CN102329415A - Porphyrin-quinoxaline copolymer containing carbazole, preparation method thereof and application thereof - Google Patents
Porphyrin-quinoxaline copolymer containing carbazole, preparation method thereof and application thereof Download PDFInfo
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- CN102329415A CN102329415A CN201010226058XA CN201010226058A CN102329415A CN 102329415 A CN102329415 A CN 102329415A CN 201010226058X A CN201010226058X A CN 201010226058XA CN 201010226058 A CN201010226058 A CN 201010226058A CN 102329415 A CN102329415 A CN 102329415A
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- 0 CC(*)(*)C([C@@]1NC(C(c2ccc(c3ccccc3[n]3*)c3c2)=C2N=C3C=C2)=CC1)=C(C=C1)N=C1C([C@]1C=C2N(*)c(cccc4)c4C2=CC1)=C(C=C1)NC1=C3c1c2nc(-c3ccccc3)c(-c3c(C4*)cccc3)nc2c4cc1 Chemical compound CC(*)(*)C([C@@]1NC(C(c2ccc(c3ccccc3[n]3*)c3c2)=C2N=C3C=C2)=CC1)=C(C=C1)N=C1C([C@]1C=C2N(*)c(cccc4)c4C2=CC1)=C(C=C1)NC1=C3c1c2nc(-c3ccccc3)c(-c3c(C4*)cccc3)nc2c4cc1 0.000 description 2
- LELMSURPXIAXOW-UHFFFAOYSA-N Brc(c1c2nc(-c3ccccc3)c(-c3ccccc3)n1)ccc2Br Chemical compound Brc(c1c2nc(-c3ccccc3)c(-c3ccccc3)n1)ccc2Br LELMSURPXIAXOW-UHFFFAOYSA-N 0.000 description 1
- VPMJBJSLTPBZLR-UHFFFAOYSA-N Nc(c(N)c(cc1)Br)c1Br Chemical compound Nc(c(N)c(cc1)Br)c1Br VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a porphyrin-quinoxaline copolymer containing carbazole, a preparation method thereof and an application thereof. The structural formula of the copolymer is shown in the specification. In the structural formula, n is an integer between 1 and 100, and R1 and R2 are hydrogen or C1-C32 alkyl. The porphyrin-quinoxaline copolymer containing carbazole, which has the advantages of good dissolvability, wide spectral absorption range and high energy conversion efficiency, can be applied to fields of organic solar cell devices, organic electroluminescent devices, organic field effect transistor devices and the like as an organic semiconductor material.
Description
[technical field]
The present invention relates to the organic semiconductor material field, relate in particular to a kind of carbazole porphyrin-quinoxaline multipolymer that contains.
[background technology]
Utilize cheap material preparation low cost, dynamical solar cell is photovoltaic hot research fields and difficult point always.Polymer materials is on the one hand because the environmental stability of organic materials is good, preparation cost is low, function is easy to modulation, snappiness and good film-forming property; On the other hand because the organic solar batteries course of processing is simple relatively, but cold operation, and advantage such as the element manufacturing cost is also lower and receiving much concern becomes cheap and attractive solar cell material.
The porphyrin molecule is the general name that on porphin ring, is connected with substituent one type of macrocylc compound, and porphines is by four pyrrole rings and four the big ring delocalized of Dan Shuanjian alternative two dimensional structure conjugated systems that the methyne bridging gets up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electron resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, porphyrin class organic semiconductor material is one type of up-and-coming material, and its application in the photovoltaic field has obtained broad research.
Carbazole is one type of good cavity transport material: on the one hand, because the pi-conjugated effect of p-, the N atom on the carbazole is supplied with two keys with unshared-electron, makes two key electron riches; On the other hand, the N atom of parent electricity absorbs the electronics on two keys through inductive effect again, and wherein conjugative effect is greater than inductive effect, so carbazole has very strong cavity transmission ability, and this just makes it that very big potential using value is arranged aspect organic semiconductor material.
