CN104744676B - Conjugated polymer containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline and application - Google Patents

Conjugated polymer containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline and application Download PDF

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CN104744676B
CN104744676B CN201510147716.9A CN201510147716A CN104744676B CN 104744676 B CN104744676 B CN 104744676B CN 201510147716 A CN201510147716 A CN 201510147716A CN 104744676 B CN104744676 B CN 104744676B
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diketone
polymer
quinoxaline
pyrrolo
thiophene
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CN104744676A (en
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黄飞
兰柳元
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a kind of contain 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer of 8-diketone and application, its structural formula is as follows；Copolymer prepared by the present invention, with fluorescence, has wide absorption to sunlight, therefore can be applicable to make polymer LED device, and the active layer of polymer field effect transistor and polymer solar battery.

Description

Conjugated polymer containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline and application
Technical field
The present invention relates to a kind of new polymer for being applied to photoelectron material and devices field, more particularly to containing 7H-pyrrole Cough up the simultaneously Optical Properties of Novel Conjugated of [3,4-g]-6,8-diketone of quinoxaline and its preparation and application.
Background technology
In past ten years, organic sun hull cell is very burning hot, and the efficiency of organic thin film cells is also hit new peak frequently, Single layer device peak efficiency has broken through 10% at present, and market-oriented prospect is very bright.In order to obtain the efficient polymer sun Energy battery device, material is one of most important factor.In general, a preferable material will have wide absorption, it is high Carrier mobility, suitable energy level.So this is accomplished by us carries out the innovation of material, develop more new conjugation and gather Compound material.In numerous photoelectric materials, the photoelectricity containing quinoxaline group or imide group (such as benzo acid imide) Material is in organic electroluminescent, organic solar batteries, chemistry and the material such as biosensor and organic field effect tube In be widely used.Due to the modifiability of benzo imide group N atoms, therefore difference can be connected with N atoms The alkyl chain of shape and length carries out solubilising to which, so as to improve the dissolubility and machinability of corresponding photoelectric material.However, benzene And acid imide this chemical functional group also has its limitation, it is not very strong to essentially consist in electron-withdrawing power, with other aromatic groups After copolymerization, it is difficult to form the wide polymer for absorbing.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, in order to further improve the unit material of acid imide containing benzo Photoelectric properties, benzo acid imide and quinoxaline be combined together by this patent, there is provided a class novel condensed ring photoelectric material：7H– Pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.The conjugated polymer has fluorescence, has wide absorption to sunlight.
Another object of the present invention is to provide the described conjugation containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline The preparation method of polymer.
It is still another object of the present invention to provide the described conjugation containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline Application of the polymer in polymer LED, polymer field effect transistor and polymer solar battery.
The purpose of the present invention is achieved through the following technical solutions：
Containing 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer of 8-diketone, its structural formula is：
Wherein, R1、R2And R3For hydrogen atom or alkyl chain；The alkyl chain is the straight chain with 1～24 carbon atom, props up Chain or cyclic alkyl chain, or wherein one or more carbon atoms are by oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl Base, carboxyl, ester group, cyano group or nitro replace, and hydrogen atom is replaced by halogen atom or above-mentioned functional group；Ar is aromatic group；Institute State the natural number that n is 1～10000,0 ＜ x ＜, 1,0 ＜ y ＜ 1, x+y=1.X, y are respectively 7H-pyrrole in described conjugated polymer Cough up the relative amount of simultaneously [3,4-g]-6,8-dione unit of quinoxaline and aromatic group Ar；Aromatic group Ar and 7H-pyrrolo- [3, 4-g] quinoxaline-6,8-diketone with conjugated manner be connected, n is the degree of polymerization of the conjugated polymer.
The aromatic group Ar is as follows one or more of structure：
Wherein, R, Ra～RdFor hydrogen atom or alkyl chain.Described R, Ra～RdBe the straight chain with 1～24 carbon atom, Side chain or cyclic alkyl chain, or wherein one or more carbon atoms are by oxygen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl Base, carboxyl, ester group, cyano group or nitro replace, and hydrogen atom is replaced by halogen atom or above-mentioned functional group.
Described conjugated polymer is preparing the luminescent layer of polymer LED device, is preparing polymer field effect crystalline substance Semiconductor active layer in body pipe or the application in preparing the active layer of polymer solar photovoltaic cell.
The present invention by select various conjugation fragrant monomers respectively with containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline Monomer carry out Still and be coupled copolymerization, obtain containing 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer of 8-diketone.
