CN104072730A - Silole dithiophene-benzodi(benzoselenadiazole) copolymer material as well as preparation method and application thereof - Google Patents
Silole dithiophene-benzodi(benzoselenadiazole) copolymer material as well as preparation method and application thereof Download PDFInfo
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- CN104072730A CN104072730A CN201310109554.0A CN201310109554A CN104072730A CN 104072730 A CN104072730 A CN 104072730A CN 201310109554 A CN201310109554 A CN 201310109554A CN 104072730 A CN104072730 A CN 104072730A
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- 0 C*(C)c1cc([Si](*)(*C2CC2)c2c-3[s]c(-c(c4n[s]nc4c4c(c5n[s]nc5c(*(C)C)c5)c5c5*)cc4c5I)c2)c-3[s]1 Chemical compound C*(C)c1cc([Si](*)(*C2CC2)c2c-3[s]c(-c(c4n[s]nc4c4c(c5n[s]nc5c(*(C)C)c5)c5c5*)cc4c5I)c2)c-3[s]1 0.000 description 2
- MIAWACVRYNLNNZ-UHFFFAOYSA-N C=[Br]c(c1n[s]nc11)cc([N+]([O-])=O)c1Br Chemical compound C=[Br]c(c1n[s]nc11)cc([N+]([O-])=O)c1Br MIAWACVRYNLNNZ-UHFFFAOYSA-N 0.000 description 1
- LYTBMLCMMFRBFS-UHFFFAOYSA-N Cc(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O Chemical compound Cc(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O LYTBMLCMMFRBFS-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a silole dithiophene-benzodi(benzoselenadiazole) copolymer material. The structural formula of the material is shown in the specification, wherein in the structural formula, R1, R2, R3 and R4 are C1-C20 alkyls; n is an integer from 1 to 100. The copolymer material formed by the compounds including silole dithiophene and benzodi(benzoselenadiazole) can form a strong donor-receptor structure which is beneficial for improving the stability of the material on the one hand and is beneficial for reducing the band gap of the material on the other hand, thus expanding the sunlight absorption range and improving the photoelectric conversion efficiency. Besides, the invention also relates to a preparation method of the copolymer material and an application of the copolymer material in the fields of polymer solar cell devices, organic electroluminescence devices and the like.
Description
Technical field
The present invention relates to copolymer material field, especially relate to a kind of thiophene and cough up two thiophene-benzo two (selenole) copolymer material and its preparation method and application.
Background technology
The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point in photovoltaic field always.Business-like silicon solar cell, because complex manufacturing, cost are high, is restricted its application at present.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Polymer solar cell device has superior market outlook because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated copolymer material and C
60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar cell device, and have obtained development at full speed.But the effciency of energy transfer of traditional polymer solar cell device is still lower, be on the one hand due to the carrier mobility of copolymer material than the mobility of inorganic monocrystal material low several orders of magnitude; The absorption spectrum of the conjugated copolymer material photocell material that used on the other hand can not mate well with solar spectrum.
Summary of the invention
Based on this, be necessary to provide a kind of thiophene that can improve photoelectric transformation efficiency to cough up two thiophene-benzo two (selenole) copolymer material and its preparation method and application.
Thiophene is coughed up two thiophene-benzo two (selenole) copolymer material, and structural formula is:
Wherein, R
1, R
2, R
3and R
4for C
1～C
20alkyl; N is the integer between 1～100.
Phenanthrene is by three six-rings and becomes, all atoms are in same plane, there is good electronics cavity transmission ability, and the rigidity of molecule is conducive to improve the thermal stability of material, in addition 9,10 luxuriant and rich with fragrance easily modifications,, can utilize easy method to introduce electron-donating group and electron-accepting group, regulate its confession/electrophilic performance.Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathodes such as magnesium, aluminium, it belongs to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, it is a kind of good body unit that is subject to, there is good electronic transport property, can also regulate the energy gap of material simultaneously.And the sulphur atom in the radius ratio diazosulfide of selenium atom is large in selenole, the molecule that more can strengthen between copolymer material and copolymer material chain is overlapping, promotes the hopping process of electric charge.Thiophene is five-membered ring structure, has moderate band gap, wider spectral response, preferably thermostability and film forming properties.Benzo two (selenole) is a kind of very excellent donor material, and benzo two (selenole) has the advantages such as simple in structure, symmetrical, electron delocalization performance is good, and has two dimensional structure, is a kind of very excellent acceptor material.Thiophene is coughed up molecule can form σ
*-π
*conjugation, makes thiophene cough up the minimum occupied orbital (LUMO) of molecule lower, has good electron affinity and electronic mobility simultaneously.Thiophene is coughed up two thiophene and is had three five-membered ring structures, has narrow band gap and strong conjugated nature.The copolymer material of being coughed up two thiophene and benzo two (selenole) formation by compound thiophene can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand sunlight absorption region, improve electricity conversion.