Yet the effciency of energy transfer of traditional organic semiconductor material that contains carbazole or porphyrin is lower, big limitations the range of application of this type material.
[summary of the invention]
Based on this, be necessary to provide a kind of effciency of energy transfer higher contain carbazole porphyrin-quinoxaline multipolymer.
A kind of carbazole porphyrin-quinoxaline multipolymer that contains has following structural formula (III):
Wherein, n is 1～100 a integer; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
Through introduce increasing the group of solubility, alkyl for example can improve the solubility and the film-forming properties of polymer materials and the extinction scope of adjustable carbazole porphyrin.Therefore, the above-mentioned carbazole porphyrin-quinoxaline multipolymer that contains has good solubility, lower energy gap, the spectral absorption scope of broad, helps current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
A kind of preparation method who contains carbazole porphyrin-quinoxaline multipolymer; Be in oxygen-free environment; With 5,15-two bromo-10,20-alkyl carbazole porphyrin or derivatives thereof (I) carries out the Stille coupling reaction with two tributyl tin-quinoxalines (II) under catalyzer and solvent existence condition; Obtain containing carbazole porphyrin-quinoxaline multipolymer (III), reaction formula is following:
Wherein, n is 1～100 a integer; R
1And R
2Identical or inequality, be hydrogen or C
1～C
32Alkyl.
Wherein, 5,15-two bromo-10,20-alkyl carbazole porphyrin (I) is 1: 1.5～1.5: 1 with the mol ratio of two tributyl tin-quinoxalines (II); Temperature of reaction is 50-130 ℃, and the time is 12～72 hours.
Wherein, catalyzer is the mixture of organic palladium and organophosphor ligand.
Wherein, organic palladium is Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2In at least a; Organophosphor ligand is tricyclohexyl phosphine or P (o-Tol)
3In at least a; The mol ratio of organic palladium and organophosphor ligand is 1: 2～1: 20.
Wherein, the molar weight of catalyzer be two tributyl tin-quinoxalines (II) molar weight 0.05%～30%.
Wherein, solvent is at least a in benzene, toluene, glycol dimethyl ether, the THF.
Above-mentioned preparation method utilizes the Stille reaction principle, and technology is simple, low for equipment requirements.
A kind of organic solar batteries device; Comprise glass baseplate successively, be located at conductive layer on the glass baseplate, be coated in and gather (3 on the conductive layer; The 4-Ethylenedioxy Thiophene): gather (styrene sulfonic acid) layer, be coated in and gather (3, the 4-Ethylenedioxy Thiophene): gather active coating on (styrene sulfonic acid) layer, be deposited on the metal Al layer on the active coating and be used to encapsulate the epoxy resin of above-mentioned each layer.Active coating comprises electron donor material and electron acceptor material.Electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate.Electron donor material is the aforesaid carbazole porphyrin-quinoxaline multipolymer that contains.
A kind of organic electroluminescence device comprises glass baseplate successively, is located at conductive layer on the glass baseplate, is coated in luminescent layer on the conductive layer, vapor deposition is at the LiF impact plies on the luminescent layer and be deposited on the metal Al layer on the LiF impact plies.Luminescent layer is the aforesaid carbazole porphyrin-quinoxaline multipolymer that contains.
A kind of organic field effect tube device comprises the doped silicon wafer base material successively, is located at the SiO of doped silicon wafer substrate surface
2Insulation layer, be coated in said SiO
2The octadecyl trichlorosilane decorative layer on surface, be coated in the organic semiconductor layer on the octadecyl trichlorosilane decorative layer and the source electrode and the drain electrode of organic semiconductor layer surface are set.Organic semiconductor layer is the aforesaid carbazole porphyrin-quinoxaline multipolymer that contains.
Above-mentioned polymer materials is high, easy to utilize as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation.
[description of drawings]
Fig. 1 is the structural representation of the organic solar batteries device that contains carbazole porphyrin-quinoxaline multipolymer of an embodiment.
