphenylamine-perylene bisimide is an electron donor. The organic dye has a wider spectrum response range and a higher molar absorption coefficient, and has good light stability, thermal stability and chemical stability. Therefore, a dye sensitized solar cell prepared by such dyes has a higher short-circuit photoelectric-current density, and functional conversion efficiency thereof can reach up to 11%.
Description
Technical field
The present invention relates to technical field of solar cells, more particularly to a kind of organic dyestuff, its preparation method and its apply.
Background technology
The energy is the foundation stone that the mankind develop rapidly, either the industrial revolution, electric power revolution or information technology revolution, the mankind
The innovation of all greatnesses, the progress of technology are all built upon on the basis of the continuous expansion of energy demand.Technological revolution is given
The tremendous influence that the mankind and earth zone come is also more urgent than ever to the demand of the energy beyond any epoch before this.
Highly developed today's society, with non-renewable three macrofossil fuel-coal, oil, the consumption of natural gas and is brought
Environmental problem, makes energy crisis and environmental protection become a most important difficult problem for 21 century facing mankind.Solar energy is used as one kind
Clean reproducible energy, its exploitation are a kind of important means for solving the current energy crisis of the mankind and environmental problem.
Since finding photovoltaic effect from French scientist Becquerel in 1839, Optical Electro-Chemistry research has gone through 100
History for many years.Solar cell in the market is main or based on silicon solar cell, wherein the skill of crystal silicon solar battery
Art is most widely used, and accounts for more than the 80% of solar cell；But it is high to there is manufacturing cost, and process conditions are harsh, and refining silicon
During energy consumption it is big, it is seriously polluted the shortcomings of.Exciton solar cell based on organic photoelectric functional material, cheap is subject to state
Inside and outside extensive concern and research.1991,The three core ruthenium dye RuL that seminar reported Amadelli et al.2
(μ-(CN)Ru(CN)L′2)2(L=2,2 '-bipyridyl -4,4 '-dicarboxylic acids, L '=2,2 '-bipyridyl) adsorbs as sensitizer
The high-quality TiO that they develop with great concentration for many years2Device is made on nano-crystal thin-film, under simulated solar irradiation 7.1% photoelectricity is obtained
Conversion efficiency, the meaning with milestone, has thus started dye sensitization too in the development course of dye-sensitized solar cells
The research boom in positive electricity pond.
Compared with traditional inorganic semiconductor solar cell, the manufacturing cost of dye-sensitized solar cells is relatively low, and face
Color is abundant, attractive in appearance, can be made into translucent product.Flexible dye-sensitized solar cells lighter in weight, can fold, crimp and
It is widely applied in daily life.Dye sensitizing agent is one of important composition of dye-sensitized solar cells, and is commercialized at present
Dyestuff mostly be the complex containing noble ruthenium.But due to metal Ru resource-constrained and costliness, ruthenium radical dye itself absorbs
The limited space that coefficient is lifted, between the past more than ten years, metal-free organic dyestuff sets by its abundant raw materials, molecule
The advantages of counting versatile and flexible obtains extensive concern.But, at present in the world the photoelectricity of device prepared by pure organic dye turns
Change efficiency only very few several more than 10%, efficiency has become the very crux of long-standing problem pure organic dye development.
And at present people study it is more be dyestuff electron donor moiety, to the less of electron acceptor moiety research, so exploitation is new
Type electron acceptor dye sensitizer may bring the breakthrough development in this field.
The content of the invention
Present invention solves the technical problem that being to provide a kind of organic dyestuff, the organic dyestuff that the application is provided is used as dyestuff
Solar cell prepared by sensitizer has preferable performance.
In view of this, this application provides organic dyestuff of the one kind as shown in formula (I) or formula (II)；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36；
Y is carboxyl, phosphorous acidic group or sulfonic group.
Preferably, the R1For the alkoxyl of C6～C18；The R2For the alkyl of C5～C25.
