CN103804656A - Selenophen bithiophene-benzodi(diazosulfide) copolymer as well as preparation method and application thereof - Google Patents
Selenophen bithiophene-benzodi(diazosulfide) copolymer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a selenophen bithiophene-benzodi(diazosulfide) copolymer as well as a preparation method and an application thereof. The copolymer has a structure as shown in formula (I) in the specification and is prepared from benzodi(diazosulfide) and selenophen bithiophene through a Stille coupling reaction. The copolymer disclosed by the invention simultaneously contains selenophen bithiophene and benzodi(diazosulfide) and contains a new benzodi(diazosulfide) conjugated unit, thus a powerful donator-acceptor structure can be formed and is favorable for improving the stability of a material and reducing an energy band gap of the material, so that the sunshine absorption range is widened and the photoelectric conversion efficiency is improved. In the preparation method of the copolymer disclosed by the invention, the Stille reaction is a quite mature polymerization reaction which is high in yield, moderate in condition and easy to control.
Description
Technical field
The invention belongs to organic materials technical field, specifically, the present invention relates to a kind of selenophen bithiophene-benzo two (diazosulfide) multipolymer 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 battery 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.Above report conjugated polymers and C from N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474)
60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed.At present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be due to the carrier mobility of polymkeric substance than the mobility of inorganic monocrystal material low several orders of magnitude.The absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor on the one hand, raising absorbs sun power, can adopt on the other hand annealing, add the materials such as tensio-active agent to be optimized device.
Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathode such as magnesium, aluminium; Belonging to short of electricity subtype aromatic cycle compound, have strong electron-withdrawing power, is that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.
Luxuriant and rich with fragrance by three six-rings one-tenth, 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, and luxuriant and rich with fragrance 9, easily modify for 10, can utilize easy method to introduce electron-donating group and electron-accepting group, regulate its confession/electrophilic performance.Therefore it has a wide range of applications in the photoelectric materials such as Organic Light Emitting Diode, organic solar batteries, field-effect transistor
The radius ratio sulphur atom of selenium atom large, can strengthen molecule between polymer poly compound chain overlapping more, promotes the hopping process of electric charge.Because selenophen has low band gap and 2,3,4,5 easily modify and replace, easily film forming and processing.Selenophen has five-membered ring structure, has narrow band gap and strong conjugated nature, at present in the photoelectric material such as widespread use and Organic Light Emitting Diode, organic solar batteries, field-effect transistor.And thiophene is good photoelectric material, there is narrow being with, easily modifying and film forming, cause the extensive concern of researcher.
But the polymkeric substance that contains selenophen bithiophene-benzo two (diazosulfide) multipolymer does not still have document and patent report at present simultaneously, this has just limited its range of application greatly.
Summary of the invention
Based on this, the invention provides a kind of containing selenophen bithiophene-benzo two (diazosulfide) multipolymer.
It is a kind of that containing selenophen bithiophene-benzo two (diazosulfide) multipolymer, described multipolymer has the structure of formula (I),
Wherein, R
1, R
2identical or different, be selected from C
1～C
20alkyl; R
3, R
4identical or different, be selected from H or C
1～C
20alkyl; N is the integer of 1-100.
Therein in an embodiment, described R
1, R
2, R
3, R
4be selected from C
1～C
10alkyl; N is 25～76 integer.
The present invention also provides the above-mentioned preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer.