Fig. 2 be an embodiment contain the structural representation of carbazole porphyrin-quinoxaline multipolymer as the organic electroluminescence device of luminescent layer.
Fig. 3 be an embodiment contain the structural representation of carbazole porphyrin-quinoxaline multipolymer as the organic field effect tube of organic semiconductor layer.
[embodiment]
Mainly combine below accompanying drawing and embodiment to this embodiment contain carbazole porphyrin-quinoxaline multipolymer and its production and application be further described.
Carbazole porphyrin-quinoxaline the multipolymer that contains of this embodiment has following structural formula (III):
Wherein, n is the integer between 1～100; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
Through introduce increasing the group of solubility, alkyl for example can improve the solubility and the film-forming properties of polymer materials and the extinction scope of adjustable carbazole porphyrin.Therefore, the above-mentioned carbazole porphyrin-quinoxaline multipolymer that contains has good solubility, lower energy gap, the spectral absorption scope of broad, helps current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
The above-mentioned preparation process that contains carbazole porphyrin-quinoxaline multipolymer comprises the steps:
Step S1: following structural formula (I) and raw materials of compound (II) are provided:
Wherein, R
1And R
2Be hydrogen or C
1～C
32Alkyl;
Step S2: in oxygen-free environment (oxygen-free environment of the present invention is made up of nitrogen and/or rare gas element); With structural formula (I) and (II) compound under catalyzer and solvent existence condition; Raw material is that 1: 1.5～1.5: 1 ratio is carried out the Stille coupling reaction in molar ratio under 50～130 ℃ of conditions, reacts obtained having structural formula in 12～72 hours multipolymer of (III);
Reaction formula is:
Catalyzer can be the mixture of organic palladium or organic palladium and organophosphorus ligand.Catalyst consumption be structural formula (II) the compound molar weight 0.05%～30%.Wherein, organic palladium is Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2Organophosphorus ligand is tricyclohexyl phosphine or P (o-Tol)
3In at least a.When catalyzer was the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand was 1: 2～20.
Preferably, solvent is at least a in THF, glycol dimethyl ether, benzene or the toluene.
After the crude product in solution that obtains the Stille coupled reaction, also need carry out sedimentation, drying treatment to crude product in solution: at first, drips of solution is added in the methyl alcohol, carries out sedimentation and handle, suction filtration then, methanol wash, drying must contain assorted copolymer colloid; With the toluene dissolving, get the toluene solution of multipolymer subsequently; Then, this toluene solution is joined in the aqueous solution of Thiocarb, 90 ℃ of heated and stirred mixed solutions with the column chromatography of mixed solution through aluminum oxide, are isolated multipolymer, chlorobenzene drip washing then, and organic solvent is removed in decompression subsequently; Repeat above-mentioned sedimentation treatment step, and extract multipolymer, obtain copolymer solids with acetone Suo Shi.
Above-mentioned preparation method utilizes the Stille reaction principle, and technology is simple, low for equipment requirements.
Further specify the above-mentioned carbazole porphyrin-quinoxaline multipolymer that contains through specific embodiment below.
Embodiment 1
Present embodiment disclose a kind of structure following 10,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer:
The preparation process of above-mentioned multipolymer is following:
Step S11, synthetic 5,8-two bromo-2, two (phenyl) quinoxalines of 3-, reaction formula is following:
120 ℃ with 3, (1.01g, (0.39g is in acetic acid soln 1.8mmol) 3.7mmol) to join the 20ml diphenylthanedione for 6-two bromo-O-Phenylene Diamines.Backflow is spent the night, and reaction solution is poured in the water, is neutralized to neutrality with sodium hydrogencarbonate.Chloroform extraction, saturated common salt water washing, anhydrous sodium sulfate drying.Rotary evaporation removes and desolvates, and thick product column chromatography gets white solid.Be to obtain the white solid powder then with chloroform/normal hexane recrystallization.The productive rate 86% of above-mentioned reaction.