Preferably, the organic dyestuff is the compound with formula (I) structure；
Preferably, the organic dyestuff is the compound with formula (II) structure；
Present invention also provides the preparation method of organic dyestuff of the one kind as shown in formula (I), comprises the following steps：
Compound with formula (III) structure is carried out into coupling reaction with the compound with formula (V) structure, obtains organic
The prodrug esters of dyestuff；
The prodrug esters of the organic dyestuff and highly basic are reacted, the organic dyestuff as shown in formula (I) is obtained；
Wherein, R1Selected from the alkyl or the alkoxyl of C1～C36 of H, C1～C36；
X is halogen.
Present invention also provides the preparation method of organic dyestuff of the one kind as shown in formula (II), comprises the following steps：
To react with the compound of formula (IV) structure and N- N-halosuccinimides, by the product for obtaining and with formula
(V) compound of structure carries out coupling reaction, obtains the prodrug esters of organic dyestuff；
The prodrug esters of the organic dyestuff and highly basic are reacted, the organic dyestuff as shown in formula (II) is obtained；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36；
Y is carboxyl, phosphorous acidic group or sulfonic group.
Preferably, the preparation of the compound with formula (IV) structure is carried out by the following method：
Under catalyst action, will with the compound of formula (VI) structure with formula (VII) structure compound molten
Coupling reaction is carried out in liquid, the compound with formula (IV) structure is obtained；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36.
Preferably, the preparation of the compound with formula (V) structure is prepared by the following method：
In the presence of catalyst, will be with the compound of formula (VIII) structure and 4,7- dibromo diazosulfide in the solution
Coupling reaction is carried out, the compound with formula (Ⅸ) structure is obtained；
In the presence of catalyst, the compound with formula (Ⅸ) structure and triisopropylsilyl acetylene are entered in the solution
Row coupling reaction, obtains the compound with formula (Ⅹ) structure；
To react under tetrabutyl ammonium fluoride effect with the compound of formula (Ⅹ) structure, obtain with formula (V) structure
Compound；
Wherein, Y is carboxyl, phosphorous acidic group or sulfonic group.
Present invention also provides described organic dyestuff or the organic dyestuff prepared by such scheme are in the dye sensitization sun
Application in battery.
This application provides a kind of organic dyestuff, its preparation method and its application in solar cell.The application is carried
For organic dyestuff using aryne and thiadiazoles aryne formic acid as acceptor, using triphenylamine or the perylene diimide of triphenylamine-as
Electron donor, this kind of structure makes organic dyestuff have wider spectral response range and higher molar absorption coefficient, while tool
There are good light, heat and chemical stability, then the solar cell for preparing using this kind of dyestuff has higher short-circuit photocurrent close
Degree and function transformation efficiency.Test result indicate that, solar cell function prepared by the organic dyestuff provided using the application turns
Change efficiency up to 11%.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
The embodiment of the invention discloses organic dyestuff of the one kind as shown in formula (I) or formula (II)；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36；
Y is carboxyl, phosphorous acidic group or sulfonic group.
This application provides a kind of contain aryne and thiadiazoles aryne formic acid novel electron acceptors organic dyestuff.
Well known to those skilled in the art, electron acceptor refers to and nucleophobic material is connect in electron transmission and is reduced
Material；And electron donor refers to the side for providing electronics.Aryne simultaneously as electronics receive by thiadiazoles aryne formic acid in the application
Body, and triphenylamine or the perylene diimide of triphenylamine-are used as electron donor.
In the application in the organic dyestuff with formula (I) structure, R1The preferably alkyl of C5～C25 or C5～C25
Alkoxyl；In certain embodiments, the R1The preferably alkoxyl of the alkyl of C6～C18 or C6～C18；In some embodiments
In, the R1Preferably-C6H13O, Y are preferably carboxyl, then the organic dyestuff for obtaining has the structure shown in formula (I)：
In the organic dyestuff with formula (II) structure, the R1The preferably alcoxyl of the alkyl of C5～C25 or C5～C25
Base；In certain embodiments, the R1The preferably alkoxyl of the alkyl of C6～C18 or C6～C18；Institute in certain embodiments
State R2The preferably alkoxyl of the alkyl of C5～C25 or C5～C25.It is described with the organic of formula (II) structure in embodiment
Dyestuff is preferably following organic dyestuff：
Present invention also provides the preparation method of the organic dyestuff with formula (I) structure, comprises the following steps：
Compound with formula (III) structure is carried out into coupling reaction with the compound with formula (V) structure, obtains organic
The prodrug esters of dyestuff；
The prodrug esters of the organic dyestuff and highly basic are reacted, the organic dyestuff as shown in formula (II) is obtained；
Wherein, R1Selected from the alkyl or the alkoxyl of C1～C36 of H, C1～C36；
X is halogen.