A kind of preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer, comprises the following steps:
(1), in inert gas environment, by structural formula be
4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, structural formula be
acetylene compound, the first catalyzer and alkali join in the first solvent, 130 ℃ reaction 4h, obtain compound 3, the structural formula of described compound 3 is:
described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are 1: 2 with the mole dosage ratio of acetylene compound, and described alkali is 1: 1 with the mole dosage ratio of acetylene compound;
(2), in inert gas environment, compound 4 is joined in the second solvent, add butyllithium reaction 1-2h at-78 ℃, then add SnBu at-78 ℃
3after Cl reaction 1h, be warming up to room temperature, after reaction 6h, obtain compound 5 through neutral alumina column chromatography; The structural formula of described compound 4 is:
the structural formula of described compound 5 is:
described compound 4 is 1: 2 with the mole dosage ratio of butyllithium, described SnBu
3the mole dosage of Cl is 2 times of compound 4;
(3), in inert gas environment, compound 3, compound 5, the second catalyzer are added in the 3rd solvent, 50-120 ℃ of reaction 6～100 hours, obtains containing selenophen bithiophene-benzo two (diazosulfide) multipolymer; Described compound 3 is 1: 1.5～1.5: 1 with the mole dosage ratio of compound 5;
In above-mentioned corresponding formula, R
1, R
2identical or different, be selected from C
1～C
20alkyl; R
3, R
4identical or different, be selected from H or C
1～C
20alkyl; N is the integer of 1-100.
In an embodiment, in step (1), described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are to adopt following steps to make therein:
By structural formula be
compd E add in thionyl chloride, stir and drip pyridine in thionyl chloride, back flow reaction at 85 ℃, makes structural formula and is
compound F 17-hydroxy-corticosterone;
Compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, and at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, and obtains structural formula and is
compound G;
Compound G is added in the DMF solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be
compound H;
Compound H is added to SnCl
2in the tetrahydrofuran solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, makes described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.
In an embodiment, in step (1), described the first catalyzer is Pd (OAc) therein
2the mole dosage of (palladium) described first catalyzer is 10% of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.
In some embodiment, described the second catalyzer is Pd therein
2(dba)
3(three (diphenylene acetone) two palladiums), Pd (PPh
3)
4(tetrakis triphenylphosphine palladium) or Pd (PPh
3)
2cl
2(two (triphenylphosphine) palladium chloride), the mole dosage of described the second catalyzer is the 0.05%-20% of compound 3.
In an embodiment, described the second catalyzer is Pd (PPh therein
3)
2cl
2.
In some embodiment, in step (1), described alkali is Bu therein
3n, described acetylene compound is 2,6,13,17-tetramethyl--9-octadecyne, 2,6-dimethyl-9-30 alkynes or valerylene.
Therein in some embodiment, described in step (1), the first solvent is DMF (N, dinethylformamide), the second solvent described in step (2) is THF (tetrahydrofuran (THF)), and described in step (3), the 3rd solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
Step (1) is to step (3), and described rare gas element is nitrogen or argon gas.
The present invention also provides containing the application of selenophen bithiophene-benzo two (diazosulfide) multipolymer in the fields such as solar cell, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or organic laser.
Multipolymer of the present invention contains selenophen bithiophene, benzo two (diazosulfide) simultaneously.Benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, the polymkeric substance being made up of selenophen bithiophene, benzo two (diazosulfide) contains new benzo two (diazosulfide) conjugate unit, 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 the preparation method of multipolymer of the present invention, the route of synthetic benzo two (diazosulfide) is fairly simple and ripe, easily improves solvability and the molecular weight of product by introducing alkyl, is conducive to film forming processing; Stille reaction is a kind of very ripe polyreaction, and productive rate is high, and mild condition, is easy to control.
Accompanying drawing explanation
Fig. 1 is the structural representation using the multipolymer in embodiment of the present invention 1-3 as the organic solar batteries device of active coating;
Fig. 2 is the structural representation using the multipolymer in the embodiment of the present invention 1 as the organic electroluminescence device of luminescent layer.
Embodiment
In order to understand better the content of patent of the present invention, further illustrate the present invention below by specific embodiment and accompanying drawing, but these embodiment do not limit the present invention.
Involved in the present invention containing selenophen bithiophene-benzo two (diazosulfide) multipolymer, there is following structure:
Wherein, R
1, R
2identical or different, be selected from C
1～C
20alkyl; R
3, R
4identical or different, be selected from H or C
1～C
20alkyl; N is the integer of 1-100.
Preferably, R
1, R
2, R
3, R
4be selected from G
1～C
10alkyl; N is 25～76 integer;
Preferred, R
1, R
2, R
3, R
4be selected from C
10alkyl; N is 58.
Preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer of the present invention, comprises the following steps:
(1), in inert gas environment, by 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, acetylene compound, the first catalyzer and alkali join in the first solvent, 130 ℃ of reaction 4h, obtain compound 3, and the structural formula of described compound 3 is:
Described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are 1: 2 with the mole dosage ratio of acetylene compound, and described alkali is Bu
3n, described alkali is 1: 1 with the mole dosage ratio of acetylene compound.Described the first catalyzer is Pd (OAc)
2, the mole dosage of described the first catalyzer is 10% of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, described the first solvent is DMF.
The reaction equation of this step is:
(2), in inert gas environment, compound 4 is joined in the second solvent, at-78 ℃, add butyllithium reaction 1-2h, then add SnBu at-78 ℃
3after Cl reaction 1h, be warming up to room temperature, after reaction 6h, obtain compound 5 through neutral alumina column chromatography; The structural formula of described compound 4 is:
The structural formula of described compound 5 is:
Described compound 4 is 1: 2 with the mole dosage ratio of butyllithium, described SnBu
3the mole dosage of Cl be compound 42 times; Described the second solvent is THF.
The reaction equation of this step is:
(3), in inert gas environment, compound 3, compound 5, the second catalyzer are added in the 3rd solvent, 50-120 ℃ of reaction 6～100 hours, obtains containing selenophen bithiophene-benzo two (diazosulfide) multipolymer;
Described compound 3 is 1: 1.5～1.5: 1 with the mole dosage ratio of compound 5; Described the second catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, be preferably Pd (PPh
3)
2cl
2, described the second catalyzer
Mole dosage is the 0.05%-20% of compound 3, and described the 3rd solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
The reaction equation of this step is:
In above-mentioned steps, described rare gas element is nitrogen or argon gas.
Following examples contribute to understand the present invention, but do not limit the scope of the invention.
Embodiment 1
The polymkeric substance of this embodiment is: gather { 2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }, have the structure of following formula:
The preparation method of the polymkeric substance of the present embodiment comprises the following steps:
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
(1) prepare 5-nitro-2,1,3 diazosulfide
In there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline (22.95g, 0.15mol) and 100mL thionyl chloride SOCl
2, stir and slowly drip 2mL pyridine, under room temperature, O-Phenylene Diamine can not all dissolve, and in 80～90 ℃ of back flow reaction 24h, stopped reaction, steams excessive SOCl
2after, mixture is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%;
(2) prepare the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide
In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and 40% Hydrogen bromide 15ml, be warming up to 127 ℃ of backflows, in 30min, slowly drip bromine 11.3ml the 4h that refluxes, heat filtering, refilters after filtrate is cooling, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide 10.2g, productive rate: 50%.
(3) prepare 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides
In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF of 90mL, is heated to 120 ℃ of reactions after 3 hours, stopped reaction, be cooled to room temperature, add 90mL toluene, stir 30 minutes, filter, filtrate, with saturated aqueous common salt and water washing, merges organic layer, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtain product 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.
(4) prepare 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), add the tetrahydrofuran THF that 300mL is dry, add 40g SnCl
2(200mmol), be warming up to 100 ℃, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtains solid crude product, be put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58ml, agitation and dropping sodium nitrite solution 20mL (37.7mmol) in 30 minutes, 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, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, with silica gel column chromatography separation, then carry out recrystallizing methanol, obtain 4.1g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
Two, preparation 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides (3.4g,
5mmol), add 2,6,13,17-tetramethyl--9-octadecyne (3.07g, 10mmol) (synthetic method with reference to Chem.Commun., 2011,47,8850-8852), 25mL DMF, passes into nitrogen gas stirring 20min, adds Bu
3n (0.907g, 10mmol), Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide) 2.4g, productive rate 70%.
Three, preparation 5,5 '-bis-(tributyl tinbases)-2,2 '-selenophen bithiophene
Under the protection of nitrogen, in there-necked flask, add 5,5 '-bis-bromo-2; 2 '-selenophen bithiophene (5.56g; 0.015mol), add the tetrahydrofuran solvent of 60mL, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (12.6mL with syringe again; 2.5M; 0.03mol), continue stirring reaction 2h, under-78 ℃ of conditions, inject tributyltin chloride (8.4mL with syringe; 0.03mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.Add saturated sodium-chloride water solution (30mL) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, 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 74%.