Step S12, synthetic 5,8-two (tributyl tin)-2, two (phenyl) quinoxalines of 3-, reaction formula is following:
In the 500ml there-necked flask, add 5,8-two bromo-2, (1.32g, 3mmol), the 300ml THF is cooled to system-30 ℃ to two (phenyl) quinoxalines of 3-, drips the n-Butyl Lithium 2.5ml of 2.5mol/L, then at-30 ℃ of reactions 1h, property adding SnBu again
3(2.08g 6.4mmol), at-30 ℃ of reaction 30min, is warming up to room temperature to Cl then naturally, and stirring reaction spends the night.Reactant is poured in the frozen water, used extracted with diethyl ether, anhydrous magnesium sulfate drying, underpressure distillation removes and desolvates, and carries out column chromatography for separation with silica gel/sherwood oil (30～60 ℃), obtains product, productive rate 89.0%.
Step S13, synthetic 5,15-two (9-octyl group carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, (0.31g, 1mmol) (0.15g 1mmol), is dissolved in the 250ml methylene dichloride with two pyrroles's methane to take by weighing midbody 2-aldehyde-9-octyl group carbazole.Feed nitrogen 30min, use syringe to add propionic acid 1ml, 20 ℃ are stirred 24h down, and (0.91g 4mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then.Add the 1ml triethylamine then and carry out the cancellation reaction, concentrated solvent filters, and collects filtrating and revolves dried solvent, with methylene dichloride drip washing fast on silicagel column, revolves dried solvent, and to product, productive rate is about 86.4% with ether/recrystallizing methanol.
Step S14, synthetic 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, take by weighing 5, (0.17g 0.2mmol) is dissolved in the 80ml chloroform 15-two (9-octyl group carbazole) porphyrin; Add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g; 0.4mmol), behind the stirring 72h, mixture returns to room temperature.Continue to stir 4h then, add 5ml acetone termination reaction, remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product 0.18g, productive rate 88.2%.
Step S15, synthetic 10,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer, reaction formula is following:
Under nitrogen protection, add 5,8-two (tributyl tin)-2, two (phenyl) quinoxaline (172mg of 3-; 0.2mmol), 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin (204mg; 0.2mmol) and toluene solvant 80ml, vacuumize deoxygenation and charge into nitrogen, add 5mg Pd (PPh then
3)
2Cl
2, be heated to 100 ℃ of reaction 56h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 80.1%.Molecular weight (GPC, THF, R.I): M
n=38100, M
w/ M
n=3.37.
Embodiment 2
Present embodiment discloses the following 10-of a kind of structure (9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin quinoxaline multipolymer:
The preparation process of above-mentioned multipolymer is following:
Step S21, synthetic 5,8-two (tributyl tin)-2, two (phenyl) quinoxalines of 3-.
Its preparation method is with step S11, the step S 12 of embodiment 1.
Step S22, synthetic 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, take by weighing midbody 2-aldehyde-9-methyl carbazole (0.21g, 1mmol), 2-aldehyde-9-dotriacontyl carbazole (0.65g, 1mmol), (0.30g 2mmol), is dissolved in the 250ml methylene dichloride two pyrroles's methane.Feed nitrogen 30min, use syringe to add trifluoroacetic acid 2ml, 100 ℃ are stirred 1h down.(1.82g 8mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then.Add 2ml pyridine cancellation reaction then, concentrated solvent filters, and collects filtrating and revolves dried solvent, with methylene dichloride drip washing fast on silicagel column, revolves dried solvent, and to product, productive rate is about 74.3% with ether/recrystallizing methanol.
Step S23, synthetic 5,15-two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, (0.22g 0.2mmol) is dissolved in the 80ml chloroform, adds the 1ml pyridine, and reactant is dropped to 0 ℃ to take by weighing 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin.(0.07g, 0.4mmol), behind the stirring 0.5h, mixture is warming up to 120 ℃, after continuing then to stir 1h, adds 5ml acetone termination reaction, removes and desolvates, and carries out recrystallization with ether/methyl alcohol and obtains product, productive rate 83.3% to add the N-bromo-succinimide.