Thiophene is coughed up a preparation method for two thiophene-benzo two (selenole) copolymer material, comprises the steps:
Compd A and compd B are provided, and the structural formula of described compd A is:
The structural formula of described compd B is:
R
1, R
2, R
3and R
4for C
1～C
20alkyl;
In inert protective gas atmosphere; the ratio that is 1:1.5～1.5:1 according to mol ratio by compd A and compd B; in catalysts and solvents, carry out Stille coupling reaction, after separation and purification, obtain the following described thiophene of structural formula and cough up two thiophene-benzo two (selenole) copolymer material:
N is the integer between 1～100.
In an embodiment, described catalyzer is Pd therein
2(dba)
3(three (dibenzalacetone) two palladiums), Pd (PPh
3)
2cl
2(two (triphenylphosphine) palladium chloride) or Pd (PPh
3)
4(tetrakis triphenylphosphine palladium); The consumption of described catalyzer is 0.05%～20% of compd A molar weight.
In an embodiment, described solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene therein.
Therein in an embodiment, the purification procedures that described thiophene is coughed up two thiophene-benzo two (selenole) copolymer material is: in the mixed solution after Stille coupling reaction, add water and toluene to extract, collect organic phase, underpressure distillation concentrates described organic phase, again the described organic phase after concentrated is joined in dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected described solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained carries out methyl alcohol sedimentation after extracting with acetone apparatus,Soxhlet's more successively, suction filtration, the described thiophene of the purifying obtaining is coughed up two thiophene-benzo two (selenole) copolymer material.
In an embodiment, described compd A prepares as follows therein:
The Compound C with following structural formula is provided:
R
3and R
4for C
1～C
20alkyl;
In inert protective gas atmosphere; under-78 ℃ of conditions; the ratio that is 1:2 according to mol ratio by described Compound C and n-Butyl Lithium; in solvent, react 1～2 hour, then in reacted mixed solution, add tributyltin chloride, after continuation is reacted 1 hour under-78 ℃ of conditions, be warming up to room temperature reaction 6 hours; add again saturated sodium-chloride water solution termination reaction; after separation and purification, obtain described compd A, wherein, the molar weight of described tributyltin chloride is 2 times of described Compound C molar weight.
Therein in an embodiment, the purification procedures of described compd A is: in reacted mixed solution, add anhydrous diethyl ether extraction, collect organic phase, and remove the moisture in described organic phase with anhydrous sodium sulfate drying, suction filtration, collects liquid phase, and described liquid phase is rotated to evaporation concentration, the crude product obtaining is crossed to neutral alumina column chromatography, obtain the described compd A of purifying.
In an embodiment, described compd B prepares as follows therein:
Compound D and compd E are provided, and wherein, the structural formula of Compound D is:
The structural formula of compd E is:
R
1and R
2for C
1～C
20alkyl;
In inert protective gas atmosphere, in the mixing solutions of Compound D and compd E, add Bu
3n and Pd (OAc)
2(acid chloride (II)) carries out ring closure reaction, obtains described compd B after separation and purification, and wherein, the mol ratio of Compound D and compd E is 1:2, and the solvent in mixing solutions is dimethyl formamide, Bu
3the mol ratio of N and compd E is 1:1, Pd (OAc)
2molar weight be 10% of Compound D molar weight.
In an embodiment, the purification procedures of described compd B is therein:
To reacted mixed solution, water and methylene dichloride are extracted, collect organic phase, and remove the moisture in described organic phase with anhydrous sodium sulfate drying, filter, collect liquid phase, the unnecessary solvent in described liquid phase is removed in underpressure distillation, crosses silica gel column chromatography, obtains the described compd B of purifying.
Above-mentioned preparation method's technique is simple, mild condition, reaction is easy to control, be suitable for suitability for industrialized production, the thiophene preparing is coughed up two thiophene-benzo two (selenole) copolymer material and can be applied in the fields such as polymer solar cell device, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties and organic laser apparatus.
Accompanying drawing explanation
Fig. 1 is the structural representation of the polymer solar cell device in embodiment 6;
Fig. 2 is the structural representation of the organic electroluminescence device in embodiment 7.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments thiophene being coughed up to two thiophene-benzo two (selenole) copolymer material and its preparation method and application is below described in further detail.
The thiophene of one embodiment is coughed up two thiophene-benzo two (selenole) copolymer material, and structural formula is:
Wherein, R
1, R
2, R
3and R
4for C
1～C
20alkyl; N is the integer between 1～100; Preferably, n is the integer between 19～50.