Four, preparation poly-{ 2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }
Under nitrogen protection, add 5,5 '-bis-(tributyl tinbases)-2; 2 '-selenophen bithiophene (158.2mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl octyl group)-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and tetrahydrofuran solvent 40mL; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2cl
2, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
By poly-{ 2 after purifying, 2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } polymkeric substance (P1) carries out GPC test, number-average molecular weight Mn ≈ 20350, n=25, polymkeric substance monodispersity is 2.3.
Embodiment 2
The polymkeric substance of this embodiment is: gather { 4,4 '-didecyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }, have the structure of following formula:
The preparation method of the polymkeric substance of the present embodiment comprises the following steps:
One, preparation 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides)
With the step 2 of embodiment 1.
Two, preparation 4,4 '-didecyl-5,5 '-bis-(tributyl tinbases)-2,2 '-selenophen bithiophene
Under the protection of nitrogen; in there-necked flask, add 4; 4 '-didecyl-5; 5 '-bis-bromo-2; 2 '-selenophen bithiophene (6.51g; 0.01mol); add the tetrahydrofuran solvent of 80mL; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL, 2.5M, 0.02mol) with syringe again; continue stirring reaction 1h; under-78 ℃ of conditions, inject tributyltin chloride (5.6mL, 0.02mol) with syringe, react and after 1 hour, be warming up to stirring at room temperature reaction 6 hours.Add saturated sodium-chloride water solution (30mL) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain 4,4 '-didecyl-5,5 '-bis-(tributyl tinbases)-2,2 '-selenophen bithiophene, productive rate 68%.
Three, preparation poly-{ 4,4 '-didecyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }
Under nitrogen protection, add 4,4 '-didecyl-5; 5 '-bis-(tributyl tinbases)-2,2 '-selenophen bithiophene (214.4mg, 0.2mmol), 4; 9-bis-bromo-6; 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3; 4-e] two (diazosulfide) (146.6mg; 0.2mmol), with tetrahydrofuran solvent 40mL, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2cl
2, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night is gathered { 4,4 '-didecyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }.
By poly-{ 4 after purifying, 4 '-didecyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } polymkeric substance (P2) carries out GPC test, number-average molecular weight Mn ≈ 63510, n=58, polymkeric substance monodispersity is 2.2.
Embodiment 3
The polymkeric substance of this embodiment is: gather { 4,4 '-didecyl-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }, have the structure of following formula:
The preparation method of the polymkeric substance of the present embodiment comprises the following steps:
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
With the step 1 of embodiment 1.
Two, the preparation bromo-6-of 4,9-bis-(3,7-dimethyl octyl group)-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), (synthetic method is with reference to Chem.Commun. to add 2,6-dimethyl-9-, 30 alkynes (4.47g, 10mmol), 2011,47,8850-8852), 25mL DMF, pass into nitrogen gas stirring 20min, add Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 2.7g4, the bromo-6-of 9-bis-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 62%.
Three, preparation 4,4 '-didecyl-5,5 '-bis-(tributyl tinbases)-2,2 '-selenophen bithiophene
With the step 2 of embodiment 2.
Four, preparation poly-{ 4,4 '-didecyl-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }
Under nitrogen protection, add 4,4 '-didecyl-5; 5 '-bis-(tributyl tinbases)-2; 2 '-selenophen bithiophene (214.4mg, 0.2mmol), 4, the bromo-6-(3 of 9-bis-; 7-dimethyl octyl group)-7-NSC 62789 base-benzo [2; 1-e:3,4-e] two (diazosulfide) (174.6mg, 0.2mmol) and tetrahydrofuran solvent 40mL; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2cl
2, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night is gathered { 4,4 '-didecyl-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }.
By poly-{ 4 after purifying, 4 '-didecyl-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } polymkeric substance (P3) carries out GPC test, number-average molecular weight Mn ≈ 93860, n=76, polymkeric substance monodispersity is 2.2.