Step S24, synthetic 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin quinoxaline multipolymer, reaction formula is following:
Mixed gas protected down at nitrogen and argon gas, add 5,8-two (tributyl tin)-2; Two (phenyl) quinoxaline (172mg of 3-; 0.2mmol), 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin (252mg; 0.2mmol) and toluene solvant 80ml, vacuumize deoxygenation and charge into nitrogen and the argon gas mixed gas.Add Pd (OAc) then
2(2.5mg)/tricyclohexyl phosphine (6.5mg) and 2ml 20% (wt) Et
4NOH solution is heated to 120 ℃ of reaction 24h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 78.3%.Molecular weight (GPC, THF, R.I): M
n=34100, M
w/ M
n=3.64.
Embodiment 3
Present embodiment discloses the following 10-carbazole-20-of a kind of structure (9-hexadecyl carbazole) porphyrin quinoxaline multipolymer:
The preparation process of above-mentioned multipolymer is following:
Step S31, synthetic 5,8-two (tributyl tin)-2, two (phenyl) quinoxalines of 3-.
Its preparation is with embodiment 1 step S11, S12.
Step S32, synthetic 5-carbazole-15-(9-hexadecyl carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, take by weighing midbody 2-aldehyde carbazole (0.20g, 1mmol), 2 aldehyde-9-hexadecyl carbazole (0.42g, 1mmol), (0.30g 2mmol), is dissolved in the 300ml methylene dichloride two pyrroles's methane.Feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stirs 3h under the room temperature, adds DDQ (DDQ) (1.82g then; 8mmol), continue at room temperature to stir 30min, add the 2ml triethylamine then and carry out cancellation reaction, concentrated solvent; Filter, collect filtrating and revolve dried solvent, with methylene dichloride drip washing fast on silicagel column; Revolve dried solvent, to product, productive rate is about 86.8% with ether/recrystallizing methanol.
Step S33, synthetic 5,15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin, reaction formula is following:
Put up the anhydrous and oxygen-free device, (0.17g 0.2mmol) is dissolved in the 80ml chloroform, adds the 1ml pyridine, and reactant is dropped to 0 ℃ to take by weighing 5-carbazole-15-(9-hexadecyl carbazole) porphyrin.(0.07g, 0.4mmol), behind the stirring 0.5h, mixture is warming up to 30 ℃, continues to stir 48h then, adds 5ml acetone termination reaction, removes and desolvates, and carries out recrystallization with ether/methyl alcohol and obtains product, productive rate 78.2% to add the N-bromo-succinimide.
Step S34, synthetic 10-carbazole-20-(9-hexadecyl carbazole) porphyrin quinoxaline multipolymer, reaction formula is following:
Under argon shield, add 5,8-two (tributyl tin)-2; Two (phenyl) quinoxalines of 3-(172mg, 0.2mmol), 5,15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin (205mg; 0.2mmol) and toluene solvant 100ml, vacuumize deoxygenation and charge into argon gas.Add 8mg Pd (PPh then
3)
4, be heated to 50 ℃ of reaction 72h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 300ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 73.9%.Molecular weight (GPC, THF, R.I): M
n=35200, M
w/ M
n=3.38.
Embodiment 4
With 10 of embodiment 1,20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer is as the organic solar batteries device of active layer material, and its structure is as shown in Figure 1.
Active layer material comprises above-mentioned multipolymer as electron donor material, [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM) is as electron acceptor material; Be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ITO is that square resistance is the tin indium oxide of 10-20 Ω/, and PEDOT is for gathering (3; The 4-Ethylenedioxy Thiophene), PSS is for gathering (styrene sulfonic acid); Ito glass is through after the ultrasonic cleaning; Handle with oxygen-Plasma; On ITO, coat PEDOT:PSS; Active coating adopts spin coating technique as electron donor material and PCBM as electron acceptor material with multipolymer of the present invention, and metal aluminium electrode obtains the organic solar batteries device through the vacuum evaporation technology preparation.With device with epoxy encapsulation after, place under 110 ℃ of air tight conditions annealing 4 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved the transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Embodiment 5
With 10 of embodiment 1, porphyrin-quinoxaline multipolymer is as the luminescent layer organic electroluminescence device for 20-two (9-octyl group carbazole), and its structure is as shown in Figure 2.