The conjugated polymer containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline of the present invention can be adopted and be made with the following method It is standby：
(1) with 4,7-two (- 2-yl of thiophene)-1,2,5-diazosulfide-N-R1- 5,6-dicarboxylic acids of base acid imide is mother Body, is reacted by iron powder reducing, obtains 4,7-two (- 2-yls of thiophene)-5,6-diaminourea-N-R1Base-iso-indoles-1,3-diketone, Again this monomer and even acyl class compound are carried out dehydration condensation and synthesize 5,9-two (- 2-yl of thiophene)-7-R1- 2-R of base2Base- 3–R3Base-7H-pyrrolo- [3,4-g] quinoxaline-6,8-diketone, finally by NBS brominations obtain final monomer 5,9-two (5- Bromo--2-yl of thiophene)-7-R1- 2-R of base2- 3-R of base3Base-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.
(2) metal catalyzed coupling reaction：By the monomer with metal catalyzed coupling reaction active function groups containing Ar structures React under metallic catalyst with the brominated product in step (1), obtain the structure containing Ar and 7H-pyrrolo- of just one-step functional The conjugated polymer of [3,4-g]-6,8-diketone of quinoxaline.
7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline can be made by the regulation of Ar structures conversion in step (2) Derivant has good solution processability and photoelectric properties, finally successfully by 7H-pyrrolo- [3,4-g] quinoxaline-6,8-two Ketone structure is incorporated in polymer, is prepared series and is contained 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer of 8-diketone.
The structure of small molecule and polymeric material is characterized by nuclear magnetic resonance, NMR (NMR) and gel chromatography (GPC), by purple The spectral quality of outer visible spectrophotometer test polymer material, while obtained polymer is prepared into photoelectric device characterizes it Photoelectric properties.
Compare with traditional benzo acid imide, 7H-pyrrolo- [3,4-g] quinoxaline-6 of the present invention, the electrophilic of 8-diketone Ability is significantly improved, and is expected to develop the more preferable narrow band gap solar cell material of performance.It is expected that containing 7H-pyrrole Simultaneously [3,4-g] quinoxaline-6 are coughed up, the conjugated polymer material of 8-diketone has good photoelectric properties, be that a class has commercialization The material of application prospect.
The structural formula of benzo acid imide and 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline is as follows：
Conjugated polymer material based on 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline is used as the promising light of a class In the field, someone does not report electric material so far.The present invention has synthesized first containing 7H-pyrrolo- [3,4-g] quinoline The conjugated polymer of-6,8-diketone of quinoline is simultaneously successfully applied in photoelectric field.
Compared with prior art, the present invention has advantages below：
Containing 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer structure of 8-diketone is novel, with originality.Contain 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer of 8-diketone has several functions, with fluorescence, can apply to system Make the luminescent layer of polymer LED；With higher mobility, polymer field effect transistor is can apply to；To the sun Light has absorbability, can apply to the active layer of polymer solar cells, and relevant solar cell has higher energy conversion effect Rate.
Description of the drawings
Fig. 1 is absorption spectrogram of the polymer prepared by embodiment 4～7 in tetrahydrofuran solution；
Film absorption spectrograms of the Fig. 2 for polymer prepared by embodiment 4～7；
Fig. 3 is the J-V curve charts of device prepared by 4～7 resulting polymers of embodiment.
Specific embodiment
In order to be better understood from present disclosure, the technology of the present invention is further illustrated below by specific example Scheme, specifically includes synthesis, characterizes and device preparation, but not limited to this.
Embodiment 1
4,7-two (- 2-yl of thiophene)-5,6-diaminourea-N-R1Base-iso-indoles-1, the preparation of 3-diketone, reaction equation such as Formulas I It is shown：
(- 2-yl of thiophene)-1,2,5-diazosulfide-N-R 4,7-two in Formulas I1Base-5,6-dicarboxylic acids acid imide (a) Synthesis reference literature [Wang LX, Cai DD, Zheng QD, et al.ACS Macro Lett.2013,2,605-608].
Said as a example by preparing 4,7-two (- 2-yl of thiophene)-5,6-diaminourea-N-octyl group-- 1,3-diketone of iso-indoles It is bright.Add 4,7-two (- 2-yl of thiophene)-1,2,5-diazosulfide-N-- 5,6-dicarboxylic acids of octyl group acyl sub- in 50ml two-mouth bottles Amine (0.87g, 1.82mmol) and iron powder (1.22g, 21.8mmol), add and are stirred at reflux under 30ml glacial acetic acids, condition of nitrogen gas After 5h, reactant liquor is poured into water, separates out greenish yellow solid, filtered, take filtering residue, obtained with silica gel column chromatography chromatographic column separating-purifying (0.6g, yield is 73%) for yellow solid 4,7-two (- 2-yl of thiophene)-5,6-diaminourea-N-octyl group-- 1,3-diketone of iso-indoles.
1H NMR(300MHz,CDCl3)：δ=7.54 (d, 2H), δ=7.20 (t, 2H), δ=7.13 (d, 2H), δ=3.99 (s, 4H), δ=3.41 (t, 2H), δ=1.53 (m, 2H), δ=1.12-1.25 (m, 10H), δ=0.84 (t, 3H).
13C NMR(151MHz,CDCl3)δ167.71,138.53,133.19,128.57,127.60,127.54, 122.36,117.76,37.79,31.75,29.15,29.12,28.57,26.95,22.61,14.08.