Embodiment 4
The polymkeric substance of this embodiment is: poly-{ 4,4 '-bis-(NSC 62789 bases)-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) }, there is the structure of following formula:
The preparation method of the polymkeric substance of the present embodiment comprises the following steps:
One, the preparation bromo-6-of 4,9-bis-(3,7-dimethyl octyl group)-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides)
With the step 2 of embodiment 3.
Two, preparation 4,4 '-bis-(NSC 62789 base)-5,5 '-bis-(tributyl tinbases)-2,2 '-selenophen bithiophene
Under the protection of nitrogen; in there-necked flask, add 4; 4 '-bis-(NSC 62789 bases)-5; 5 '-bis-bromo-2; 2 '-selenophen bithiophene (9.32g; 0.01mol); add the tetrahydrofuran solvent of 100ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL, 2.5M, 0.02mol) with syringe again; continue stirring reaction 1.5h; under-78 ℃ of conditions, inject tributyltin chloride (5.6mL, 0.02mol) with syringe, react and after 1 hour, be warming up to stirring at room temperature reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after suction filtration 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 62%
Three, preparation poly-{ 4,4 '-bis-(NSC 62789 bases)-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }
Under nitrogen protection; add 4; 4 '-bis-(NSC 62789 bases)-5; 5 '-bis-(tributyl tinbases)-2; 2 '-selenophen bithiophene (405.6mg; 0.3mmol), 4; the bromo-6-(3 of 9-bis-; 7-dimethyl octyl group)-7-NSC 62789 base-benzo [2; 1-e:3,4-e] two (diazosulfide) (174.6mg, 0.2mmol) and tetrahydrofuran solvent 40mL; vacuumize deoxygenation and be filled with nitrogen, then add 28.04mg Pd (PPh
3)
2cl
2, be heated to 120 ℃ of reaction 100h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
By poly-{ 4 after purifying, 4 '-bis-(NSC 62789 bases)-2,2 '-selenophen bithiophene-6-(3,7-dimethyl octyl group)-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } polymkeric substance carries out GPC test, number-average molecular weight Mn ≈ 151500, n=100, polymkeric substance monodispersity is 4.5.
Embodiment 5
The polymkeric substance of this embodiment is: gather { 4,4 '-dimethyl-2,2 '-selenophen bithiophene-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }, have the structure of following formula:
The preparation method of the polymkeric substance of the present embodiment comprises the following steps:
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
With the step 1 of embodiment 1.
Two, preparation 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (6.8g, 10mmol), add valerylene (1.36g, 20mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 50mL DMF, passes into nitrogen gas stirring 20min, adds Bu
3n (1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 2.6g product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 52.6%
Three, preparation 4,4 '-dimethyl-5,5 '-bis-(tributyl tin)-2,2 '-selenophen bithiophene
Under the protection of nitrogen; in there-necked flask, add 4; 4 '-dimethyl-5; 5 '-bis-bromo-2; 2 '-selenophen bithiophene (8.00g; 0.02mol); add the tetrahydrofuran solvent of 100mL; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (16.8mL, 2.5M, 0.04mol) with syringe again; continue stirring reaction 2h; under-78 ℃ of conditions, inject tributyltin chloride (11.2mL, 0.04mol) with syringe, react and after 1 hour, be warming up to stirring at room temperature reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after suction filtration 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 68%.
Four, preparation poly-{ 4,4 '-dimethyl-2,2 '-selenophen bithiophene-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }
Under nitrogen protection; add 4,4 '-dimethyl-5,5 '-bis-(tributyl tin)-2; 2 '-selenophen bithiophene (163.8mg; 0.2mmol), 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3; 4-e] two (diazosulfide) (148.2mg; 0.3mmol), with tetrahydrofuran solvent 40mL, vacuumize deoxygenation and be filled with nitrogen, then add 0.11mg Pd (PPh
3)
2cl
2, be heated to 50 ℃ of reaction 6h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 100mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
Poly-{ 4,4 '-dimethyl-2,2 '-selenophen bithiophene-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) } polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 604, n=1.
Embodiment 6
The polymkeric substance of this embodiment is: gather { 4,4 '-dimethyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }, have the structure of following formula:
The preparation method of the polymkeric substance of the present embodiment comprises the following steps:
One, preparation 4,4 '-dimethyl-5,5 '-bis-(tributyl tin)-2,2 '-selenophen bithiophene
With the step 3 of embodiment 5.
Two, preparation 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides)
With the step 2 of embodiment 1.
Three, poly-{ 4,4 '-dimethyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } polymkeric substance of preparation
Under nitrogen protection, add 4,4 '-dimethyl-5; 5 '-bis-(tributyl tin)-2,2 '-selenophen bithiophene (163.8mg, 0.2mmol), 4; 9-bis-bromo-6; 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3; 4-e] two (diazosulfide) (160mg; 0.2mmol), with tetrahydrofuran solvent 40mL, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2cl
2, be heated to 90 ℃ of reaction 48h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
By poly-{ 4 after purifying, 4 '-dimethyl-2,2 '-selenophen bithiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } polymkeric substance carries out GPC test, number-average molecular weight Mn ≈ 29470, n=35, polymkeric substance monodispersity is 2.5.
The organic solar batteries device of the active coating that embodiment 7 contains multipolymer of the present invention
The multipolymer of preparing take embodiment of the present invention 1-3 is active coating, prepares respectively organic solar cell device 1-3, and all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.
The structure of organic solar batteries device 1-3 as shown in Figure 1, comprises stacked substrate of glass from bottom to up successively, anode, middle supplementary layer, active coating and negative electrode.Wherein, anode is ITO, is that square resistance is the tin indium oxide of 10-20 Ω/mouth; Middle supplementary layer adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, is called for short PEDOT:PSS (CLEVIOS P VP Al4083); Active coating comprises electron donor material and electron acceptor material, and electron donor material is polymkeric substance prepared by the embodiment of the present invention, and electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM); Negative electrode is aluminium, and this device architecture can briefly be described as glass/ITO/PEDOT:PSS/ active coating/Al.
The preparation method of this organic solar batteries device is: substrate of glass is as bottom, when making, choose ito glass (with anode ITO layer, can buy, ito glass in this embodiment is purchased from China Nanbo Group Co), thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma processing; Then supplementary layer PEDOT:PSS in the middle of applying on ito glass, thickness is 100nm; The multipolymer of again being prepared by the 10mg embodiment of the present invention is dissolved in 0.4mL dimethylbenzene, and the solution blending with the 8mg PCBM that is dissolved in 0.4mL chlorobenzene obtains, is spun on PEDOT:PSS rete, and thickness is about 120nm, obtains active coating; At vacuum condition (2 × 10
-3pa) lower evaporation cathodic metal aluminium, thickness is 120nm, obtains organic solar batteries device.
By the I-E characteristic of Keithley236 current/voltage source-measuring system and test organic solar batteries device 1-3, obtain the performance data of device 1-3 in table 1.
The performance data of table 1 organic solar batteries device 1-3
As shown in Table 1, the energy conversion efficiency of the organic solar batteries device 1-3 preparing as active coating with the multipolymer of embodiment of the present invention 1-3 is 1.12～1.23%, show that selenophen bithiophene-benzo two (diazosulfide) multipolymer that contains of the present invention is owing to containing new benzo two (diazosulfide) conjugate unit, 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 improve effciency of energy transfer.
The organic electroluminescence device of the active coating that embodiment 8 contains multipolymer of the present invention
The copolymer 1 of preparing take embodiment 1 is luminescent layer, is prepared with organic electroluminescence devices, and its structure as shown in Figure 2, comprises the glass substrate stacking gradually, transparent anode, luminescent layer, cathode buffer layer, negative electrode.Wherein, transparent anode be square resistance be 10-20 Ω/mouth tin indium oxide (ITO) (150nm), luminescent layer is copolymer 1 (90nm) prepared by the embodiment of the present invention 1, buffer layer is LiF (1.5nm), negative electrode is metal A l (150nm), the structure of device is: ITO/PEDOT:PSS/ copolymer 1/LiF/Al, but the structure of practical devices is not limited to this.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley2400Sourcemeter), 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 13.8cd/A, and high-high brightness is 1220cd/m
2.