This device is followed successively by glass/ITO/ multipolymer/LiF/Al of the present invention; Promptly deposition one deck square resistance is that the tin indium oxide (ITO) of 10-20 Ω/mouth is as transparent anode on a glass substrate; On ITO, prepare one deck copolymer material of the present invention as luminescent layer through spin coating technique, vacuum evaporation LiF on this luminescent layer again is as impact plies; On impact plies, adopt vacuum coating technology metal refining Al at last, as the negative electrode of device.
Embodiment 6
Containing 10 of embodiment 1, the organic field effect tube of 20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer, its structure is as shown in Figure 3.
Adopt highly doped silicon chip (Si) as substrate, the SiO that 450nm is thick
2As insulation layer, source electrode (S) and drain electrode (D) all adopt gold or copper as electrode, and multipolymer of the present invention is spun to the SiO after octadecyl trichlorosilane (OTS) is modified as organic semiconductor layer
2On, contain 10 thereby make, the organic field effect tube of 20-two (9-octyl group carbazole) porphyrin-quinoxaline multipolymer.
High, easy to utilize with above-mentioned polymer materials as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation.
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.
Claims (10)
1. one kind contains carbazole porphyrin-quinoxaline multipolymer, it is characterized in that, has following structural formula (III):
Wherein, n is 1～100 a integer; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
2. preparation method who contains carbazole porphyrin-quinoxaline multipolymer; It is characterized in that, be in oxygen-free environment, with 5; 15-two bromo-10; 20-alkyl carbazole porphyrin or derivatives thereof (I) carries out the Stille coupling reaction with two tributyl tin-quinoxalines (II) under catalyzer and solvent existence condition, obtain containing carbazole porphyrin-quinoxaline multipolymer (III), and reaction formula is following:
Wherein, n is 1～100 a integer; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
3. the preparation method who contains carbazole porphyrin-quinoxaline multipolymer according to claim 2 is characterized in that: said 5, and 15-two bromo-10,20-alkyl carbazole porphyrin (I) is 1: 1.5～1.5: 1 with the mol ratio of said pair of tributyl tin-quinoxaline (II); Said Stille coupling reaction temperature is 50-130 ℃, and the reaction times is 12～72 hours.
4. the preparation method who contains carbazole porphyrin-quinoxaline multipolymer according to claim 2 is characterized in that: said catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand.
5. the preparation method who contains carbazole porphyrin-quinoxaline multipolymer according to claim 4 is characterized in that: said organic palladium is Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2In at least a; Said organophosphor ligand is tricyclohexyl phosphine or P (o-Tol)
3In at least a; The mol ratio of said organic palladium and said organophosphor ligand is 1: 2～1: 20.
6. according to claim 2 or the 4 or 5 described preparing methods that contain carbazole porphyrin-quinoxaline multipolymer, it is characterized in that: the molar weight of said catalyzer be said pair of tributyl tin-quinoxaline (II) molar weight 0.05%～30%.
7. the preparation method who contains carbazole porphyrin-quinoxaline multipolymer according to claim 2 is characterized in that: said solvent is at least a in benzene, toluene, glycol dimethyl ether, the THF.