In above process, the compound with formula (V) structure is electron acceptor compound, with formula (III) structure
Compound is electronic donor compound, and during reaction, above two compound occurs Sonogashira coupling reactions,
Organic dyestuff prodrug esters are obtained, it is acted on again with highly basic, obtains organic dyestuff.The Sonogashira coupling reactions are by Pd/
Cross-coupling reaction between the terminal alkyne and the halide of sp2 type carbon of the catalysis of Cu mixed catalysts.Above-mentioned halogen is excellent
Elect iodine as.The compound with formula (V) structure carries out the catalyst of coupling reaction with the compound with formula (III) structure
System is preferably organophosphorus ligand Pd (dba)3With P (t-Bu)3, preferably carry out in the Isosorbide-5-Nitrae-dioxane solution of cesium carbonate.This
Apply for that the highly basic is preferably potassium hydroxide.In order to avoid there is side reaction during the course of the reaction, the application is preferably protected in argon gas
Reacted under shield.
Present invention also provides the preparation method of the organic dyestuff as shown in formula (II), comprises the following steps：
To react with the compound of formula (IV) structure and N- N-halosuccinimides, by the product for obtaining and with formula
(V) compound of structure carries out coupling reaction, obtains the prodrug esters of organic dyestuff；
The prodrug esters of the organic dyestuff and highly basic are reacted, the organic dyestuff as shown in formula (II) is obtained；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36；
Y is carboxyl, phosphorous acidic group or sulfonic group.
During the organic dyestuff with formula (II) structure is prepared, the compound with formula (IV) structure is given for electronics
Body compound.The N- N-halosuccinimides are preferably N- bromo-succinimides.The compound of formula (IV) structure with
There is bromo-reaction in N- bromo-succinimides, the bromination product for obtaining occurs with the compound with formula (V) structure
Sonogashira coupling reactions, obtain organic dyestuff prodrug esters, and it is acted on again with highly basic, that is, obtain with formula (II) structure
Organic dyestuff.Herein described bromination product and the compound with formula (V) structure react the caltalyst of employing
System is preferably organophosphorus ligand Pd (dba)3With P (t-Bu)3, preferably carry out in the Isosorbide-5-Nitrae-dioxane solution of cesium carbonate.This Shen
Please the highly basic be preferably potassium hydroxide.In order to avoid there is side reaction during the course of the reaction, the application is preferably protected in argon gas
Under reacted.
In above-mentioned reaction, the compound with formula (V) structure is prepared by the following method：
In the presence of catalyst, will be with the compound of formula (VIII) structure and 4,7- dibromo diazosulfide in the solution
Coupling reaction is carried out, the compound with formula (Ⅸ) structure is obtained；
In the presence of catalyst, the compound with formula (Ⅸ) structure and triisopropylsilyl acetylene are entered in the solution
Row coupling reaction, obtains the compound with formula (Ⅹ) structure；
To react under tetrabutyl ammonium fluoride effect with the compound of formula (Ⅹ) structure, obtain with formula (V) structure
Compound；
Wherein, Y is carboxyl, phosphorous acidic group or sulfonic group.
In the compound with formula (V) structure is prepared, the step of obtain the compound with formula (Ⅸ) structure in, institute
State catalyst system and be preferably Pd (PPh3)Cl2, CuI and PPh3, the solution is preferably diisopropylamine and the mixing of toluene is molten
Agent.In the compound with formula (Ⅹ) structure is obtained, the catalyst system is preferably Pd (PPh3)Cl2, CuI and PPh3, institute
State the organic solution that solution is preferably diisopropylamine and toluene.Finally the compound with formula (Ⅹ) structure is fluorinated in the tetrabutyl
There is desiliconization in the presence of ammonium, that is, obtain the compound with formula (V) structure.