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. containing selenophen bithiophene-benzo two (diazosulfide) multipolymer, it is characterized in that, described multipolymer has the structure of formula (I),
Wherein, R
1, R
2identical or different, be selected from C
1～C
20alkyl; R
3, R
4identical or different, be selected from H or C
1～C
20alkyl; N is the integer of 1-100.
2. according to claim 1 containing selenophen bithiophene-benzo two (diazosulfide) multipolymer, it is characterized in that described R
1, R
2, R
3, R
4be selected from C
1～C
10alkyl; N is 25～76 integer.
3. containing a preparation method for selenophen bithiophene-benzo two (diazosulfide) multipolymer, it is characterized in that, comprise the following steps:
(1), in inert gas environment, by structural formula be
4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, structural formula be
acetylene compound, the first catalyzer and alkali join in the first solvent, 130 ℃ reaction 4h, obtain compound 3, the structural formula of described compound 3 is:
described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are 1: 2 with the mole dosage ratio of acetylene compound, and described alkali is 1: 1 with the mole dosage ratio of acetylene compound;
(2), in inert gas environment, compound 4 is joined in the second solvent, add butyllithium reaction 1-2h at-78 ℃, then add SnBu at-78 ℃
3after Cl reaction 1h, be warming up to room temperature, after reaction 6h, obtain compound 5 through neutral alumina column chromatography; The structural formula of described compound 4 is:
the structural formula of described compound 5 is:
described compound 4 is 1: 2 with the mole dosage ratio of butyllithium, described SnBu
3the mole dosage of Cl is 2 times of compound 4;
(3), in inert gas environment, compound 3, compound 5, the second catalyzer are added in the 3rd solvent, 50-120 ℃ of reaction 6～100 hours, obtains containing selenophen bithiophene-benzo two (diazosulfide) multipolymer; Described compound 3 is 1: 1.5～1.5: 1 with the mole dosage ratio of compound 5;
In above-mentioned corresponding formula, R
1, R
2identical or different, be selected from C
1～C
20alkyl; R
3, R
4identical or different, be selected from H or C
1～C
20alkyl; N is the integer of 1-100.
4. the preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer according to claim 3, is characterized in that, in step (1), described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide is to adopt following steps to make:
By structural formula be
compd E add in thionyl chloride, stir and drip pyridine in thionyl chloride, back flow reaction at 85 ℃, makes structural formula and is
compound F 17-hydroxy-corticosterone;
Compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, and at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, and obtains structural formula and is
compound G;
Compound G is added in the DMF solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be
compound H;
Compound H is added to SnCl
2in the tetrahydrofuran solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, makes described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.
5. the preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer according to claim 3, is characterized in that, in step (1), described the first catalyzer is Pd (OAc)
2, the mole dosage of described the first catalyzer is 10% of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.
6. the preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer according to claim 3, is characterized in that, in step (3), described the second catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, the mole dosage of described the second catalyzer is the 0.05%-20% of compound 3.
7. the preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer according to claim 6, is characterized in that, in step (3), and described the second catalyst P d (PPh
3)
2cl
2.
8. the described preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer according to claim 3, is characterized in that, in step (1), described alkali is Bu
3n, described acetylene compound is 2,6,13,17-tetramethyl--9-octadecyne, 2,6-dimethyl-9-30 alkynes or valerylene.
9. the preparation method containing selenophen bithiophene-benzo two (diazosulfide) multipolymer according to claim 3, is characterized in that, described in step (1), the first solvent is DMF; Described in step (2), the second solvent is tetrahydrofuran (THF); Described in step (3), the 3rd solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
Described in claim 1 or 2 containing the application of selenophen bithiophene-benzo two (diazosulfide) multipolymer in solar cell, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or organic laser field.
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|---|---|---|---|
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