CN113831511B - A composition comprising a dithiophene [3,2-f:2',3' -h ] quinoxaline polymer and preparation method and application thereof - Google Patents

A composition comprising a dithiophene [3,2-f:2',3' -h ] quinoxaline polymer and preparation method and application thereof Download PDF

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CN113831511B
CN113831511B CN202111052246.XA CN202111052246A CN113831511B CN 113831511 B CN113831511 B CN 113831511B CN 202111052246 A CN202111052246 A CN 202111052246A CN 113831511 B CN113831511 B CN 113831511B
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何凤
赵廷兴
曹聪聪
王恒涛
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Southwest University of Science and Technology
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Abstract

The invention discloses a compound containing dithiophene [3,2-f:2',3' -h]A polymer of quinoxaline unit, a preparation method and an application thereof are disclosed, wherein the molecular structure general formula of the polymer is as follows:
Figure DDA0003253156850000011
wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is hydrogen or methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S, Y is O or S, when R is 2 Y may be Se when hydrogen is present. The invention constructs a new compound containing dithiophene [3,2-f:2',3' -h]The polymer donor of the quinoxaline unit is matched with the polymer receptor in the aspects of absorption spectrum and energy level by finely adjusting the molecular structure of the polymer donor, and simultaneously forms a morphology beneficial to carrier transmission, so that the all-polymer solar cell with higher photoelectric conversion efficiency is realized.

Description

A composition comprising a dithiophene [3,2-f:2',3' -h ] quinoxaline polymer and preparation method and application thereof
Technical Field
The invention relates to the field of all-polymer solar cells, in particular to a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline and a preparation method and application thereof.
Background
All-polymer solar cells, which consist of polymers as donors and acceptors, are of great interest due to their unique mechanical and morphological stability. In the past, research on all-polymer solar cells has mainly focused on Naphthalimides (NDI) and Perylenediimides (PDI), dicyanobenzothiazoles and B → N complexes, and the photoelectric conversion efficiency has been lower than 12% since the first all-polymer solar cell in 1995. The factors that limit the photoelectric conversion efficiency are two: (i) low electron mobility and poor molar absorption coefficient of the polymer acceptor, (ii) poor morphology due to entanglement of the polymer donor and the long alkyl chain of the polymer acceptor. In 2017, the Zhang Shi task group reports a new strategy for polymerizing a non-fullerene small molecule receptor to construct a polymer receptor, and the polymer receptor maintains the advantages of high electron mobility, low band gap and strong absorption in the near infrared region of corresponding small molecules. Recently, based on the polymerization non-fullerene small molecule strategy, the full polymer solar cell has made great progress.
Although the full polymer solar cell has been greatly developed and the photoelectric conversion efficiency is improved based on the polymerized non-fullerene acceptor strategy, the development of the matched polymer donor material is relatively delayed, the available polymer donor material is less, and the photoelectric conversion rate of the full polymer solar cell based on the reported polymer donor material is still at a lower level.
Thus, existing polymer donor materials have yet to be developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the existing polymer donor materials, the present invention aims to provide a polymer donor containing dithiophene [3,2-f:2',3' -h ] quinoxaline unit, a preparation method thereof and an application thereof in polymer solar cells.
The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a composition comprising a dithiophene [3,2-f:2',3' -h]Polymers of quinoxaline units, said polymers containing dithiophenes [3,2-f:2',3' -h]The general formula of the molecular structure of the polymer of the quinoxaline unit is
Figure BDA0003253156830000021
Wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is hydrogen or methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S, Y is O or S, when R is 2 Y may be Se when hydrogen is present.
In a second aspect, the present invention also provides a method for preparing a polymer containing dithieno [3,2-f:2',3' -h ] quinoxaline units, comprising the steps of:
s11: will be provided with
Figure BDA0003253156830000022
Reacting in ethanol to generate a molecular structure of
Figure BDA0003253156830000023
A first intermediate of (1), R 3 Is methyl or other alkyl chain;
s12: dissolving the first intermediate in CH 3 Cl and acetic acid, then adding NBS for reaction to generate a molecular structure of
Figure BDA0003253156830000024
A second intermediate of (a);
s13: reacting the second intermediate in Pd (Ph) 3 P) 4 Under the catalysis of (2), adding into a nitrogen atmosphere
Figure BDA0003253156830000025
Toluene and DMF react to generate a molecular structure of
Figure BDA0003253156830000026
A third intermediate of (5), R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain, Y is O or S, when R is 2 Y may be Se when hydrogen;
s14: dissolving the third intermediate in THF, adding NBS to react to generate a product with a molecular structure of
Figure BDA0003253156830000031
The fourth intermediate of (1);
s15: reacting said fourth intermediate with
Figure BDA0003253156830000032
In Pd 2 (dba) 3 、P(o-Tol) 3 Adding toluene to react under a catalytic system and a nitrogen atmosphere to prepare a mixture, and performing Soxhlet extraction on the mixture to obtain a compound with a molecular structural formula
Figure BDA0003253156830000033
Wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S,y is O or S, when R 2 Y may be Se when hydrogen is present.
The present invention also provides another method for preparing a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, comprising the steps of:
s21: will be provided with
Figure BDA0003253156830000034
Adding into THF solution, adding LiAlH under nitrogen atmosphere 4 The reaction product has a molecular structural formula
Figure BDA0003253156830000035
Wherein R is 2 Is straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, Y is O or S, when R is 2 Y may be Se when hydrogen;
s22: dissolving the first intermediate product in CHCl 3 Adding 1, 4-dioxane-2, 3-diol into acetic acid to react to produce the product with molecular structural formula
Figure BDA0003253156830000041
A second intermediate product of (a);
s23: dissolving the second intermediate product in THF, adding NBS for reaction to generate a molecular structural formula of
Figure BDA0003253156830000042
A third intermediate product of (a);
s24: the third intermediate product and
Figure BDA0003253156830000043
in Pd 2 (dba) 3 、P(o-Tol) 3 Under the catalysis, toluene is added in a nitrogen atmosphere for reaction to generate a molecular structural formula of
Figure BDA0003253156830000044
Wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl with 4-20 carbon atoms, and n is a natural number which is more than or equal to 5; x is O or S, Y is O or S, when R 2 When hydrogen Y may beSe, also soxhlet extraction of the polymer.
In a third aspect, the present invention provides an all-polymer photovoltaic device, which comprises an active layer, wherein the active layer comprises a polymer electron donor and a polymer electron acceptor, and the polymer electron donor is the polymer containing the dithiophene [3,2-f:2',3' -h ] quinoxaline unit, or the polymer containing the dithiophene [3,2-f:2',3' -h ] quinoxaline unit prepared by the preparation method.
Has the advantages that: the invention constructs a polymer donor containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, the molecular structure of the polymer donor is finely adjusted to enable the polymer donor to be more matched with a polymer acceptor in the aspects of absorption spectrum and energy level, and meanwhile, the appearance beneficial to carrier transmission is formed, so that the full polymer solar cell with higher photoelectric conversion efficiency is realized.
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FIG. 1 is a graph showing the UV-VIS absorption of polymers contained in examples 1-3 of the present invention in solution;
FIG. 2 is a graph showing the UV-VIS absorption of films of polymers included in examples 1-3 of the present invention;
FIG. 3 is a graph of electrochemical cyclic voltammograms of the polymers contained in examples 1-3 of the present invention;
FIG. 4 is a J (current power) -V (voltage) graph of a device of example 4 of the present invention;
FIG. 5 is a graph showing the external electron efficiency of the device of example 4 of the present invention.
Detailed Description
The invention provides a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, a preparation method and application thereof, and the invention is further detailed below in order to make the purposes, technical schemes and effects of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, based on a polymerization non-fullerene receptor strategy, the full polymer solar cell is greatly developed, and the photoelectric conversion efficiency is improved. However, the development of the matched polymer donor materials is relatively delayed, relatively few polymer donor materials are available, and the photoelectric conversion rate of all-polymer solar cells based on the reported polymer donor materials is still at a low level.
Based on the above, the invention provides a compound containing dithiophene [3,2-f:2',3' -h]The general formula of the molecular structure of the polymer of the quinoxaline unit is
Figure BDA0003253156830000051
Wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is hydrogen or methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S, Y is O or S, when R is 2 Y may be Se when hydrogen is present.
According to the invention, a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units is constructed, and the polymer shows strong aggregation in both solution and film states, and proper aggregation is beneficial to forming a morphology beneficial to carrier transmission, and the molar absorption coefficient is higher, so that the absorption of sunlight is facilitated, more excitons are generated, and meanwhile, the Highest Occupied Molecular Orbital (HOMO) is lower, so that the open-circuit voltage of the polymer is effectively improved. The polymer material can realize the full polymer solar cell with higher photoelectric conversion efficiency.
In some embodiments, the polymer comprising dithiophene [3,2-f:2',3' -h ] quinoxaline units has a number average molecular weight of 38000-100000, a weight average molecular weight of 60000-500000, and a dispersity of 1.8-4.3.
In some embodiments, the polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units is one of the following structural formulas:
Figure BDA0003253156830000061
Figure BDA0003253156830000071
wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is hydrogen or methyl or other alkyl chain, and n is a natural number greater than or equal to 5.
The embodiment of the invention also provides a preparation method of a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline unit, which comprises the following steps:
s11: will be provided with
Figure BDA0003253156830000072
Reacting in ethanol to generate a molecular structure of
Figure BDA0003253156830000073
A first intermediate of (1), R 3 Is methyl or other alkyl chain;
s12: dissolving the first intermediate in CH 3 Cl and acetic acid, then adding NBS to react to generate a molecular structure of
Figure BDA0003253156830000074
A second intermediate of (a);
s13: reacting the second intermediate in Pd (Ph) 3 P) 4 Under the catalysis of (2), adding into a nitrogen atmosphere
Figure BDA0003253156830000075
Toluene and DMF react to generate a molecular structure of
Figure BDA0003253156830000076
A third intermediate of (5), R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain, Y is O or S, when R is 2 Y may be Se when hydrogen;
s14: dissolving the third intermediate in THF, adding NBS for reaction to generate a molecular structure of
Figure BDA0003253156830000081
The fourth intermediate of (1);
s15: reacting said fourth intermediate with
Figure BDA0003253156830000082
In Pd 2 (dba) 3 、P(o-Tol) 3 Adding toluene to react under a catalytic system and a nitrogen atmosphere to prepare a mixture, and performing Soxhlet extraction on the mixture to obtain a compound with a molecular structural formula
Figure BDA0003253156830000083
Wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S, Y is O or S, when R is 2 Y may be Se when hydrogen is present.
In some embodiments, the step of post-treating the reaction mixture in step S15 comprises:
s151: pouring the reaction mixture into chlorobenzene, and heating until all solids are dissolved to obtain a solution a;
s152: dropwise adding the solution a into methanol to obtain a precipitate a;
s153: sequentially using methanol and CH for the sediment a 2 Cl 2 、CHCl 3 Performing Soxhlet extraction on chlorobenzene to obtain a solution b;
s154: and dropwise adding the solution b into methanol to obtain a sediment b, and drying the sediment b to obtain the polymer.
In some embodiments, a method of making the polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, comprises the steps of:
s21: will be provided with
Figure BDA0003253156830000091
Adding into THF solution, adding LiAlH under nitrogen atmosphere 4 The molecular structural formula of the reaction product is
Figure BDA0003253156830000092
Wherein R is 2 Is straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, Y is O or S, when R is 2 Y may be Se when hydrogen;
s22: the first middleThe product was dissolved in CHCl 3 Adding 1, 4-dioxane-2, 3-diol into acetic acid to react to produce the product with molecular structural formula
Figure BDA0003253156830000093
A second intermediate product of (a);
s23: dissolving the second intermediate product in THF, adding NBS for reaction to generate a molecular structural formula of
Figure BDA0003253156830000094
A third intermediate product of (a);
s24: the third intermediate product and
Figure BDA0003253156830000095
in Pd 2 (dba) 3 、P(o-Tol) 3 Under the catalysis, toluene is added in a nitrogen atmosphere for reaction to generate a molecular structural formula of
Figure BDA0003253156830000096
Wherein R is 1 、R 2 Is a straight-chain alkyl or branched-chain alkyl with 4-20 carbon atoms, n is a natural number which is more than or equal to 5, X is O or S, Y is O or S, when R is 2 In the case of hydrogen, Y may be Se, and the polymer is likewise subjected to Soxhlet extraction.
The embodiment of the invention also provides an all-polymer photovoltaic device which comprises an active layer, wherein the active layer comprises a polymer electron donor and a polymer electron acceptor, the polymer electron donor is the polymer containing the dithiophene [3,2-f:2',3' -h ] quinoxaline unit, or the polymer containing the dithiophene [3,2-f:2',3' -h ] quinoxaline unit prepared by the preparation method. The polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units can be combined with a polymer electron acceptor as an electron donor to have a smaller chi value, and the characteristics enable the material to have a smaller fibrous domain, a smoother appearance and smaller appearance roughness, so that the photoelectric efficiency of the all-polymer photovoltaic device can be improved.
In some embodiments, the mass ratio of the polymer donor containing dithiophene [3,2-f:2',3' -h ] quinoxaline units to the polymer electron acceptor is from 1:1 to 2. Preferably, the mass ratio of the polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units to the polymer electron acceptor is 1:1.
In some embodiments, the molecular structural formula of the polymer electron acceptor is:
Figure BDA0003253156830000101
wherein n is a natural number greater than or equal to 5. Further, in some embodiments, the polymer electron donor of the all-polymeric photovoltaic device is preferably a polymer electron donor
Figure BDA0003253156830000102
Wherein n is a natural number greater than or equal to 5, the ratio of the polymer donor to the polymer acceptor is 1:1, and the photoelectric conversion efficiency of the fully-polymerized photovoltaic device is high and can reach 14.21%.
In some embodiments, the method of preparing the polymeric electron acceptor comprises the steps of:
s31: in Pd (PPh) 3 ) 2 Cl 2 Under the catalysis of
Figure BDA0003253156830000111
Figure BDA0003253156830000112
Reacting in toluene to obtain a reaction mixture;
s32: heating and refluxing the reaction mixture, and adding the reaction mixture into MeOH to obtain a product a;
s33: performing Soxhlet extraction on the product a with MeOH, n-hexane and DCM to obtain a product b;
s34: adding the product b into MeOH, filtering and drying to obtain the polymer acceptor.
The present invention will be described in detail below with reference to specific examples.
Example 1
The polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units of this example was prepared as follows:
1. a100 mL round bottom flask that had been oven dried with a magnetic stir bar and benzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione (1.1g,5mmol) was purged with nitrogen 3 times. Ethanol (15mL) was then added followed by propane-1, 2-diamine (371mg, 5 mmol). After stirring at room temperature for 2 min, then heating at 100 ℃ overnight, the reaction mixture was cooled to room temperature and concentrated in vacuo, and the residue was purified by silica gel column chromatography (PE: DCM ═ 2:1V/V) to give the desired product a (640mg) as a light yellow solid in 50% yield.
Wherein, the detection data of the compound A are as follows:
1 H NMR(CDCl 3 ,400MHz,δ/ppm):2.84(s,3H),7.55(t,J＝10.8Hz,2H),8.26(d,J＝5.6Hz,1H),8.30(d,J＝5.2Hz,1H),8.77(s,1H)。
the synthetic route of the compound A is as follows:
Figure BDA0003253156830000121
2. compound A (128.0mg,0.5mmol) was dissolved in 20mL CHCl 3 And 20mL of acetic acid, cooled to 0 deg.C, NBS (392mg,2.2mmol) was added in 3 portions, each at 1 hour intervals. After removal of the solvent, the crude product was purified by column chromatography (silica gel) using petroleum ether/dichloromethane (3/1) as eluent to give B as a pale yellow solid (100mg, 49%).
Wherein, the detection data of the compound B are as follows:
1 H NMR(CDCl 3 ,400MHz,δ/ppm):2.83(s,3H),8.23(s,1H),8.27(s,1H),8.76(s,1H)。
the synthetic route of the compound B is as follows:
Figure BDA0003253156830000122
3. to an oven dried 100mL round bottom flask was added a magnetic stir bar, Pd (Ph) 3 P) 4 (358mg, 10 mol%) and compound B (1.28g, 3.1 mmol). Flask is put inThe nitrogen was purged three times. Tributyl (4- (2-butyloctyl) thiophen-2-yl) stannane (4.37g, 8.06mmol, 2.6equiv), toluene (30mL) and DMF (6mL) were added under a nitrogen atmosphere. Stirred at room temperature for 2 minutes and then heated at 120 ℃ for 24 hours. The reaction mixture was cooled to room temperature, then poured into saturated aqueous NaCl (200mL) and extracted 3 times with ethyl acetate. The combined organic layers were washed with saturated aqueous NaCl solution (200 mL. times.6), anhydrous MgSO 4 Dry, concentrate the solvent in vacuo, and purify the residue by silica gel column chromatography (PE: DCM ═ 4:1V/V) to obtain compound C (2g, 87%) as a viscous yellow liquid.
Wherein, the detection data of the compound C are as follows:
1 H NMR(CDCl 3 ,400MHz,δ/ppm):0.88-0.93(m,12H),1.25-1.32(m,32H),1.66(s,2H),2.55(d,J＝6.8Hz,4H),2.76(s,3H),6.87(s,2H),7.12(dd,J＝3.6,0.8Hz,2H),8.10-8.14(m,2H),8.64(s,1H)。
the synthetic route of the compound C is as follows:
Figure BDA0003253156830000131
4. compound C (378mg,0.5mmol) was dissolved in 30mL THF, then cooled to 0 deg.C and NBS (196mg,1.1mmol) was added 3 times at intervals. The reaction was kept stirring overnight, then quenched with water and extracted with DCM. The DCM extract was concentrated under vacuum and the residue was purified by silica gel column chromatography (PE: DCM ═ 4:1V/V) to give the desired product D as a yellow solid (319mg, 70%).
Wherein, the detection data of the compound D are as follows:
1 H NMR(CDCl 3 ,400MHz,δ/ppm):0.85-0.90(m,12H),1.23-1.28(m,32H),1.86(s,2H),2.51(d,J＝6.4Hz,2H),2.61(d,J＝7.2Hz,2H),2.84(s,3H),6.98-7.00(m,1H),8.13(s,1H),8.19(s,1H),8.40-8.45(m,1H),8.72-8.73(m,1H)。
the synthetic route of the compound D is as follows:
Figure BDA0003253156830000132
5. a mixture of Compound D (50.2mg,0.055mmol), BDT-F-Sn (51.8mg,0.055mmol), Pd 2 (dba) 3 (1.5mg,0.00165mmol,3 mol%) and P (o-Tol) 3 (5.05mg,0.0165mmol,30 mol%) was added to an oven dried Schlenk tube equipped with a magnetic stirrer. The nitrogen was purged 3 times. Toluene (3mL) was added under a nitrogen atmosphere. The reaction was stirred at room temperature for 2 minutes and then heated at 130 ℃ for 24 hours. The reaction mixture was cooled to room temperature, poured into chlorobenzene (100mL) and heated to 150 ℃ until all solids were dissolved, then added dropwise to methanol. Then the sediment is sequentially treated with methanol and CH 2 Cl 2 、CHCl 3 And carrying out Soxhlet extraction on chlorobenzene. The chlorobenzene solution was then added dropwise to methanol and the precipitate was collected and dried under vacuum overnight to give G (35mg, 46%) as a red-brown solid.