The above-mentioned compound with formula (IV) structure is prepared by the following method：
Under catalyst action, will with the compound of formula (VI) structure with formula (VII) structure compound molten
Coupling reaction is carried out in liquid, the compound with formula (IV) structure is obtained；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36.
In above-mentioned preparation has the compound of formula (VI) structure, the catalyst system is preferably Pd (OAc)2With
Sphos, the solution is preferably K3PO4Organic solution.
Present invention also provides application of the organic dyestuff in dye-sensitized solar cells.
The present invention provides a kind of organic dyestuff containing aryne and thiadiazoles aryne formic acid and its in the dye sensitization sun
Application in battery.Such organic dyestuff using aryne and thiadiazoles aryne formic acid as acceptor, with triphenylamine or triphenylamine-
Perylene diimide is used as electron donor.Such dyestuff has wider spectral response range and higher molar absorption coefficient, while
With good light, heat and chemical stability.The solar cell prepared using such dyestuff has higher short-circuit photocurrent close
Degree, its function transformation efficiency can reach 11%.
For a further understanding of the present invention, with reference to organic dyestuff, its preparation method that embodiment is provided the present invention
It has been described in detail with its application, protection scope of the present invention is not limited by the following examples.
Embodiment 1：The preparation of organic dyestuff (i)
The synthetic route of the present embodiment organic dyestuff (i) is as follows：
Raw materials used 1 and 4 in the present embodiment, respectively according to document R.H.Pawle, V.Eastman and
S.W.Thomas, J.Mater.Chem., 2011,21,14041 and R.Li, J.Liu, N.Cai, M.Zhang and P.Wang,
J.Phys.Chem.B, 2010,114,4461 prepare.Other reaction reagents can be obtained by commercially available mode.
The synthesis of intermediate 2：
In three neck round bottom, 850 milligrams of intermediates, 1,1.49 grams of 4,7- dibromo diazosulfides are dissolved in into 2 milliliters
In the mixed solvent of diethyl propyl group amine and 10 milliliters of toluene, add under argon gas protection 63 milligrams of triphenyl phosphorus palladiums of dichloro two, 48
Milligram triphenyl phosphorus, 17 milligrams of cuprous iodides, then argon gas protection under 80 DEG C react 2 hours, be cooled to room temperature.Add 200
Milliliter water, with chloroform, (3 × 100 milliliters) extract three times, merge organic phase, are filtered with after anhydrous sodium sulfate drying.Concentration filtrate
The crude product for obtaining afterwards chloroform/petroleum ether (volume ratio 3/1) is separated as eluant, eluent by silica gel column chromatography, obtains target product
Thing 2 is yellow solid, and yield is 83%.
The structural characterization of target product 2：Nuclear-magnetism：1H NMR(400MHz,CDCl3)δ:8.05 (d, J=8.0Hz, 2H),
7.84 (d, J=8.0Hz, 1H), 7.71～7.67 (m, 3H), 4.34 (t, J=6.6Hz, 2H), 1.80～1.73 (m, 2H),
1.53～1.44 (m, 2H), 0.99 (t, J=7.4Hz, 3H)；13C NMR(100MHz,CDCl3)δ:166.10,154.18,
153.25,133.28,132.06,131.95,130.80,129.67,126.98,116.28,115.47,95.95,87.24,
65.27,30.88,19.40,13.89；Mass spectrum：415.01([M+H]+)；Elementary analysis：C,54.94；H,3.65；N, 6.74%.