The copolymer material of being coughed up two thiophene and benzo two (selenole) formation by compound thiophene can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand sunlight absorption region, improve electricity conversion.
In addition, present embodiment also provides a kind of thiophene to cough up the preparation method of two thiophene-benzo two (selenole) copolymer material, comprises the steps:
Compd A and compd B are provided, and the structural formula of compd A is:
The structural formula of compd B is:
R
1, R
2, R
3and R
4for C
1～C
20alkyl;
In inert protective gas atmosphere; the ratio that is 1:1.5～1.5:1 according to mol ratio by compd A and compd B; in catalysts and solvents, carry out Stille coupling reaction, after separation and purification, obtain the following thiophene of structural formula and cough up two thiophene-benzo two (selenole) copolymer material:
N is the integer between 1～100.
In the present embodiment, the catalyzer that above-mentioned preparation process is used is for organic palladium catalyzer, as Pd
2(dba)
3, Pd (PPh
3)
2cl
2or Pd (PPh
3)
4.The consumption of catalyzer is 0.05%～20% of compd A molar weight.Solvent can be tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene, and in reaction process, solvent needs enough, is also the complete solubilizing reaction thing of used in amounts and the product of solvent.The temperature of Stille reaction is 50～120 ℃, and the reaction times is 6～100 hours.
Further, the purification procedures that above-mentioned thiophene is coughed up two thiophene-benzo two (selenole) copolymer material is: in the mixed solution after Stille coupling reaction, add water and toluene to extract, collect organic phase, underpressure distillation concentrates organic phase, again the organic phase after concentrated is joined in dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained carries out methyl alcohol sedimentation after extracting with acetone apparatus,Soxhlet's more successively, suction filtration, the thiophene of the purifying obtaining is coughed up two thiophene-benzo two (selenole) copolymer material.
In the present embodiment, compd A is to prepare as follows:
The Compound C with following structural formula is provided:
R
3and R
4for C
1～C
20alkyl;
In inert protective gas atmosphere; under-78 ℃ of conditions; the ratio that is 1:2 according to mol ratio by Compound C and n-Butyl Lithium; in solvent, react 1～2 hour, then in reacted mixed solution, add tributyltin chloride, after continuation is reacted 1 hour under-78 ℃ of conditions, be warming up to room temperature reaction 6 hours; add again saturated sodium-chloride water solution termination reaction; after separation and purification, obtain compd A, wherein, the molar weight of tributyltin chloride is 2 times of Compound C molar weight.
Wherein, the purification procedures of compd A is: in reacted mixed solution, add anhydrous diethyl ether extraction, collect organic phase, and remove the moisture in organic phase with anhydrous sodium sulfate drying, suction filtration, collects liquid phase, and liquid phase is rotated to evaporation concentration, the crude product obtaining is crossed to neutral alumina column chromatography, obtain the compd A of purifying.
Compd B is to prepare as follows:
Compound D and compd E are provided, and wherein, the structural formula of Compound D is:
The structural formula of compd E is:
R
1and R
2for C
1～C
20alkyl;
In inert protective gas atmosphere, in the mixing solutions of Compound D and compd E, add Bu
3n and Pd (OAc)
2carry out ring closure reaction, obtain compd B after separation and purification, wherein, the mol ratio of Compound D and compd E is 1:2, and the solvent in mixing solutions is dimethyl formamide, Bu
3the mol ratio of N and compd E is 1:1, Pd (OAc)
2molar weight be 10% of Compound D molar weight.
Wherein, the purification procedures of compd B is:
To reacted mixed solution, water and methylene dichloride are extracted, collect organic phase, and remove the moisture in organic phase with anhydrous sodium sulfate drying, filter, collect liquid phase, the unnecessary solvent in liquid phase is removed in underpressure distillation, cross silica gel column chromatography, obtain the compd B of purifying.
The inert protective gas atmosphere that above-mentioned each compound preparation process is used can be the atmosphere of inert gases such as nitrogen atmosphere or argon gas etc.
Above-mentioned preparation method's technique is simple, mild condition, reaction is easy to control, be suitable for suitability for industrialized production, the thiophene preparing is coughed up two thiophene-benzo two (selenole) copolymer material and can be applied in the fields such as polymer solar cell device, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties and organic laser apparatus.
It is below specific embodiment part
Embodiment 1 is poly-, and { 4,4-dioctyl-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }:
The preparation process of this copolymer material is as follows:
One, 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole synthetic
1, compound 5-nitro-2,1,3 diazosulfide synthetic:
In there-necked flask, add 22.95g2-amino-5-N-methyl-p-nitroaniline (0.15mol) and 100ml thionyl chloride (SOCl
2), stir and slowly drip 2ml pyridine, after heating in 80～90 ℃ of back flow reaction 24h; Stopped reaction, is heated to 80 ℃ and revolves and steam excessive SOCl
2after, reaction product is cooled to room temperature, and is added in large water gaging, stir, there is throw out to occur, filter the solids of collecting dry through washing final vacuum, obtain 21.7g product 5-nitro-2,1,3 diazosulfide, productive rate 80%.