8. organic solar batteries device; Comprise glass baseplate successively, be located at conductive layer on the said glass baseplate, be coated in and gather (3 on the said conductive layer; The 4-Ethylenedioxy Thiophene): gather (styrene sulfonic acid) layer, be coated in and saidly gather (3; The 4-Ethylenedioxy Thiophene): gather active coating on (styrene sulfonic acid) layer, be deposited on the metal Al layer on the said active coating and be used to encapsulate the epoxy resin of above-mentioned each layer; Said active coating comprises electron donor material and electron acceptor material, and said electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate is characterized in that, said electron donor material contains carbazole porphyrin-quinoxaline multipolymer for what have a structural formula (III):
Wherein, n is 1～100 a integer; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
9. organic electroluminescence device; Comprise glass baseplate successively, be located at conductive layer on the said glass baseplate, be coated in luminescent layer on the said conductive layer, vapor deposition is at the LiF impact plies on the said luminescent layer and be deposited on the metal Al layer on the said LiF impact plies; It is characterized in that said luminescent layer contains carbazole porphyrin-quinoxaline multipolymer for what have a structural formula (III):
Wherein, n is 1～100 a integer; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
10. organic field effect tube device comprises the doped silicon wafer base material successively, is located at the SiO of said doped silicon wafer substrate surface
2Insulation layer, be coated in said SiO
2The octadecyl trichlorosilane decorative layer on surface, be coated in the organic semiconductor layer on the said octadecyl trichlorosilane decorative layer and the source electrode and the drain electrode of organic semiconductor layer surface are set; It is characterized in that said organic semiconductor layer contains carbazole porphyrin-quinoxaline multipolymer for what have a structural formula (III):
Wherein, n is 1～100 a integer; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617833A (en) * | 2012-03-22 | 2012-08-01 | 北京化工大学 | Quinoxaline porphyrin unit based conjugated polymer as well as preparation method and application thereof |
| CN105431467A (en) * | 2013-07-31 | 2016-03-23 | 株式会社Lg化学 | Copolymer and organic solar cell comprising same |
| CN108530609A (en) * | 2018-03-22 | 2018-09-14 | 南京邮电大学 | The preparation and application of porphyrin polymer and synthetic method and memristor and memristor |
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|---|---|---|---|---|
| CN1887033A (en) * | 2003-10-31 | 2006-12-27 | 日产化学工业株式会社 | Charge-transporting organic material containing compound having 1,4-dithiin ring |
| US7300731B2 (en) * | 2004-08-10 | 2007-11-27 | E.I. Du Pont De Nemours And Company | Spatially-doped charge transport layers |
| CN101208815A (en) * | 2005-03-04 | 2008-06-25 | 赫里亚泰克有限责任公司 | Organic photoactive component |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887033A (en) * | 2003-10-31 | 2006-12-27 | 日产化学工业株式会社 | Charge-transporting organic material containing compound having 1,4-dithiin ring |
| US7300731B2 (en) * | 2004-08-10 | 2007-11-27 | E.I. Du Pont De Nemours And Company | Spatially-doped charge transport layers |
| CN101208815A (en) * | 2005-03-04 | 2008-06-25 | 赫里亚泰克有限责任公司 | Organic photoactive component |
Non-Patent Citations (1)
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| FLORENCE SZYDLO, ET AL.: "Facile Preparation of Doubly Dipyrrolylquinoxaline-Bridged Expanded Porphyrins. Synthesis and Structural Characterization of an Unprecedented [20]Tetraphyrin-(2.1.2.1)", 《ORGANIC LETTERS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617833A (en) * | 2012-03-22 | 2012-08-01 | 北京化工大学 | Quinoxaline porphyrin unit based conjugated polymer as well as preparation method and application thereof |
| CN102617833B (en) * | 2012-03-22 | 2014-01-22 | 北京化工大学 | Quinoxaline porphyrin unit based conjugated polymer as well as preparation method and application thereof |
| CN105431467A (en) * | 2013-07-31 | 2016-03-23 | 株式会社Lg化学 | Copolymer and organic solar cell comprising same |
| CN108530609A (en) * | 2018-03-22 | 2018-09-14 | 南京邮电大学 | The preparation and application of porphyrin polymer and synthetic method and memristor and memristor |
| CN108530609B (en) * | 2018-03-22 | 2020-08-14 | 南京邮电大学 | Porphyrin polymer and synthesis method thereof, memristor and preparation and application of memristor |
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| CN102329415B (en) | 2013-04-17 |
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