The synthesis of intermediate 3：
In three neck round bottom, 1.00 grams of intermediates, 2,1.32 grams of triisopropylsilyl acetylene are dissolved in into 2 milliliter two
In the mixed solvent of second propyl group amine and 10 milliliters of toluene, 35 milligrams of triphenyl phosphorus palladiums of dichloro two, 27 millis are added under argon gas protection
Gram triphenyl phosphorus, 10 milligrams of cuprous iodides, then 80 DEG C of reactions overnight, are cooled to room temperature under argon gas protection.Add 200 milliliters
Water, with chloroform, (3 × 100 milliliters) extract three times, merge organic phase, are filtered with after anhydrous sodium sulfate drying.After concentration filtrate
To crude product it is not separated be directly used in next step reaction.
In three neck round bottom, by 1.07 grams of crude products obtained above, the dissolving of 5.41 grams of tetra-n-butyl ammonium fluoride
In 50 milliliters of dichloromethane, under argon gas protection 3 hours are stirred at room temperature.200 milliliters of water are added, with chloroform (3 × 100 milliliters)
Extraction three times, merges organic phase, is filtered with after anhydrous sodium sulfate drying.Crude product chloroform/the oil obtained after concentration filtrate
Ether (volume ratio 3/1) is separated as eluant, eluent by silica gel column chromatography, obtains yellow solid target product 3, and yield is 82%.
The product structure of target product 3 is characterized：Nuclear-magnetism：1H NMR(400MHz,CDCl3)δ:8.06 (d, J=8.0Hz,
2H), 7.78 (s, 2H), 7.71 (d, J=8.1Hz, 2H), 4.34 (t, J=6.6Hz, 2H), 3.69 (s, 1H), 1.80～1.73
(m, 2H), 1.53～1.44 (m, 2H), 0.99 (t, J=7.3Hz, 3H)；13C NMR(100MHz,CDCl3)δ:165.96,
154.53,154.11,133.42,132.52,131.92,130.74,129.58,126.85,117.57,116.36,96.74,
87.59,85.44,79.18,65.18,30.80,19.32,13.82；Mass spectrum：361.08([M+H]+)；Elementary analysis：C,
69.99；H,4.48；N, 7.76%.
The synthesis of organic dyestuff (I)：
In dry Schlenk reaction bulbs, by 220 milligrams of intermediates 3,350mg intermediates 4 and 216 milligrams of cesium carbonates
In being dissolved in 12 milliliters of Isosorbide-5-Nitrae-dioxane, 29 milligrams of catalyst Pd are added in the glove box full of nitrogen2(dba)3With 6 millis
Gram organophosphorus ligand P (t-Bu)3, argon gas protection under back flow reaction overnight.
After reaction terminates, reaction system is cooled to into room temperature, adds 20 milliliters of water, with (3 × 100 milliliters) extractions three of chloroform
It is secondary, merge organic phase, filtered with after anhydrous sodium sulfate drying.The 426 milligrams of dyestuff former butyl esters for obtaining are directly used in next step
Reaction.
In three neck round bottom, 426 milligrams of dyestuff former butyl esters obtained above are dissolved in into 15 milliliters of tetrahydrofurans
In the mixed solvent of 5 milliliters of water, 297 milligrams of potassium hydroxide are added in reaction system, back flow reaction 8 is little under argon gas protection
When.
Then reaction system is down to into room temperature, adds 20 milliliters of phosphate aqueous solutions (0.2mol/L), the mixed liquor for obtaining is used
(3 × 100 milliliters) of chloroform is extracted three times, merges organic phase, is filtered with after anhydrous sodium sulfate drying.What is obtained after concentration filtrate is thick
Product chloroform/methyl alcohol (volume ratio 1/20) is separated as eluant, eluent by silica gel column chromatography, and the target product for obtaining is
Violet solid, gross production rate is 83%.
The structural characterization of product (I)：Nuclear-magnetism：1H NMR(400MHz,THF-d8)δ:8.09 (d, J=8.2Hz 2H),
7.75-7.67 (m, 4H), 7.42 (d, J=8.6Hz, 2H), 7.07 (d, J=8.8,4H), 6.86-6.84 (m, 6H), 3.94 (t,
), J=6.4,4H 1.81-1.74 (m, 4H), 1.48-1.45 (m, 4H), 1.36-1.34 (m, 4H), 1.27 (br, 4H), 0.93-
0.89(m,6H)；13C NMR(100MHz,THF-d8)δ:171.24,156.28,154.44,154.40,149.76,139.74,
133.17,133.09,131.98,131.57,130.22,129.99,129.41,128.17,127.46,118.76,118.63,
115.53,112.58,99.81,95.99,88.75,84.71,68.38,32.02,31.72,29.89,29.64,29.58,
29.42,29.30,27.33,25.87,25.59,22.80,22.73,14.23,14.16.；Mass spectrum：747.31295([M+H
]+)；Elementary analysis：C,75.46；H,6.07；N, 5.63%.