2, compound 4, the bromo-5-of 7-bis-nitro-2, and 1,3 diazosulfide synthetic:
In there-necked flask, add 10.35g5-nitro-2, the Hydrogen bromide of 1,3 diazosulfide (60mmol) and 15ml40wt%, be warming up to 127 ℃ of backflows, in 30min, slowly drip 11.3ml bromine the 4h that refluxes, heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, again with Gossypol recrystallized from chloroform once, obtain 10.2g product 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfides, productive rate: 50%.
3,4,4 '-bis-is bromo-6, and 6 '-dinitrobenzene-Lian 2,1,3 diazosulfides synthetic:
In there-necked flask, add successively 10.2g4, the bromo-5-of 7-bis-nitro-2, 1, 3 diazosulfides (30mmol), 9.5g copper powder and 90ml N, dinethylformamide (DMF), be heated to 120 ℃ of reactions after 3 hours, stopped reaction, be cooled to room temperature, add 90ml toluene, stir 30 minutes, filter, liquid is used saturated aqueous common salt and water washing successively, merge organic phase, with anhydrous magnesium sulfate drying, remove the moisture in organic phase, filter, rotary evaporation is removed organic solvent, the product obtaining dehydrated alcohol recrystallization, obtain 4.7g4, 4 '-bis-bromo-6, 6 '-dinitrobenzene-Lian 2, 1, 3 diazosulfides, productive rate 30.2%.
4,4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-diazosulfide synthetic:
In there-necked flask, add 10.3g4,4 '-bis-is bromo-6, and 6 '-dinitrobenzene-Lian 2,1,3 diazosulfides (20mmol), tetrahydrofuran (THF) (THF) and 40g SnCl that 300ml is dry
2(200mmol), be warming up to 100 ℃, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution, adjust reacted pH of mixed value to 8.0, then anhydrous diethyl ether extraction collection organic phase, revolve steaming gained organic phase and remove organic solvent, obtain solid crude product; Solid crude product is placed in there-necked flask, adds the hydrochloric acid (21.7mmol) of 58ml, and in 30 minutes agitation and dropping sodium nitrite solution 20ml(37.7mmol), temperature is controlled at below 5 ℃, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide+100ml water) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, collects organic phase with anhydrous diethyl ether extraction, again organic phase is collected to filtrate through washing, anhydrous magnesium sulfate drying, filtration successively, revolve evaporate to dryness filtrate, separated with silica gel column chromatography, then carry out recrystallizing methanol, obtain 4.1g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
5, synthesizing of 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine):
In there-necked flask, add 6.80g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1, the ethanol of 3 diazosulfides (0.01mol) and 200ml, form suspension, 0 ℃ drips 14g sodium borohydride (0.37mol), and under room temperature, mixture stirring reaction is 20 hours, stopped reaction, with anhydrous diethyl ether extraction, collect organic phase, then organic phase is processed through washing, anhydrous magnesium sulfate drying successively, filter and collect filtrate, revolve evaporate to dryness filtrate, obtain bromo-6,6 '-bis-iodo-di-s (1 of 5.49g product 4,4 '-bis-, 2-phenylenediamine), productive rate 88%.
6,4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole synthetic:
In there-necked flask, add 3.12g4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) (5mmol) and the ethanol of 60ml, reflux, and drip 1.17g SeO
2(10.5mmol) aqueous solution (hot water 22ml), reaction mixture refluxed 2 hours, stopped reaction, filters, and obtains 3.48g product 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3-selenole, productive rate 90%.
Two, compound 4, and 9-bis-is bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) synthetic:
In there-necked flask, add 3.87g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles (5mmol), 3.07g2,6,13, (synthetic method is with reference to Chem.Commun. for 17-tetramethyl--9-octadecyne (10mmol), 2011,47,8850-8852) and 25ml DMF, pass into nitrogen gas stirring 20min, then add 0.907g Bu
3n (10mmol) and 115mg Pd (OAc)
2(0.5mmol), be warming up to 130 ℃, heating 4h, after reaction finishes, be cooled to room temperature, reacted mixed solution is collected to organic phase with dichloromethane extraction after washing, by anhydrous sodium sulfate drying organic phase, remove unnecessary moisture, filter and collect filtrate, underpressure distillation concentrated filtrate, silica gel column chromatography is separated, obtain 2.48g product 4,9-bis-is bromo-6, and 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 60%.