To prepare 4,7-two (- 2-yl of thiophene)-5,6-diaminourea-N-- 1,3-diketone of (2-ethylhexyl)-iso-indoles it is again Example is explained.In 50ml two-mouth bottles add 4,7-two (- 2-yl of thiophene)-1,2,5-diazosulfide-N-(2-ethylhexyl)- 5,6-acid imide (0.6g, 1.25mmol) and iron powder (0.83g, 14.97mmol), add 30ml glacial acetic acids, under condition of nitrogen gas After being stirred at reflux 5h, reactant liquor is poured into water, separates out greenish yellow solid, filtered, take filtering residue, with silica gel column chromatography chromatograph post separation Purification obtains yellow solid 4,7-two (- 2-yl of thiophene)-5,6-diaminourea-N-- 1,3-diketone of (2-ethylhexyl)-iso-indoles (0.42g, yield is 75%).
1H NMR(300MHz,CDCl3)：δ=7.54 (d, 2H), δ=7.20 (t, 2H), δ=7.13 (d, 2H), δ=3.99 (s, 4H), δ=3.34 (d, 2H), δ=1.70 (m, 1H), δ=1.20-1.22 (m, 8H), δ=0.81 (m, 6H).
13C NMR(151MHz,CDCl3)δ167.98,138.56,133.26,128.55,127.63,127.56, 122.29,117.70,41.82,38.08,30.57,28.51,23.93,23.06,14.06,10.49.
4,7-two (- 2-yl of thiophene)-5,6-diaminourea-N-alkyl-- 1,3-diketone of iso-indoles is not limited only to this.
Embodiment 2
5,9-two (- 2-yl of thiophene)-7-R1- 2-R of base2- 3-R of base3Base-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline Preparation, reaction equation is as shown in Formula II：
To prepare 5,9-two (- 2-yl of thiophene)-7-octyl group-2,3-two (4- octyloxyphenyls)-7H-pyrrolo- [3,4-g] It is explained as a example by-6,8-diketone of quinoxaline.4,7-two (- 2-yl of thiophene)-5,6-diamino is separately added in 100ml two-mouth bottles Base-N-octyl group-- 1,3-diketone of iso-indoles (0.38g, 0.83mmol) and 1,2- bis- (4-octyloxyphenyl)-1,2-diketone of ethane (0.42g, 0.87mmol), adds after being stirred at reflux overnight under 45ml glacial acetic acids, condition of nitrogen gas, reactant liquor is poured into water, Extracted with dichloromethane.Anhydrous magnesium sulfate is dried organic faciess, filters, is spin-dried for organic faciess, then is carried with silica gel column chromatography chromatograph post separation It is pure to obtain orange solids 5,9-two (- 2-yl of thiophene)-7-octyl group-2,3-two (4-octyloxyphenyl)-7H-pyrrolo- [3,4-g] (0.63g, yield is 86%) for-6,8-diketone of quinoxaline.
1H NMR(300MHz,CDCl3)：δ=7.68-7.74 (m, 4H), δ=7.60 (d, 4H), δ=7.25 (t, 2H), δ =6.83 (d, 4H), δ=3.95 (t, 4H), δ=3.67 (t, 2H), δ=1.74 (m, 4H), δ=1.63 (m, 2H), δ=1.09- 1.25 (m, 30H), δ=0.83 (m, 9H).
13C NMR(151MHz,CDCl3)δ166.33,160.62,152.38,140.78,132.63,132.33, 131.85,131.17,130.08,130.00,126.74,126.03,114.32,68.10,38.68,31.81,31.77, 29.35,29.24,29.20,29.17,29.15,28.38,27.04,26.03,22.66,22.62,14.11,14.09.
Again with prepare 5,9-two (- 2-yl of thiophene)-7-octyl group-2,3-two (3- octyloxyphenyls)-7H-pyrrolo- [3,4- G] it is explained as a example by-6,8-diketone of quinoxaline.4,7-two (- 2-yl of thiophene)-5,6-diamino is separately added in 100ml two-mouth bottles Base-N-octyl group-- 1,3-diketone of iso-indoles (0.38g, 0.83mmol) and 1,2-two (3-octyloxyphenyl)-1,2-diketone of ethane (0.42g, 0.87mmol), adds after being stirred at reflux overnight under 45ml glacial acetic acids, condition of nitrogen gas, reactant liquor is poured into water, Extracted with dichloromethane.Anhydrous magnesium sulfate is dried organic faciess, filters, is spin-dried for organic faciess, then is carried with silica gel column chromatography chromatograph post separation It is pure to obtain orange solids 5,9-two (- 2-yl of thiophene)-7-octyl group-2,3-two (3-octyloxyphenyl)-7H-pyrrolo- [3,4-g] (0.66g, yield is 90%) for-6,8-diketone of quinoxaline.