Test result indicate that, the present invention has prepared the organic dyestuff with formula (I) structure.
Embodiment 2：The preparation of organic dyestuff (ii)
The synthetic route of the present embodiment organic dyestuff (ii) is as follows：
Raw materials used 5 and 6 in the present embodiment, respectively according to document R.Li, J.Liu, N.Cai, M.Zhang and
P.Wang, J.Phys.Chem.B, 2010,114,4461 and Y.Li, Z.Wang, Org.Lett.2009,11,1386 are prepared into
Arrive.Other reaction reagents can be obtained by commercially available mode.
The synthesis of intermediate 7：
In three neck round bottom, 871 milligrams of intermediates, 5,723 milligrams of intermediates 6 are dissolved in into 12 milliliters of Isosorbide-5-Nitrae-dioxies
In the mixed solvent (volume ratio 5/1) of six rings/water, 13 milligrams of 2- dicyclohexyl phosphine -2', 6'- are added next time in argon gas protection
Dimethoxy-biphenyl (Sphos), 7 milligrams of palladiums and 1.35 grams of potassium phosphates, are refluxed reaction 8 hours, are subsequently cooled to room
Temperature, adds 20 milliliters of water, and with chloroform, (3 × 100 milliliters) extract three times, merge organic phase, with mistake after anhydrous sodium sulfate drying
Filter, concentrates the crude product toluene/petroleum ether (volume ratio 1/10) obtained after filtrate as eluant, eluent by silica gel column chromatography point
From, yellow oily target product 7 is obtained, yield is 95%.
The structural characterization of target product 7：Nuclear-magnetism：1H NMR(400MHz,CDCl3)δ:8.67 (t, J=7.4Hz, 2H),
8.19 (d, J=8.2,1H), 8.1 (d, J=8.0Hz, 1H), 7.88-7.83 (m, 2H), 7.80 (s, 1H), 7.76 (d, J=
7.9Hz, 1H), 7.72 (d, J=8.1Hz, 1H), 7.51 (d, J=8.6Hz, 2H), 7.15-7.08 (m, 6H), 6.89-6.85
(m, 4H), 4.60 (d, J=7.4Hz, 2H), 3.94 (t, J=6.4Hz, 4H), 2.34-2.31 (m, 1H), 1.78-1.74 (m,
4H),1.53-1.45(m,6H),1.38-1.34(m,14H),1.19-1.16(m,16H),0.94-0.91(m,6H),0.81-
0.79(m,6H)；13C NMR(100MHz,CDCl3)δ:156.59,148.92,141.65,138.31,127.30,125.81,
125.45,125.42,125.06,124.92,124.85,123.93,121.40,121.14,120.87,118.05,117.12,
115.87,114.59,114.21,68.58,50.36,40.55,32.46,30.39,30.00,26.57,23.35,23.27,
14.24,14.22；Mass spectrum：933.61([M+H]+)；Elementary analysis：C,84.92；H,8.63；N, 3.01%.
The synthesis of organic dyestuff (II)：
In dry Schlenk reaction bulbs, 1.13 grams of intermediates 7 are dissolved in 30 milliliters of tetrahydrofurans, reactant
Be ice bath to 0 DEG C, in reaction system add 216 milligrams of N- bromo-succinimides, keep 0 DEG C react 2 hours.
After reaction terminates, 20 milliliters of water are added, extracted three times with (3 × 100 milliliters) of chloroform, merge organic phase, with anhydrous
Sodium sulphate is filtered after being dried.The brominated product for obtaining is not separated to be directly used in the next step.