Three, 4,4-dioctyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene synthetic:
Under the protection of nitrogen, in there-necked flask, add 8.66g2,6-bis-is bromo-4, and 4-dioctyl-thiophene is coughed up also [2,1-b; 3,4-b '] tetrahydrofuran solvent of two thiophene (0.015mol) and 100ml, under-78 ℃ of conditions, with syringe, in there-necked flask, slowly inject n-Butyl Lithium (about 0.03mol) solution of 12.6mL2.5M, continue stirring reaction 2h, under-78 ℃ of conditions, with syringe, inject 8.4mL tributyltin chloride (0.03mol), rise under room temperature stirring reaction 6 hours, finally add 30ml saturated sodium-chloride water solution termination reaction, with anhydrous diethyl ether extraction, collect organic phase, by anhydrous sodium sulfate drying organic phase, remove unnecessary moisture, filter to collect filtrate and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product 4,4-dioctyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene, productive rate 70%.
It is four, poly-that { 4,4-dioctyl-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } synthetic:
Under nitrogen protection, in there-necked flask, add 199.4mg4,4-dioctyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene (0.2mmol), 165.2mg4,9-bis-bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) (0.2mmol) and 40ml tetrahydrofuran solvent, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2cl
2(7.1 * 10
-3mmol), be heated to 90 ℃ of reaction 72h.After reaction, toward adding water and toluene to extract in the mixed solution after Stille coupling reaction in the reaction flask of product, collect organic phase, the concentrated organic phase of underpressure distillation is to the about 5ml of volume, again the organic phase after concentrated is joined in 400ml dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained is used methyl alcohol sedimentation with the extraction of acetone apparatus,Soxhlet's after three days more successively, under vacuum pump, suction filtration spends the night, obtain the end product of purifying.
End product after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 55650, n=50, copolymer material monodispersity is 2.4.
Embodiment 2 is poly-, and { 4,4-dimethyl-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }:
The preparation process of this copolymer material is as follows:
One, 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1, the synthetic step 1 with embodiment 1 of 3-selenole;
Two, compound 4, and 9-bis-is bromo-6, the synthetic step 2 with embodiment 1 of 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles).
Three, 4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene synthetic:
Under the protection of nitrogen, in there-necked flask, add 3.80g4,4-dimethyl-2,6-dibromo thiophene is coughed up also [2,1-b; 3,4-b '] tetrahydrofuran solvent of two thiophene (0.01mol) and 40ml, under-78 ℃ of conditions, with syringe, in there-necked flask, slowly inject n-Butyl Lithium (0.02mol) solution of 8.6mL2.5M, continue stirring reaction 1.5h, under-78 ℃ of conditions, with syringe, inject 5.6mL tributyltin chloride (0.02mol), react and after 1 hour, be warming up under room temperature stirring reaction 6 hours.Finally add 30ml saturated sodium-chloride water solution termination reaction, with anhydrous diethyl ether extraction, collect organic phase, with anhydrous sodium sulfate drying organic phase, remove unnecessary moisture, filter collection filtrate and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 65%.
It is four, poly-that { 4,4-dimethyl-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } synthetic:
Under nitrogen protection, in there-necked flask, add 160mg4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene (0.2mmol), 160mg4,9-bis-bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) (0.2mmol) and 40ml tetrahydrofuran solvent, vacuumize deoxygenation and be filled with nitrogen, then add 5mgPd
2(dba)
3(5.5 * 10
-3mmol), be heated to 90 ℃ of reaction 72h.After reaction, toward adding water and toluene to extract in the mixed solution after Stille coupling reaction in the reaction flask of product, collect organic phase, the concentrated organic phase of underpressure distillation is to the about 5ml of volume, again the organic phase after concentrated is joined in 400ml dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained is used methyl alcohol sedimentation with the extraction of acetone apparatus,Soxhlet's after three days more successively, under vacuum pump, suction filtration spends the night, obtain the end product of purifying.
End product after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 19257, n=21, copolymer material monodispersity is 2.3.
Embodiment 3 is poly-, and { 4,4-bis-(NSC 62789 base) thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e], two (selenoles) }:
The preparation process of this copolymer material is as follows:
One, 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1, the synthetic step 1 with embodiment 1 of 3-selenole.
Two, 4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles) synthetic:
In there-necked flask, add 7.74g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenole (10mmol), 1.36g2-pentyne (20mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852) and 50ml DMF, pass into nitrogen gas stirring 20min, then add 1.814gBu
3n (20mmol) and 230mg Pd (OAc)
2(1.0mmol), be warming up to 130 ℃, after heating 4h reaction, be cooled to room temperature, the mixed solution obtaining is collected organic phase with dichloromethane extraction after washing, with anhydrous sodium sulfate drying, remove the moisture in organic phase again, filter and collect filtrate, it is separated that filtrate is crossed silica gel column chromatography after underpressure distillation is concentrated, obtains 5.15g product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productive rate 65%.