1H NMR(300MHz,CDCl3)：δ=7.75 (d, 2H), δ=7.69 (d, 2H), δ=7.36 (s, 2H), δ=7.28 (t, 2H), δ=7.17 (m, 4H), δ=6.91 (d, 2H), δ=3.84 (t, 4H), δ=3.68 (t, 2H), δ=1.71 (m, 6H), δ=1.25-1.41 (m, 30H), δ=0.84 (m, 9H).
13C NMR(151MHz,CDCl3)δ166.18,159.09,152.76,140.99,138.84,132.79, 132.55,130.99,130.02,129.21,127.19,126.14,122.67,117.32,115.32,68.10,38.76, 31.85,31.77,29.34,29.30,29.16,29.15,29.13,28.36,27.04,26.05,22.70,22.62, 14.13,14.09.
Again preparing 5,9-two (- 2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (4- octyloxyphenyls)-7H-pyrroles And be explained as a example by [3,4-g]-6,8-diketone of quinoxaline.4,7-two (- 2-yls of thiophene)-5 are separately added in 50ml two-mouth bottles, 6-diaminourea-N-- 1,3-diketone of (2-ethylhexyl)-iso-indoles (0.26g, 0.57mmol) and 1,2-two (4-octyloxyphenyls) Ethane-1,2-diketone (0.25g, 0.54mmol) are added after being stirred at reflux overnight under 30ml glacial acetic acids, condition of nitrogen gas, will be anti- Answer liquid to be poured into water, extracted with dichloromethane.Anhydrous magnesium sulfate is dried organic faciess, filters, is spin-dried for organic faciess, then uses silica gel column chromatography Chromatographic column separating-purifying obtains-2,3-two (4-octyloxy benzene of orange solids 5,9-two (- 2-yl of thiophene)-7-(2-ethylhexyl) Base) (0.43g, yield is 86%) for-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.
1H NMR(300MHz,CDCl3)：δ=7.71-7.73 (m, 4H), δ=7.65 (d, 4H), δ=7.28 (t, 2H), δ =6.83 (d, 4H), δ=3.95 (t, 4H), δ=3.60 (d, 2H), δ=1.87 (m, 1H), δ=1.74 (m, 4H), δ=1.29- 1.45 (m, 28H), δ=0.87 (m, 12H).
13C NMR(151MHz,CDCl3)δ166.61,160.61,152.36,140.79,132.61,132.28, 131.84,131.22,130.09,129.97,126.68,126.07,114.32,68.10,42.67,38.03,31.81, 30.65,29.35,29.24,29.20,28.56,26.03,24.00,23.06,22.66,14.11,14.07,10.49.
Again preparing 5,9-two (- 2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (3- octyloxyphenyls)-7H-pyrroles And be explained as a example by [3,4-g]-6,8-diketone of quinoxaline.Be separately added in 100ml two-mouth bottles 4,7-two (- 2-yls of thiophene)- 5,6-diaminourea-N-- 1,3-diketone of (2-ethylhexyl)-iso-indoles (0.43g, 0.95mmol) and 1,2-two (3-octyloxy benzene Base) ethane-1,2-diketone (0.42g, 0.9mmol) added after being stirred at reflux overnight under 50ml glacial acetic acids, condition of nitrogen gas, will Reactant liquor is poured into water, and is extracted with dichloromethane.Anhydrous magnesium sulfate is dried organic faciess, filters, is spin-dried for organic faciess, then uses layer of silica gel Analysis chromatographic column separating-purifying obtains-7-(2-ethylhexyl)-2,3-two (3-octyloxy of orange solids 5,9-two (- 2-yl of thiophene) Phenyl) (0.74g, yield is 88%) for-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.
1H NMR(300MHz,CDCl3)：δ=7.75 (d, 2H), δ=7.69 (d, 2H), δ=7.36 (s, 2H), δ=7.28 (t, 2H), δ=7.15 (m, 4H), δ=6.91 (d, 2H), δ=3.85 (t, 4H), δ=3.62 (d, 2H), δ=1.88 (m, 1H), δ=1.71 (m, 4H), δ=1.30-1.42 (m, 28H), δ=0.88 (m, 12H).
13C NMR(151MHz,CDCl3)δ166.46,159.09,152.74,141.01,138.86,132.78, 132.51,131.05,129.99,129.20,127.13,126.17,122.68,117.31,115.33,68.11,42.74, 38.05,31.85,30.66,29.71,29.34,29.30,29.13,28.55,26.05,24.01,23.06,22.70, 14.13,14.07,10.49.
5,9-two (- 2-yl of thiophene)-7-R1- 2-R of base2- 3-R of base3Base-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline It is not limited only to this.