In dry Schlenk reaction bulbs, by above-mentioned bromination product, 126 milligrams of compounds 3 and 124 milligrams of cesium carbonates
In being dissolved in 12 milliliters of Isosorbide-5-Nitrae-dioxane, 19 milligrams of catalyst Pd are added in the glove box full of nitrogen2(dba)3With 4 millis
Gram organophosphorus ligand P (t-Bu)3, reaction system back flow reaction is overnight.
After reaction terminates, reaction system is down to into room temperature, adds 20 milliliters of water, with (3 × 100 milliliters) extractions three of chloroform
It is secondary, merge organic phase, filtered with after anhydrous sodium sulfate drying.Obtain 393 milligrams of dyestuff former butyl ester compounds.
In three neck round bottom, the mixing that above-mentioned butyl ester compound is dissolved in into 9 milliliters of tetrahydrofurans and 3 milliliters of water is molten
In agent, 171 milligrams of potassium hydroxide are added in reaction system, be refluxed reaction 6 hours.
After reaction terminates, reaction system is down to into room temperature, 20 milliliters of phosphate aqueous solutions (0.2mol/L) is added, with chloroform (3
× 100 milliliters) extract three times, merge organic phase, filtered with after anhydrous sodium sulfate drying.The crude product obtained after concentration filtrate is used
Chloroform/methyl alcohol (volume ratio 1/20) is separated as eluant, eluent by silica gel column chromatography, and it is violet solid to obtain target product,
Gross production rate is 82%.
Product structure is characterized：Nuclear-magnetism：1H NMR(400MHz,THF-d8)δ:8.82 (d, J=7.8Hz, 1H), 8.71 (s,
2H),8.18(br,1H),8.11(br,3H),7.93-7.91(m,1H),7.85(s,2H),7.73-7.71(m,4H),7.50
(s, 2H), 7.14 (d, J=8.5Hz, 4H), 7.08 (d, J=7.8Hz, 2H), 6.89 (d, J=8.7Hz, 4H), 4.67-4.55
(m, 2H), 3.96 (t, J=6.3Hz, 4H), 2.33-2.19 (m, 1H), 2.09-2.07 (m, 2H), 2.05-2.01 (m, 4H),
1.82-1.75(m,4H),1.58-1.54(m,2H),1.52-1.47(m,6H),1.38-1.36(m,6H),1.29(br,6H),
1.18-1.13(m,8H),0.95-0.90(m,6H),0.87-0.85(m,2H),0.77-0.75(m,6H)；13C NMR
(100MHz,THF-d8)δ:156.67,155.25,149.00,141.54,139.82,134.70,134.20,133.39,
132.20,131.36,130.35,127.44,126.01,125.35,125.13,124.67,121.94,121.71,120.58,
118.85,116.69,116.45,115.91,114.33,99.90,96.72,90.75,88.76,68.61,50.28,40.36,
36.02,32.58,32.46,32.37,30.44,30.38,30.19,30.08,27.82,27.01,26.59,26.20,
23.29,14.23；High resolution mass spectrum：1234.63712([M+H]+)；Elementary analysis：C,80.67；H,7.05；N, 4.54%.
Test result indicate that, the present invention has prepared the organic dyestuff with formula (II) structure.
Embodiment 3：Dye-sensitized solar cells based on organic dyestuff (I)
By TiO2Structure bilayer membrane electrode is molten in the toluene/ethanol containing every liter of dyestuff I of 150 micromole (volume ratio 2/8)
Soak 12 hours in liquid, take out electrode, the glass electrode hot melt ring sealing of Platinum Nanoparticles will be covered, be finally injected in electrolyte
In the gap of two electrodes, that is, constitute dye-sensitized solar cells.Joined according to the dye-sensitized solar cells that the method is obtained
Number is as shown in table 1.Detailed device preparation method referring to document (Energy Environ.Sci., 2010,3,1924).