Three, 4,4-bis-(NSC 62789 base)-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene synthetic:
Under the protection of nitrogen, in there-necked flask, add 9.13g2,6-bis-is bromo-4, and 4-bis-(NSC 62789 base)-thiophene is coughed up also [2,1-b; 3,4-b '] tetrahydrofuran solvent of two thiophene (0.01mol) and 90ml, under-78 ℃ of conditions, with syringe, slowly inject 8.6mL2.5M n-Butyl Lithium (0.02mol) solution again, continue stirring reaction 1h, under-78 ℃ of conditions, with syringe, inject 5.6mL tributyltin chloride (0.02mol), react and after 1 hour, be warming up under room temperature stirring reaction 6 hours.Add 30ml saturated sodium-chloride water solution termination reaction, with anhydrous diethyl ether extraction, collect organic phase, anhydrous sodium sulfate drying is removed moisture unnecessary in organic phase, after filtering by filtrate collection and revolve and evaporate solvent, finally crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 72%.
It is four, poly-that { 4,4-bis-(NSC 62789 base) thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e], two (selenoles) synthetic:
Under nitrogen protection, in there-necked flask, add 266.8mg4,4-bis-(NSC 62789 base)-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene (0.2mmol), 117.6mg4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles) (0.2mmol) and 40ml toluene solvant, vacuumize deoxygenation and be filled with nitrogen, then add 9mg Pd (PPh
3)
4(7.8 * 10
-3mmol), be heated to 90 ℃ of reaction 72h.After reaction, toward adding water and toluene to extract in the mixed solution after Stille coupling reaction in the reaction flask of product, collect organic phase, the concentrated organic phase of underpressure distillation is to the about 5ml of volume, again the organic phase after concentrated is joined in 400ml dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained is used methyl alcohol sedimentation with the extraction of acetone apparatus,Soxhlet's after three days more successively, under vacuum pump, suction filtration spends the night, obtain the end product of purifying.
End product after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 23028, n=19, copolymer material monodispersity is 2.7.
Embodiment 4 is poly-, and { 4,4-bis-(NSC 62789 base) thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles) }:
The preparation process of this copolymer material is as follows:
One, 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1, the synthetic step 1 with embodiment 1 of 3-selenole.
Two, 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfides) synthetic:
In there-necked flask, add 3.87g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles (5mmol), 4.47g2, (synthetic method is with reference to Chem.Commun. for 6 – dimethyl-9-30 alkynes (10mmol), 2011,47,8850-8852) and 30ml DMF, pass into nitrogen gas stirring 20min, add 0.907gBu
3n (10mmol) and 115mg Pd (OAc)
2(0.5mmol), be warming up to 130 ℃, after heating 4h, be cooled to room temperature, reacted mixed solution is collected to organic phase with dichloromethane extraction after washing, and anhydrous sodium sulfate drying is removed moisture unnecessary in organic phase, filters organic phase and collects filtrate, it is separated that filtrate is crossed silica gel column chromatography after underpressure distillation is concentrated, obtain 2.7g product 4,9-bis-is bromo-6, and 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 62%.
Three, 4,4-bis-(NSC 62789 base)-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] the synthetic step 3 with embodiment 3 of two thiophene.
It is four, poly-that { 4,4-bis-(NSC 62789 base) thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles) synthetic:
Under nitrogen protection, add 400.2mg4,4-bis-(NSC 62789 base)-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene (0.3mmol), 193.4mg4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (selenoles) (0.2mmol) and 40ml glycol dinitrate ether solvents, vacuumize deoxygenation and be filled with nitrogen, then add 28.04mg Pd (PPh
3)
2cl
2(0.04mmol), be heated to 120 ℃ of reaction 100h.After reaction, toward adding water and toluene to extract in the mixed solution after Stille coupling reaction in the reaction flask of product, collect organic phase, the concentrated organic phase of underpressure distillation is to the about 5ml of volume, again the organic phase after concentrated is joined in 400ml dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained is used methyl alcohol sedimentation with the extraction of acetone apparatus,Soxhlet's after three days more successively, under vacuum pump, suction filtration spends the night, obtain the end product of purifying.
End product after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 159000, n=100, copolymer material monodispersity is 6.0.
Embodiment 5 is poly-, and { 4,4-dimethyl-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e], two (selenoles) }:
One, 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1, the synthetic step 1 with embodiment 1 of 3-selenole.