Embodiment 3
5,9-two (5-bromo--2-yl of thiophene)-7-R1- 2-R of base2- 3-R of base3Base-7H-pyrrolo- [3,4-g] quinoxaline-6, The preparation of 8-diketone, reaction equation is as shown in formula III：
With prepare 5,9-two (5-bromo--2-yl of thiophene)-7-octyl group-2,3-two (4- octyloxyphenyls)-7H-pyrrolo- [3, 4-g] it is explained as a example by-6,8-diketone of quinoxaline.5,9-two (- 2-yl of thiophene)-7-octyl group-2 are added in 100ml two-mouth bottles, 3-two (4- octyloxyphenyls)-7H-pyrrolo- [3,4-g] quinoxaline-6,8-diketone (0.63g, 0.71mmol) add 30ml Chloroform and 10ml glacial acetic acids stir.NBS (N-bromosuccinimide, N- bromo succinyl is added under condition of ice bath Imines) (0.31g, 1.71mmol), normal-temperature reaction 24h.Reactant liquor is poured into water, is extracted with dichloromethane.Anhydrous magnesium sulfate Be dried organic faciess, filter, be spin-dried for organic faciess, then with silica gel column chromatography chromatographic column separating-purifying obtain Orange red solid 5,9-two (5- Bromo--2-yl of thiophene)-7-octyl group-2,3-two (4- octyloxyphenyls)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.57g, yield is 77%).
1H NMR(300MHz,CDCl3)：δ=7.76 (d, 4H), δ=7.66 (d, 2H), δ=7.19 (d, 2H), δ=6.87 (d, 4H), δ=4.00 (t, 4H), δ=3.68 (t, 2H), δ=1.80 (m, 4H), δ=1.76 (m, 2H), δ=1.25-1.32 (m, 30H), δ=0.84 (m, 9H).
13C NMR(151MHz,CDCl3)δ166.16,160.83,152.84,140.23,133.36,132.43, 131.91,131.39,129.72,128.98,126.56,118.16,114.45,68.16,38.80,31.82,31.77, 29.36,29.24,29.21,29.16,29.14,28.35,27.02,26.04,22.67,22.62,14.11,14.08.
Again preparing 5,9-two (5-bromo--2-yl of thiophene)-7-octyl group-2,3-two (3- octyloxyphenyls)-7H-pyrrolo- It is explained as a example by [3,4-g]-6,8-diketone of quinoxaline.In 100ml two-mouth bottles add 5,9-two (- 2-yl of thiophene)-7-octyl group- 2,3-two (3- octyloxyphenyls)-7H-pyrrolo- [3,4-g] quinoxaline-6,8-diketone (0.66g, 0.75mmol) add 30ml chloroforms and 10ml glacial acetic acids stir.NBS (N-bromosuccinimide, N- bromo fourths are added under condition of ice bath Imidodicarbonic diamide) (0.32g, 1.8mmol), normal-temperature reaction 24h.Reactant liquor is poured into water, is extracted with dichloromethane.Anhydrous slufuric acid Magnesium is dried organic faciess, filters, is spin-dried for organic faciess, then obtains Orange red solid 5,9-two with silica gel column chromatography chromatographic column separating-purifying (5-bromo--2-yl of thiophene)-7-octyl group-2,3-two (3- octyloxyphenyls)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.57g, yield is 73%).
1H NMR(300MHz,CDCl3)：δ=7.65 (d, 2H), δ=7.53 (s, 2H), δ=7.16-7.22 (m, 4H), δ =7.06 (d, 2H), δ=6.98 (d, 2H), δ=3.98 (t, 4H), δ=3.70 (t, 2H), δ=1.70 (m, 6H), δ=1.25- 1.33 (m, 30H), δ=0.84 (m, 9H).
13C NMR(151MHz,CDCl3)δ166.03,159.45,153.07,140.21,138.47,133.68, 132.17,131.49,129.17,129.02,126.94,122.80,118.49,117.96,114.83,68.24,38.88, 31.86,31.77,29.41,29.30,29.14,28.35,27.02,26.17,22.70,22.62,14.14,14.09.
Again with prepare 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (4- octyloxyphenyls)- It is explained as a example by 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.Add 5,9-two in 100ml two-mouth bottles (thiophene-2- Base)-7-(2-ethylhexyl)-2,3-two (4- octyloxyphenyls)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.5g, 0.59mmol), 30ml chloroforms are added and 10ml glacial acetic acids stirs.NBS (N- are added under condition of ice bath Bromosuccinimide, N- bromo-succinimide) (0.25g, 1.41mmol), normal-temperature reaction 24h.Pour reactant liquor into water In, extracted with dichloromethane.Anhydrous magnesium sulfate is dried organic faciess, filters, is spin-dried for organic faciess, then with silica gel column chromatography chromatograph post separation Purification obtain Orange red solid 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (4- octyloxyphenyls)- (0.51g, yield is 83%) for 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.
1H NMR(300MHz,CDCl3)：δ=7.66 (d, 4H), δ=7.57 (d, 2H), δ=7.20 (d, 2H), δ=6.88 (d, 4H), δ=3.99 (t, 4H), δ=3.61 (d, 2H), δ=1.87 (m, 1H), δ=1.75 (m, 4H), δ=1.25-1.31 (m, 28H), δ=0.86 (m, 12H).
13C NMR(151MHz,CDCl3)δ166.44,160.82,152.82,140.24,133.36,132.45, 131.90,131.36,129.73,129.02,126.48,118.16,114.45,68.16,42.77,38.08,31.82, 30.65,29.36,29.24,29.21,28.55,26.04,24.00,23.05,22.67,14.12,14.07,10.49.
Again with prepare 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (3- octyloxyphenyls)- It is explained as a example by 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.Add 5,9-two in 100ml two-mouth bottles (thiophene-2- Base)-7-(2-ethylhexyl)-2,3-two (3-octyloxyphenyl)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.73g, 0.83mmol), adds 40ml chloroforms and 10ml glacial acetic acids stir.NBS (N- are added under condition of ice bath Bromosuccinimide, N- bromo-succinimide) (0.36g, 2mmol), normal-temperature reaction 24h.Reactant liquor is poured into water, Extracted with dichloromethane.Anhydrous magnesium sulfate is dried organic faciess, filters, is spin-dried for organic faciess, then is carried with silica gel column chromatography chromatograph post separation It is pure obtain Orange red solid 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (3- octyloxyphenyls)- (0.7g, yield is 81%) for 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline.
1H NMR(300MHz,CDCl3)：δ=7.63 (d, 2H), δ=7.54 (s, 2H), δ=7.18 (m, 4H), δ=7.08 (d, 2H), δ=6.91 (d, 2H), δ=3.98 (t, 4H), δ=3.63 (d, 2H), δ=1.77 (m, 5H), δ=1.20-1.30 (m, 28H), δ=0.88 (m, 12H).
13C NMR(151MHz,CDCl3)δ166.31,159.45,153.06,140.23,138.48,133.66, 132.21,131.47,129.17,129.06,126.87,122.79,118.48,117.95,114.84,68.24,42.84, 38.11,31.86,30.67,29.41,29.36,29.30,28.56,26.17,26.06,24.02,23.04,22.70, 14.13,14.07,10.49.
5,9-two (5-bromo--2-yl of thiophene)-7-R1- 2-R of base2- 3-R of base3Base-7H-pyrrolo- [3,4-g] quinoxaline-6, 8-diketone is not limited only to this.
Embodiment 4
Poly- { 4,8-two (2-ethyl hexyl oxy)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (thiophene-2- Base)-7-octyl group-2,3-two (4-octyloxyphenyl)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline } (being abbreviated as P1) Synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-octyl group-2,3-two (4- octyloxyphenyls)-7H-pyrrolo- [3, 4-g] two tin trimethyl benzo of-6,8-diketone of quinoxaline (0.104g, 0.1mmol) and 4,8-two (2-ethyl hexyl oxy)-2,6- [1,2-b:3,4-b '] Dithiophene (0.077g, 0.1mmol) and four conjunction triphenylphosphine palladium (7mg) be added to 25ml two-mouth bottles In, it is subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), after nitrogen aerofluxuss are steeped 20 minutes, rises Temperature is reacted 48 hours to 110 DEG C.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is settled out polymer.Will be poly- Compound successively uses methanol in being put into Soxhlet extractor, and acetone, normal hexane respectively extract 24h, washes away small molecule and catalyst. and then Residual polymer is dissolved with chloroform, separated out in instilling methanol again.Buchner funnel collected polymer is finally used, aubergine is obtained Polymer 104mg, yield are about 79%.The number-average molecular weight of the polymer is 27500, and weight average molecular weight is 48400.
Embodiment 5
Poly- { 4,8-two (2-ethyl hexyl oxy)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (thiophene-2- Base)-7-octyl group-2,3-two (3-octyloxyphenyl)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline } (being abbreviated as P2) Synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-octyl group-2,3-two (3- octyloxyphenyls)-7H-pyrrolo- [3, 4-g] two tin trimethyl benzo of-6,8-diketone of quinoxaline (0.104g, 0.1mmol) and 4,8-two (2-ethyl hexyl oxy)-2,6- [1,2-b:3,4-b '] Dithiophene (0.077g, 0.1mmol) and four conjunction triphenylphosphine palladium (7mg) be added to 25ml two-mouth bottles In, it is subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), after nitrogen aerofluxuss are steeped 20 minutes, rises Temperature is reacted 48 hours to 110 DEG C.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is settled out polymer.Will be poly- Compound successively uses methanol in being put into Soxhlet extractor, and acetone, normal hexane respectively extract 24h, washes away small molecule and catalyst. and then Residual polymer is dissolved with chloroform, separated out in instilling methanol again. buchner funnel collected polymer is finally used, aubergine is obtained Polymer 106mg, yield are about 80%.The number-average molecular weight of the polymer is 16000, and weight average molecular weight is 30080.
Embodiment 6
Poly- { 4,8-two (2-ethyl hexyl oxy)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (thiophene-2- Base)-7-(2-ethylhexyl)-2,3-two (4-octyloxyphenyl)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline } (write a Chinese character in simplified form For P3) synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (4- octyloxyphenyls)-7H- Two front three of pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.104g, 0.1mmol) and 4,8-two (2-ethyl hexyl oxy)-2,6- Base stannum benzo [1,2-b:3,4-b '] Dithiophene (0.077g, 0.1mmol) and four conjunction triphenylphosphine palladium (7mg) be added to 25ml In two-mouth bottle, it is subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), nitrogen aerofluxuss is steeped 20 minutes Afterwards, 110 DEG C are warming up to, are reacted 48 hours.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is settled out polymer. Polymer is put in Soxhlet extractor and successively use methanol, acetone, normal hexane respectively extract 24h, washes away small molecule and catalyst. Then residual polymer is dissolved with chloroform, separated out in instilling methanol again. buchner funnel collected polymer is finally used, purple is obtained Red polymer 108mg, yield are about 82%.The number-average molecular weight of the polymer is 12400, and weight average molecular weight is 24800.
Embodiment 7
Poly- { 4,8-two (2-ethyl hexyl oxy)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (thiophene-2- Base)-7-(2-ethylhexyl)-2,3-two (3-octyloxyphenyl)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline } (write a Chinese character in simplified form For P4) synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (3- octyloxyphenyls)-7H- Two front three of pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.104g, 0.1mmol) and 4,8-two (2-ethyl hexyl oxy)-2,6- Base stannum benzo [1,2-b:3,4-b '] Dithiophene (0.077g, 0.1mmol) and four conjunction triphenylphosphine palladium (7mg) be added to 25ml In two-mouth bottle, it is subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), nitrogen aerofluxuss is steeped 20 minutes Afterwards, 110 DEG C are warming up to, are reacted 48 hours.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is settled out polymer. Polymer is put in Soxhlet extractor and successively use methanol, acetone, normal hexane respectively extract 24h, washes away small molecule and catalyst. Then residual polymer is dissolved with chloroform, separated out in instilling methanol again. buchner funnel collected polymer is finally used, purple is obtained Red polymer 107mg, yield are about 81%.The number-average molecular weight of the polymer is 15300, and weight average molecular weight is 34272.
Embodiment 8
Poly- { 4,8-two (4,5- didecylthiophene-2- bases)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (- 2-yl of thiophene)-7-octyl group-2,3-two (4-octyloxyphenyl)-7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline } (write a Chinese character in simplified form For P5) synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-octyl group-2,3-two (4- octyloxyphenyls)-7H-pyrrolo- [3, 4-g]-6,8-diketone of quinoxaline (0.208g, 0.2mmol) and 4,8-two (4,5- didecylthiophene-2- bases) two trimethyls of-2,6- Stannum benzo [1,2-b:3,4-b '] Dithiophene (0.248g, 0.2mmol) and four conjunction triphenylphosphine palladium (8mg) be added to 25ml two In mouth bottle, it is subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), nitrogen aerofluxuss is steeped 20 minutes Afterwards, 110 DEG C are warming up to, are reacted 48 hours.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is settled out polymer. Polymer is put in Soxhlet extractor and successively use methanol, acetone, normal hexane respectively extract 24h, washes away small molecule and catalyst. Then residual polymer is dissolved with chloroform, separated out in instilling methanol again. buchner funnel collected polymer is finally used, purple is obtained Red polymer 303mg, yield are about 84%.The number-average molecular weight of the polymer is 45320, and weight average molecular weight is 71714.
Embodiment 9
Poly- { 4,8-two (4,5- didecylthiophene-2- bases)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (- 2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (4-octyloxyphenyl)-7H-pyrrolo- [3,4-g] quinoxaline-6,8-two Ketone } (being abbreviated as P6) synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (4- octyloxyphenyls)-7H- Pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.208g, 0.2mmol) and 4,8-two (4,5- didecylthiophene-2- bases)-2, Bis- tin trimethyl benzo [1,2-b of 6-:3,4-b '] Dithiophene (0.248g, 0.2mmol) and four close triphenylphosphine palladium (8mg) plus Enter in 25ml two-mouth bottles, be subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), nitrogen aerofluxuss Bubble was warming up to 110 DEG C after 20 minutes, reacted 48 hours.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is precipitated Go out polymer.Polymer is put in Soxhlet extractor and successively use methanol, acetone, normal hexane respectively extract 24h, washes away small molecule And catalyst. and then residual polymer is dissolved with chloroform, and separated out in instilling methanol again. finally collected with buchner funnel and be polymerized Thing, obtains aubergine polymer 320mg, and yield is about 89%.The number-average molecular weight of the polymer is 62026, weight average molecular weight For 89517.