Embodiment 4：Dye-sensitized solar cells based on organic dyestuff (II)
By TiO2Structure bilayer membrane electrode is in the toluene/ethanol (volume ratio 3/7) containing every liter of dyestuff of 150 micromole (II)
Soak 12 hours in solution, take out electrode, the glass electrode hot melt ring sealing of Platinum Nanoparticles will be covered, finally inject in electrolyte
To in the gap of two electrodes, that is, constitute dye-sensitized solar cells.According to the dye-sensitized solar cells that the method is obtained
Parameter is as shown in table 1.Detailed device preparation method referring to document (Energy Environ.Sci., 2010,3,1924).
The performance data table of the dye-sensitized cell of 1 embodiment of table 3～4
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen in the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope for causing.
Claims (9)
1. organic dyestuff of the one kind as shown in formula (I) or formula (II)；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36；
Y is carboxyl, phosphorous acidic group or sulfonic group.
2. organic dyestuff according to claim 1, it is characterised in that the R1For the alkoxyl of C6～C18；The R2For
The alkyl of C5～C25.
3. organic dyestuff according to claim 1, it is characterised in that the organic dyestuff is the change with formula (I) structure
Compound；
4. organic dyestuff according to claim 1, it is characterised in that the organic dyestuff is the change with formula (II) structure
Compound；
5. the preparation method of organic dyestuff of the one kind as shown in formula (I), comprises the following steps：
Compound with formula (III) structure is carried out into coupling reaction with the compound with formula (V) structure, organic dyestuff is obtained
Prodrug esters；
The prodrug esters of the organic dyestuff and highly basic are reacted, the organic dyestuff as shown in formula (I) is obtained；
Wherein, R1Selected from the alkyl or the alkoxyl of C1～C36 of H, C1～C36；
Y is carboxyl, phosphorous acidic group or sulfonic group；
X is halogen；
Y1For carboxylic acid ester groups, phosphorous acid ester group or sulfonate group.
6. the preparation method of organic dyestuff of the one kind as shown in formula (II), comprises the following steps：
To react with the compound of formula (IV) structure and N- N-halosuccinimides, by the product for obtaining and with formula (V) knot
The compound of structure carries out coupling reaction, obtains the prodrug esters of organic dyestuff；
The prodrug esters of the organic dyestuff and highly basic are reacted, the organic dyestuff as shown in formula (II) is obtained；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36；
Y1For carboxylic acid ester groups, phosphorous acid ester group or sulfonate group；
Y is carboxyl, phosphorous acidic group or sulfonic group.
7. preparation method according to claim 6, it is characterised in that the preparation of the compound with formula (IV) structure
Carry out by the following method：
Under catalyst action, will be with the compound of formula (VI) structure with the compound with formula (VII) structure in the solution
Coupling reaction is carried out, the compound with formula (IV) structure is obtained；
Wherein, R1And R2It is independently selected from the alkyl of H, C1～C36 or the alkoxyl of C1～C36.
8. the preparation method according to claim 5 or 6, it is characterised in that the compound with formula (V) structure
Preparation is prepared by the following method：
In the presence of catalyst, will in the solution carry out with the compound of formula (VIII) structure and 4,7- dibromo diazosulfide
Coupling reaction, obtains the compound with formula (Ⅸ) structure；
In the presence of catalyst, the compound with formula (Ⅸ) structure and triisopropylsilyl acetylene are carried out in the solution idol
Connection reaction, obtains the compound with formula (Ⅹ) structure；
To react under tetrabutyl ammonium fluoride effect with the compound of formula (Ⅹ) structure, obtain the chemical combination with formula (V) structure
Thing；
Wherein, Y1For carboxylic acid ester groups, phosphorous acid ester group or sulfonate group；
Y is carboxyl, phosphorous acidic group or sulfonic group.
9. the preparation method described in organic dyestuff described in any one of Claims 1 to 4 or any one of claim 5～8 is made
Application of the standby organic dyestuff in dye-sensitized solar cells.
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Effective date of registration: 20180514 Address after: 130022 No. 5625 Renmin Street, Jilin, Changchun Co-patentee after: Trina Solar Limited by Share Ltd Patentee after: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences Address before: 130022 No. 5625 Renmin Street, Jilin, Changchun Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |