CN104744676A - Conjugated polymer containing 7H-pyrrolo [3,4-g] quinoxaline-6,8-diketone and application of conjugated polymer - Google Patents

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

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CN104744676A
CN104744676A CN201510147716.9A CN201510147716A CN104744676A CN 104744676 A CN104744676 A CN 104744676A CN 201510147716 A CN201510147716 A CN 201510147716A CN 104744676 A CN104744676 A CN 104744676A
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diketone
pyrrolo
kui
lin
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CN104744676B (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 conjugated polymer containing 7H-pyrrolo [3,4-g] quinoxaline-6,8-diketone and an application thereof. A structural formula is described in the description. The prepared conjugated polymer containing 7H-pyrrolo [3,4-g] quinoxaline-6,8-diketone has fluorescence and broad sunlight absorption range, so that the conjugated polymer containing 7H-pyrrolo [3,4-g] quinoxaline-6,8-diketone can be applied to production of a polymeric light-emitting diode device and active layers of a polymer field effect transistor and a polymer solar battery. The structural formula is described in the description.

Description

Containing conjugated polymers and the application of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone
Technical field
The present invention relates to a kind of new polymkeric substance being applied to photoelectron material and devices field, particularly containing Optical Properties of Novel Conjugated and the preparation and application thereof of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone.
Background technology
In in the past 10 years, organic sun hull cell is very burning hot, and the efficiency of organic thin film cells also hits new peak frequently, and current single layer device top efficiency breaks through 10%, and market-oriented prospect is very bright.In order to obtain efficient polymer solar cell device, material is one of most important factor.Generally speaking, a desirable material will have wide absorption, high carrier mobility, suitable energy level.So this just needs us to carry out the innovation of material, develop more Optical Properties of Novel Conjugated material.In numerous photoelectric material, photoelectric material containing quinoxaline group or imide group (such as benzo imide) is at organic electroluminescent, organic solar batteries, is widely used in chemistry and the material such as biosensor and organic field effect tube.Due to the modifiability of benzo imide group atom N, therefore the alkyl chain that can be connected with different shapes and length in atom N carries out solubilising to it, thus improves solvability and the workability of corresponding light electric material.But this chemical functional group of benzo imide also has its limitation, be mainly that electron-withdrawing power is not very strong, after other aromatic group copolymerization, be difficult to the polymkeric substance forming wide absorption.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, in order to improve the photoelectric properties containing benzo imide unit material further, benzo imide and quinoxaline combine by this patent, there is provided a class novel condensed ring photoelectric material: 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone.This conjugated polymers has fluorescence, has wide absorption to sunlight.
Another object of the present invention is to provide the preparation method of the described conjugated polymers containing 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone.
Another object of the present invention is to provide the described application of conjugated polymers in polymer LED, polymer field effect transistor and polymer solar battery containing 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone.
Object of the present invention is achieved through the following technical solutions:
Containing the conjugated polymers of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone, its structural formula is:
Wherein, R 1, R 2and R 3for hydrogen atom or alkyl chain; Described alkyl chain is have the straight chain of 1 ~ 24 carbon atom, side chain or cyclic alkyl chain, or wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, hydrogen atom is replaced by halogen atom or above-mentioned functional group; Ar is aromatic group; Described n is the natural number of 1 ~ 10000,0 < x < 1,0 < y < 1, x+y=1.X, y are respectively the relative content of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – dione unit and aromatic group Ar in described conjugated polymers; Aromatic group Ar and 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone are connected with conjugated manner, and n is the polymerization degree of described conjugated polymers.
Described aromatic group Ar is one or more of structure as follows:
Wherein, R, R a~ R dfor hydrogen atom or alkyl chain.Described R, R a~ R dfor having the straight chain of 1 ~ 24 carbon atom, side chain or cyclic alkyl chain, or wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, hydrogen atom is replaced by halogen atom or above-mentioned functional group.
Described conjugated polymers is in the semiconductor active layer prepared in the luminescent layer of polymer LED device, preparation polymer field effect transistor or the application prepared in the active coating of polymer solar photovoltaic cell.
The present invention by select multiple conjugation fragrant monomer respectively with containing 7H – pyrrolo-[3,4 – g] monomer of Kui Wo Lin – 6,8 – diketone carries out Still coupling copolymerization, obtains containing 7H – pyrrolo-[3,4 – g] conjugated polymers of Kui Wo Lin – 6,8 – diketone.
Conjugated polymers containing 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone of the present invention can be prepared as follows:
(1) with 4,7 – bis-(Sai Fen – 2 – base) – 1,2,5 – Ben Sai bis-Zuo – N – R 1ji – 5,6 – di-carboxylic acid imide is parent, is reacted, obtain 4 by iron powder reducing, 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – R 1ji – Yi Yin Duo – 1,3 – diketone, then this monomer and even acyl compounds are carried out dehydration condensation synthesize 5,9 – bis-(Sai Fen – 2 – base) – 7 – R 1ji – 2 – R 2ji – 3 – R 3ji – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone, obtains final monomer 5,9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – R finally by NBS bromination 1ji – 2 – R 2ji – 3 – R 3ji – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone.
(2) metal catalyzed coupling reaction: react containing the brominated product in the monomer with metal catalyzed coupling reaction active function groups of Ar structure and step (1) under metal catalyst, what obtain first one-step functional contains Ar structure and 7H – pyrrolo-[3,4 – g] conjugated polymers of Kui Wo Lin – 6,8 – diketone.
7H – pyrrolo-[3 can be made by the adjustment conversion of Ar structure in step (2), 4 – g] Kui Wo Lin – 6,8 – derovatives have good solution processability and photoelectric properties, final successfully by 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone structure is incorporated in polymkeric substance, and preparation series is containing 7H – pyrrolo-[3,4 – g] conjugated polymers of Kui Wo Lin – 6,8 – diketone.
The structure of small molecules and polymer materials is characterized by nucleus magnetic resonance (NMR) and gel chromatography (GPC), by the spectral quality of ultraviolet-visual spectrometer test polymer material, obtained polymkeric substance is prepared into the photoelectric properties that photoelectric device characterizes them simultaneously.
Compare with traditional benzo imide, the electron-withdrawing power of 7H – pyrrolo-of the present invention [3,4 – g] Kui Wo Lin – 6,8 – diketone is significantly improved, and is expected to develop the better narrow band gap solar cell material of performance.Can predict, the conjugated polymer material containing 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone has good photoelectric properties, is the material that a class has commercial applications prospect.
The structural formula of benzo imide and 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is as follows:
Based on the conjugated polymer material of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone, as the promising photoelectric material of a class, in this field, someone did not report so far.The present invention synthesized conjugated polymers containing 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone first and successful Application at photoelectric field.
Compared with prior art, the present invention has the following advantages:
Containing the conjugated polymers novel structure of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone, there is originality.Conjugated polymers containing 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone has several functions, has fluorescence, can be applied to the luminescent layer making polymer LED; There is higher mobility, can polymer field effect transistor be applied to; Have absorptivity to sunlight, can be applied to the active coating of polymer solar cells, relevant solar cell has higher effciency of energy transfer.
Accompanying drawing explanation
Fig. 1 is the absorption spectrogram of polymkeric substance in tetrahydrofuran solution prepared by embodiment 4 ~ 7;
The film absorption spectrogram of Fig. 2 polymkeric substance prepared by embodiment 4 ~ 7;
Fig. 3 is the J-V graphic representation of device prepared by embodiment 4 ~ 7 resulting polymers.
Embodiment
Content for a better understanding of the present invention, further illustrates technical scheme of the present invention below by concrete example, specifically comprises synthesis, sign and device and prepares, but be not limited thereto.
Embodiment 1
4,7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – R 1the preparation of Ji – Yi Yin Duo – 1,3 – diketone, reaction formula is such as formula shown in I:
4,7 – bis-(Sai Fen – 2 – base) – 1,2,5 – Ben in formula I Sai bis-Zuo – N – R 1the synthesis reference literature [Wang LX, Cai DD, Zheng QD, et al.ACS Macro Lett.2013,2,605-608] of Ji – 5,6 – di-carboxylic acid imide (a).
To prepare 4,7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – Xin Ji – Yi Yin Duo – 1,3 – diketone are that example is explained.4 are added in 50ml two-mouth bottle, 7 – bis-(Sai Fen – 2 – base) – 1,2,5 – Ben Sai bis-Zuo – N – Xin Ji – 5,6 – di-carboxylic acid imide (0.87g, 1.82mmol) and iron powder (1.22g, 21.8mmol), add 30ml glacial acetic acid again, under condition of nitrogen gas after stirring and refluxing 5h, reaction solution is poured into water, separate out greenish yellow solid, filter, get filter residue, obtain yellow solid 4 with silica gel column chromatography chromatographic column separating-purifying, 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – Xin Ji – Yi Yin Duo – 1,3 – diketone (0.6g, productive rate 73%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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.
Again to prepare 4, (2 – ethylhexyl) – Yi Yin Duo – 1,3 – diketone are that example is explained to 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N –.4 are added in 50ml two-mouth bottle, 7 – bis-(Sai Fen – 2 – base) – 1, 2, 5 – Ben Sai bis-Zuo – N – (2 – ethylhexyl) – 5, 6 – imide (0.6g, 1.25mmol) with iron powder (0.83g, 14.97mmol), add 30ml glacial acetic acid again, under condition of nitrogen gas after stirring and refluxing 5h, reaction solution is poured into water, separate out greenish yellow solid, filter, get filter residue, yellow solid 4 is obtained with silica gel column chromatography chromatographic column separating-purifying, 7 – bis-(Sai Fen – 2 – base) – 5, 6 – bis-An Ji – N – (2 – ethylhexyl) – Yi Yin Duo – 1, 3 – diketone (0.42g, productive rate 75%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – Wan Ji – Yi Yin Duo – 1,3 – diketone are not limited only to this.
Embodiment 2
5,9 – bis-(Sai Fen – 2 – base) – 7 – R 1ji – 2 – R 2ji – 3 – R 3the preparation of Ji – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone, reaction formula is such as formula shown in II:
To prepare 5, (4-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-.4 are added respectively in 100ml two-mouth bottle, 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – Xin Ji – Yi Yin Duo – 1,3 – diketone (0.38g, 0.83mmol) He 1,2-bis-(4 – octyloxyphenyl) Yi Wan – 1,2 – diketone (0.42g, 0.87mmol), add 45ml glacial acetic acid again, after stirring and refluxing is spent the night under condition of nitrogen gas, reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained orange solids 5,9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(4 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.63g, productive rate 86%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 to prepare 5, (3-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-.4 are added respectively in 100ml two-mouth bottle, 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – Xin Ji – Yi Yin Duo – 1,3 – diketone (0.38g, 0.83mmol) He 1,2 – bis-(3 – octyloxyphenyl) ethane-1,2 – diketone (0.42g, 0.87mmol), add 45ml glacial acetic acid again, after stirring and refluxing is spent the night under condition of nitrogen gas, reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained orange solids 5,9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(3 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.66g, productive rate 90%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 to prepare 5, ((4-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 2 – ethylhexyl) – 2,3 – bis-to 9 – bis-(Sai Fen – 2 – base) – 7 –.4 are added respectively in 50ml two-mouth bottle, 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – (2 – ethylhexyl) – Yi Yin Duo – 1,3 – diketone (0.26g, 0.57mmol) He 1,2 – bis-(4 – octyloxyphenyl) ethane-1,2 – diketone (0.25g, 0.54mmol), add 30ml glacial acetic acid again, after stirring and refluxing is spent the night under condition of nitrogen gas, reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained orange solids 5,9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(4 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.43g, productive rate 86%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 to prepare 5, ((3-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 2 – ethylhexyl) – 2,3 – bis-to 9 – bis-(Sai Fen – 2 – base) – 7 –.4 are added respectively in 100ml two-mouth bottle, 7 – bis-(Sai Fen – 2 – base) – 5,6 – bis-An Ji – N – (2 – ethylhexyl) – Yi Yin Duo – 1,3 – diketone (0.43g, 0.95mmol) He 1,2 – bis-(3 – octyloxyphenyl) ethane-1,2 – diketone (0.42g, 0.9mmol), add 50ml glacial acetic acid again, after stirring and refluxing is spent the night under condition of nitrogen gas, reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained orange solids 5,9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(3 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.74g, productive rate 88%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 – bis-(Sai Fen – 2 – base) – 7 – R 1ji – 2 – R 2ji – 3 – R 3ji – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is not limited only to this.
Embodiment 3
5,9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – R 1ji – 2 – R 2ji – 3 – R 3the preparation of base – 7H – pyrrolo-[3,4 – g] quinoline quinoline – 6,8 – diketone, reaction formula is as shown in formula III:
To prepare 5, ((4-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-to 9 – bis-.5 are added in 100ml two-mouth bottle, 9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone (0.63g, 0.71mmol), then add 30ml chloroform and 10ml glacial acetic acid stirs.NBS (N-bromosuccinimide, N-bromo-succinimide) (0.31g, 1.71mmol) is added, normal-temperature reaction 24h under condition of ice bath.Reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained Orange red solid 5,9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.57g, productive rate 77%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 to prepare 5, ((3-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-to 9 – bis-.5 are added in 100ml two-mouth bottle, 9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(3-octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone (0.66g, 0.75mmol), then add 30ml chloroform and 10ml glacial acetic acid stirs.NBS (N-bromosuccinimide, N-bromo-succinimide) (0.32g, 1.8mmol) is added, normal-temperature reaction 24h under condition of ice bath.Reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained Orange red solid 5,9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(3-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.57g, productive rate 73%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 to prepare 5, (((4-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 2 – ethylhexyl) – 2,3 – bis-to 5 – Xiu – Sai Fen – 2 – base) – 7 – to 9 – bis-.5 are added in 100ml two-mouth bottle, 9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone (0.5g, 0.59mmol), then add 30ml chloroform and 10ml glacial acetic acid stirs.NBS (N-bromosuccinimide, N-bromo-succinimide) (0.25g, 1.41mmol) is added, normal-temperature reaction 24h under condition of ice bath.Reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained Orange red solid 5,9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.51g, productive rate 83%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 to prepare 5, (((3-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is that example is explained to 2 – ethylhexyl) – 2,3 – bis-to 5 – Xiu – Sai Fen – 2 – base) – 7 – to 9 – bis-.5 are added in 100ml two-mouth bottle, 9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(3 – octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone (0.73g, 0.83mmol), then add 40ml chloroform and 10ml glacial acetic acid stirs.NBS (N-bromosuccinimide, N-bromo-succinimide) (0.36g, 2mmol) is added, normal-temperature reaction 24h under condition of ice bath.Reaction solution is poured into water, uses dichloromethane extraction.Anhydrous magnesium sulfate drying organic phase, filter, be spin-dried for organic phase, recycle silicon glue-line is analysed chromatographic column separating-purifying and is obtained Orange red solid 5,9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(3-octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone (0.7g, productive rate 81%).
1H NMR(300MHz,CDCl 3)：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,CDCl 3)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 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – R 1ji – 2 – R 2ji – 3 – R 3ji – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone is not limited only to this.
Embodiment 4
Poly-{ 4,8 – bis-(2 – ethyl hexyl oxy) – benzos [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(4 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P1).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2, 3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.104g, 0.1mmol) He 4, 8 – bis-(2 – ethyl hexyl oxy) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.077g, 0.1mmol) and four close triphenylphosphine palladium (7mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, each extracting 24h of normal hexane, washes away small molecules and catalyzer. and then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol.Finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 104mg, productive rate is about 79%.The number-average molecular weight of this polymkeric substance is 27500, and weight-average molecular weight is 48400.
Embodiment 5
Poly-{ 4,8 – bis-(2 – ethyl hexyl oxy) – benzos [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(3 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P2).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2, 3 – bis-(3-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.104g, 0.1mmol) He 4, 8 – bis-(2 – ethyl hexyl oxy) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.077g, 0.1mmol) and four close triphenylphosphine palladium (7mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, the each extracting 24h of normal hexane, wash away small molecules and catalyzer. then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol. finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 106mg, productive rate is about 80%.The number-average molecular weight of this polymkeric substance is 16000, and weight-average molecular weight is 30080.
Embodiment 6
Poly-{ 4,8 – bis-(2 – ethyl hexyl oxy) – benzos [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(4 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P3).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2, 3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.104g, 0.1mmol) He 4, 8 – bis-(2 – ethyl hexyl oxy) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.077g, 0.1mmol) and four close triphenylphosphine palladium (7mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, the each extracting 24h of normal hexane, wash away small molecules and catalyzer. then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol. finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 108mg, productive rate is about 82%.The number-average molecular weight of this polymkeric substance is 12400, and weight-average molecular weight is 24800.
Embodiment 7
Poly-{ 4,8 – bis-(2 – ethyl hexyl oxy) – benzos [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(3 – octyloxyphenyl) – 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P4).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2, 3 – bis-(3-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.104g, 0.1mmol) He 4, 8 – bis-(2 – ethyl hexyl oxy) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.077g, 0.1mmol) and four close triphenylphosphine palladium (7mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, the each extracting 24h of normal hexane, wash away small molecules and catalyzer. then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol. finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 107mg, productive rate is about 81%.The number-average molecular weight of this polymkeric substance is 15300, and weight-average molecular weight is 34272.
Embodiment 8
Poly-{ 4,8 – bis-(4,5-didecylthiophene-2-base) – benzo [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – Xin Ji – 2,3 – bis-(4 – octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P5).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – Xin Ji – 2, 3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.208g, 0.2mmol) He 4, 8 – bis-(4, 5-didecylthiophene-2-base) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.248g, 0.2mmol) and four close triphenylphosphine palladium (8mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, the each extracting 24h of normal hexane, wash away small molecules and catalyzer. then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol. finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 303mg, productive rate is about 84%.The number-average molecular weight of this polymkeric substance is 45320, and weight-average molecular weight is 71714.
Embodiment 9
Poly-{ 4,8 – bis-(4,5-didecylthiophene-2-base) – benzo [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(4 – octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P6).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2, 3 – bis-(4-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.208g, 0.2mmol) He 4, 8 – bis-(4, 5-didecylthiophene-2-base) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.248g, 0.2mmol) and four close triphenylphosphine palladium (8mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, the each extracting 24h of normal hexane, wash away small molecules and catalyzer. then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol. finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 320mg, productive rate is about 89%.The number-average molecular weight of this polymkeric substance is 62026, and weight-average molecular weight is 89517.
Embodiment 10
Poly-{ 4,8 – bis-(4,5-didecylthiophene-2-base) – benzo [1,2-b:3,4-b '] Er Sai Fen – Jiao Ti – 5,9 – bis-(Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2,3 – bis-(3 – octyloxyphenyl) – 7H – pyrrolo-es [3,4 – g] Kui Wo Lin – 6,8 – diketone } synthesis of (being abbreviated as P7).
Synthetic route is as follows:
By monomer 5, 9 – bis-(5 – Xiu – Sai Fen – 2 – base) – 7 – (2 – ethylhexyl) – 2, 3 – bis-(3-octyloxyphenyl) – 7H – pyrrolo-es [3, 4 – g] Kui Wo Lin – 6, 8 – diketone (0.208g, 0.2mmol) He 4, 8 – bis-(4, 5-didecylthiophene-2-base) – 2, 6-bis-tin trimethyl benzo [1, 2-b:3, 4-b '] two thiophene (0.248g, 0.2mmol) and four close triphenylphosphine palladium (8mg) join in 25ml two-mouth bottle, then 5ml toluene is added and it fully dissolves by 0.5ml dimethyl formamide (DMF), nitrogen exhaust bubble is after 20 minutes, be warming up to 110 DEG C, react 48 hours.Then be cooled to room temperature, reaction solution instilled in 200ml methyl alcohol and be settled out polymkeric substance.Polymkeric substance is put into Soxhlet extractor priority methyl alcohol, acetone, the each extracting 24h of normal hexane, wash away small molecules and catalyzer. then dissolve residual polymer with chloroform, again separate out in instillation methyl alcohol. finally use Büchner funnel collected polymer, obtain red-purple polymkeric substance 290mg, productive rate is about 81%.The number-average molecular weight of this polymkeric substance is 24071, and weight-average molecular weight is 44994.
Embodiment 11
The fabrication & properties of polymer solar cells device
Polymer solar cells device adopts inverted structure, and using ito glass substrate as electronic collection electrode, ito glass uses acetone, washing composition, deionized water and Virahol supersound washing successively, then puts into 80 DEG C, baking oven and to spend the night oven dry.Then, methyl alcohol and the crosslinkable PF of acetic acid mixed solvent (100:1v:v) 0.5mg/ml is dissolved in advance 3n-OX solution is spin-coated on dry cooled ITO substrate by sol evenning machine with the rotating speed of 2000rpm in the glove box of nitrogen protection, and then heats 140 DEG C of 25min and carries out crosslinking reaction, finally obtains the crosslinked PF that 5nm is thick 3n-OX film.Then, the solution (solvent is orthodichlorobenzene) of the wherein a kind of and PCBM different ratios of polymkeric substance synthesized in above embodiment is spin-coated on PF 3the active coating of about 80-90nm is obtained above N-OX film.10nm MoO subsequently 3be 3 × 10 in vacuum tightness -4the plating storehouse of Pa, is and then placed on above-mentioned device on the mask plate of customization at active layer with the speed heat deposition of 0.01nm/s, then heat deposition to obtain useful area be 0.16cm 2thickness is that 80nm metal A l is as hole-collecting electrode.Last device is covering effective device area by epoxy resin, carrys out encapsulated device with the impact of exclusion of water oxygen on device at uv oven solidification 5min.
Power conversion efficiency (PCE) records under AM 1.5G XES-40S1150W AAA Class SolarSimulator (solar simulation lamp-type number).The light intensity of solar simulation lamp is demarcated as 100mWcm by standard silicon solar cell -2.Current density-voltage (J-V) curve of battery device is recorded by Keithley2400Source Measure Unit record.Wherein, the battery efficiency based on the device of P1, P2, P3 and P4 is as shown in table 1, and corresponding J-V curve is shown in Fig. 3.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Table 1

Claims (4)

1., containing the conjugated polymers of 7H – pyrrolo-[3,4 – g] Kui Wo Lin – 6,8 – diketone, it is characterized in that structural formula is:
Wherein, R 1, R 2and R 3for hydrogen atom or alkyl chain; Described alkyl chain is have the straight chain of 1 ~ 24 carbon atom, side chain or cyclic alkyl chain, or wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, hydrogen atom is replaced by halogen atom or above-mentioned functional group; Ar is aromatic group; Described n is the natural number of 1 ~ 10000,0 < x < 1,0 < y < 1, x+y=1.
2. conjugated polymers according to claim 1, is characterized in that, described aromatic group Ar is one or more of structure as follows:
Wherein, R, R a~ R dfor hydrogen atom or alkyl chain, or wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro, and hydrogen atom is replaced by halogen atom or above-mentioned functional group.
3. conjugated polymers according to claim 1 and 2, is characterized in that, described R, R a~ R dfor having the straight chain of 1 ~ 24 carbon atom, side chain or cyclic alkyl chain.
4. claim 1 or the conjugated polymers described in 2 or 3 are in the semiconductor active layer prepared in the luminescent layer of polymer LED device, preparation polymer field effect transistor or the application prepared in the active coating of polymer solar photovoltaic cell.
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