Two, 4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles) synthetic with embodiment 3.
Three, 4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] the synthetic step 3 with embodiment 2 of two thiophene.
It is four, poly-that { 4,4-dimethyl-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e], two (selenoles) synthetic:
Under nitrogen protection, add 160mg4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene (0.2mmol), 176.4mg4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles) (0.3mmol) and 40ml benzene solvent, vacuumize deoxygenation and be filled with nitrogen, then add 1.05mg Pd (PPh
3)
2cl
2(1.5 * 10
-4mmol) be heated to 50 ℃ of reaction 6h.After reaction, toward adding water and toluene to extract in the mixed solution after Stille coupling reaction in the reaction flask of product, collect organic phase, the concentrated organic phase of underpressure distillation is to the about 5ml of volume, again the organic phase after concentrated is joined in 400ml dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained is used methyl alcohol sedimentation with the extraction of acetone apparatus,Soxhlet's after three days more successively, under vacuum pump, suction filtration spends the night, obtain the end product of purifying.
End product after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 679, n=1.
Embodiment 6
Copolymer material prepared by the embodiment 1-3 of take is active coating, prepares polymer solar cell device, and its structure as shown in Figure 1, comprises the substrate, anode, middle supplementary layer, active coating and the negative electrode that stack gradually.Wherein, substrate is glass.Anode is that square resistance is the tin indium oxide (ITO) of 10 Ω/mouths.Middle supplementary layer adopts poly-(3,4-ethylenedioxy thiophene is coughed up two thiophene): polystyrolsulfon acid matrix material (being called for short PEDOT:PSS).Active coating comprises electron donor material and electron acceptor material, and electron donor material is copolymer material prepared by embodiment 1-3, and electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM).Negative electrode is aluminium.This device architecture can briefly be described as glass/ITO/PEDOT:PSS/ active coating/Al; Wherein, brace "/" is laminate structure, lower same.
Wherein, substrate of glass, as bottom, is chosen ito glass (with the glass of anode ITO layer) during making, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma, processes; Then supplementary layer PEDOT:PSS in the middle of applying on ito glass, thickness is 120nm; The copolymer material of again being prepared by 10mg embodiment 1-3 is dissolved in 0.4ml dimethylbenzene, is dissolved in 8mg PCBM the solution blending that 0.4ml chlorobenzene obtains, and is spun on PEDOT:PSS rete, and thickness is about 150nm, obtains active coating; At vacuum condition (2 * 10
-3pa) lower evaporation cathodic metal aluminium, thickness is 120nm, obtains polymer solar cell device.
All preparation process are all carried out in the glove box that the inert protective gas atmosphere such as nitrogen are provided.
By Keithley236 current/voltage source-measuring system and test the I-E characteristic of the polymer solar cell device of above-mentioned preparation, obtain the performance data of device in Table 1.
Table 1 be take the performance data of the polymer solar cell device that copolymer material prepared by embodiment 1-3 prepared as active coating
As seen from the data in Table 1, the energy conversion efficiency of preparing the polymer solar cell device that copolymer material prepared as active coating with embodiment 1-3 is 1.03～1.98, show to cough up two thiophene-benzo two (selenole) copolymer material owing to containing new benzo two (selenole) conjugate unit containing thiophene, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and pass through the improvement of device architecture or modification, can obtain higher effciency of energy transfer.
Embodiment 7
Copolymer material 1 prepared by the embodiment 1 of take is luminescent layer, is prepared with organic electroluminescence devices, and its structure as shown in Figure 2, comprises the glass substrate, transparent anode, luminescent layer, buffer layer and the negative electrode that stack gradually.Wherein, transparent anode is that the square resistance of thickness 150nm is the tin indium oxide (ITO) of 10 Ω/mouths, luminescent layer is the copolymer material of embodiment 1 preparation of 90nm thickness, buffer layer is 1.5nm LiF, reality is cathode buffer layer, negative electrode is the metal A l of 150nm, and the structure of device can be expressed as: glass/ITO/ luminescent layer/buffer layer/Al.
By Keithley source measuring system (Keithley2400Sourcemeter), tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device, with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 13.9cd/A, and high-high brightness is 1188cd/m
2.
Be appreciated that in other embodiments, the structure of solar cell device and organic electroluminescence device is not limited to described in above-described embodiment 6 and 7.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. thiophene is coughed up two thiophene-benzo two (selenole) copolymer material, and structural formula is:
Wherein, R
1, R
2, R
3and R
4for C
1～C
20alkyl; N is the integer between 1～100.
2. thiophene is coughed up a preparation method for two thiophene-benzo two (selenole) copolymer material, it is characterized in that, comprises the steps:
Compd A and compd B are provided, and the structural formula of described compd A is:
The structural formula of described compd B is:
R
1, R
2, R
3and R
4for C
1～C
20alkyl;
In inert protective gas atmosphere; the ratio that is 1:1.5～1.5:1 according to mol ratio by compd A and compd B; in catalysts and solvents, carry out Stille coupling reaction, after separation and purification, obtain the following described thiophene of structural formula and cough up two thiophene-benzo two (selenole) copolymer material:
N is the integer between 1～100.
3. thiophene is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material as claimed in claim 2, it is characterized in that, described catalyzer is Pd
2(dba)
3, Pd (PPh
3)
2cl
2or Pd (PPh
3)
4; The consumption of described catalyzer is 0.05%～20% of compd A molar weight.
4. thiophene as claimed in claim 2 is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material, it is characterized in that, described solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene.
5. thiophene as claimed in claim 2 is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material, it is characterized in that, the purification procedures that described thiophene is coughed up two thiophene-benzo two (selenole) copolymer material is:
In the mixed solution after Stille coupling reaction, add water and toluene to extract, collect organic phase, underpressure distillation concentrates described organic phase, again the described organic phase after concentrated is joined in dehydrated alcohol, stir, there is solid precipitation to separate out, suction filtration is collected described solid precipitation and is dried, the solids obtaining is crossed neutral alumina chromatography column after dissolving with chloroform, collect solution, solvent unnecessary in solution is removed in decompression, carry out successively again methyl alcohol sedimentation, suction filtration, the solids of gained carries out methyl alcohol sedimentation after extracting with acetone apparatus,Soxhlet's more successively, suction filtration, the described thiophene of the purifying obtaining is coughed up two thiophene-benzo two (selenole) copolymer material.
6. thiophene as claimed in claim 2 is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material, it is characterized in that, described compd A prepares as follows:
The Compound C with following structural formula is provided:
R
3and R
4for C
1～C
20alkyl;
In inert protective gas atmosphere; under-78 ℃ of conditions; the ratio that is 1:2 according to mol ratio by described Compound C and n-Butyl Lithium; in solvent, react 1～2 hour, then in reacted mixed solution, add tributyltin chloride, after continuation is reacted 1 hour under-78 ℃ of conditions, be warming up to room temperature reaction 6 hours; add again saturated sodium-chloride water solution termination reaction; after separation and purification, obtain described compd A, wherein, the molar weight of described tributyltin chloride is 2 times of described Compound C molar weight.
7. thiophene as claimed in claim 6 is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material, it is characterized in that, the purification procedures of described compd A is:
In reacted mixed solution, add anhydrous diethyl ether extraction, collect organic phase, and remove the moisture in described organic phase with anhydrous sodium sulfate drying, suction filtration, collect liquid phase, described liquid phase is rotated to evaporation concentration, the crude product obtaining is crossed to neutral alumina column chromatography, obtain the described compd A of purifying.
8. thiophene as claimed in claim 2 is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material, it is characterized in that, described compd B prepares as follows:
Compound D and compd E are provided, and wherein, the structural formula of Compound D is:
The structural formula of compd E is:
R
1and R
2for C
1～C
20alkyl;
In inert protective gas atmosphere, in the mixing solutions of Compound D and compd E, add Bu
3n and Pd (OAc)
2carry out ring closure reaction, obtain described compd B after separation and purification, wherein, the mol ratio of Compound D and compd E is 1:2, and the solvent in mixing solutions is dimethyl formamide, Bu
3the mol ratio of N and compd E is 1:1, Pd (OAc)
2molar weight be 10% of Compound D molar weight.
9. thiophene as claimed in claim 8 is coughed up the preparation method of two thiophene-benzo two (selenole) copolymer material, it is characterized in that, the purification procedures of described compd B is:
To reacted mixed solution, water and methylene dichloride are extracted, collect organic phase, and remove the moisture in described organic phase with anhydrous sodium sulfate drying, filter, collect liquid phase, the unnecessary solvent in described liquid phase is removed in underpressure distillation, crosses silica gel column chromatography, obtains the described compd B of purifying.
10. thiophene as claimed in claim 1 is coughed up the application of two thiophene-benzo two (selenole) copolymer material in polymer solar cell device, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties and organic laser apparatus.
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| CN102898626A (en) * | 2012-10-13 | 2013-01-30 | 华南理工大学 | Naphtho[1,2-c:5,6-c]bis(2-alkyl-[1,2,3]triazole)-containing organic semiconductor materials and use thereof |
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| CN102898626A (en) * | 2012-10-13 | 2013-01-30 | 华南理工大学 | Naphtho[1,2-c:5,6-c]bis(2-alkyl-[1,2,3]triazole)-containing organic semiconductor materials and use thereof |
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