Embodiment 10
Poly- { 4,8-two (4,5- didecylthiophene-2- bases)-benzo [1,2-b:3,4-b '] Dithiophene-alternating-5,9-two (- 2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (3-octyloxyphenyl)-7H-pyrrolo- [3,4-g] quinoxaline-6,8-two Ketone } (being abbreviated as P7) synthesis.
Synthetic route is as follows：
By monomer 5,9-two (5-bromo--2-yl of thiophene)-7-(2-ethylhexyl)-2,3-two (3- octyloxyphenyls)-7H- Pyrrolo- [3,4-g]-6,8-diketone of quinoxaline (0.208g, 0.2mmol) and 4,8-two (4,5- didecylthiophene-2- bases)-2, Bis- tin trimethyl benzo [1,2-b of 6-:3,4-b '] Dithiophene (0.248g, 0.2mmol) and four close triphenylphosphine palladium (8mg) plus Enter in 25ml two-mouth bottles, be subsequently adding 5ml toluene and which is fully dissolved by 0.5ml dimethylformamides (DMF), nitrogen aerofluxuss Bubble was warming up to 110 DEG C after 20 minutes, reacted 48 hours.Room temperature is subsequently cooled to, reactant liquor is instilled in 200ml methanol and is precipitated Go out polymer.Polymer is put in Soxhlet extractor and successively use methanol, acetone, normal hexane respectively extract 24h, washes away small molecule And catalyst. and then residual polymer is dissolved with chloroform, and separated out in instilling methanol again. finally collected with buchner funnel and be polymerized Thing, obtains aubergine polymer 290mg, and yield is about 81%.The number-average molecular weight of the polymer is 24071, weight average molecular weight For 44994.
Embodiment 11
The preparation of polymer solar cells device and performance
Polymer solar cells device adopts inverted structure, using ito glass substrate as electronic collection electrode, ito glass Acetone, detergent, deionized water and isopropanol supersound washing are used successively, are then placed in 80 DEG C of baking oven and are overnight dried.Then, in advance It is dissolved in methanol and acetic acid mixed solvent (100:1v:V) the crosslinkable PF of 0.5mg/ml3The glove box that N-OX solution is protected in nitrogen In by sol evenning machine be spin-coated on the rotating speed of 2000rpm be dried cooling after ITO substrates on, and then heat 140 DEG C of 25min enter Row cross-linking reaction, finally obtains the PF of the thick crosslinkings of 5nm3N-OX films.Then, by above example synthesized polymer its Middle a kind of and PCBM different proportions solution (solvent is o-dichlorohenzene) is spin-coated on PF3N-OX films are obtained above 80-90nm or so Active layer.Subsequent 10nm MoO3It is 3 × 10 in vacuum-4The plating storehouse of Pa is with the speed heat deposition of 0.01nm/s in active layer Above, and then above-mentioned device is placed on the mask plate of customization, then heat deposition obtains effective area for 0.16cm2Thickness is 80nm metal Al are used as hole-collecting electrode.Last device is covering effective device area by epoxy resin, in ultra-violet curing Stove solidification 5min carrys out encapsulated device to completely cut off impact of the water oxygen to device.
Power conversion efficiency (PCE) is in AM 1.5G XES-40S1150W AAA Class Solar Simulator Measure under (solar simulation lamp-type number).The light intensity of solar simulation lamp is demarcated as 100mWcm by standard silicon solar cell-2.Electricity Current density-voltage (J-V) curve of pond device is measured by Keithley2400Source Measure Unit records 's.Wherein, the battery efficiency based on the device of P1, P2, P3 and P4 is as shown in table 1, and corresponding J-V curves are shown in Fig. 3.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.
Table 1

Claims (4)

1. 7H-pyrrolo- [3,4-g] quinoxaline-6, the conjugated polymer of 8-diketone are contained, it is characterised in that structural formula is：
Wherein, R1、R2And R3For hydrogen atom or alkyl chain；The alkyl chain be the straight chain with 1～24 carbon atom, side chain or Person's cyclic alkyl chain, or wherein one or more carbon atoms, by oxygen atom replacement, hydrogen atom is by halogen atom, thiazolinyl, alkynyl, virtue Base, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro replace；Ar is aromatic group；The n is 1～10000 nature Number, 0 ＜ x ＜, 1,0 ＜ y ＜ 1, x+y=1.
2. conjugated polymer according to claim 1, it is characterised in that the aromatic group Ar is as follows structure One or more：
Wherein, R, Ra～RdReplaced by oxygen atom for hydrogen atom or alkyl chain, or wherein one or more carbon atoms, hydrogen atom Replaced by halogen atom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
3. conjugated polymer according to claim 1 and 2, it is characterised in that described R, Ra～RdIt is with 1～24 carbon The straight chain of atom, side chain or cyclic alkyl chain.
4. the conjugated polymer described in claim 1 or 2 or 3 is preparing the luminescent layer of polymer LED device, is preparing Semiconductor active layer in polymer field effect transistor or the application in preparing the active layer of polymer solar photovoltaic cell.
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