Wherein, the detection data of the compound G are as follows:
M n ＝38.5kDa，
Figure BDA0003253156830000141
the synthetic route of the compound G is as follows:
Figure BDA0003253156830000142
example 2
1. Reacting 5, 8-bis (4- (2-butyloctyl) thiophen-2-yl) dithieno [3',2':3, 4; 2",3":5,6]Benzo [1,2-c ]][1,2,5]Thiadiazole (645mg, 0.86mmol) and magnetons were added to a 100mL round bottom flask that had been oven dried. The flask was purged with nitrogen three times. 30mL of THF were added, followed by continuous N 2 Dropwise adding LiAlH under atmosphere 4 (655mg, 17.2mmol), a large number of bubbles were generated during the dropwise addition, and then the system was protected with a nitrogen balloon and then heated at 75 ℃ overnight. The reaction mixture was cooled to room temperature, poured into saturated aqueous NaCl solution (200mL), extracted 3 times with ethyl acetate and anhydrous NaSO 4 Drying, vacuum concentrating the solvent, and purifying the residueThe application is as follows. An oven dried 100mL round bottom flask equipped with a magnetic stir bar and the previous product (0.86mmol) was purged with nitrogen 3 times. Then 30mL of CHCl was added 3 And 10mL of acetic acid and 1, 4-dioxane-2, 3-diol (206.4mg,1.72mmol) were added, followed by heating to 60 ℃ for reaction overnight. The reaction was then poured into saturated aqueous NaCl solution (200mL) and extracted 3 times with ethyl acetate. The combined organic phases were treated with NaSO 4 Drying, concentration of the solvent in vacuo and purification of the residue by column chromatography on silica gel (PE: DCM ═ 4:1V/V) gave the desired product E as a viscous yellow liquid (265mg, 42%).
Wherein, the nuclear magnetic data of the compound E are as follows:
1 H NMR(CDCl 3 ,400MHz,δ/ppm):0.88-0.94(m,12H),1.30-1.31(m,32H),1.65(s,2H),2.55(d,J＝6.8Hz,4H),6.86(s,2H),7.10(s,2H),8.10(s,2H),8.75(s,2H). 13 C NMR(100MHz,CDCl 3 )δ143.24,142.92,138.49,137.33,136.39,135.48,133.48,126.99,121.52,119.15,39.00,35.12,33.48,33.17,32.08,29.87,29.03,26.77,23.22,22.86,14.33,14.29。
the synthetic route of the compound E is as follows:
Figure BDA0003253156830000151
2. compound E (265mg,0.36mmol) was dissolved in 30mL THF, then cooled to 0 deg.C and NBS (146mg,0.82mmol) was added 3 times at intervals of one hour. After removal of the solvent, the crude product was purified by column chromatography (silica gel) using petroleum ether to petroleum ether/dichloromethane (4/1) as eluent to give compound F as an orange solid (258mg, 80%).
Wherein, the nuclear magnetic data of the compound F are as follows:
1 H NMR(CDCl 3 ,400MHz,δ/ppm):0.88-0.93(m,12H),1.26-1.32(m,32H),1.95(s,2H),2.52(d,J＝6.8Hz,4H),7.01(s,2H),8.21(s,2H),8.88(s,2H). 13 C NMR(100MHz,CDCl 3 )δ143.16,142.67,138.49,136.39,136.07,135.64,133.42,126.43,119.48,110.29,59.66,38.70,38.29,34.39,33.49,33.20,32.08,31.39,29.86,28.93,26.68,23.23,22.87,14.32。
the synthetic route of the compound F is as follows:
Figure BDA0003253156830000161
3. a mixture of compound F (49.4mg,0.055mmol), BDT-F-Sn (51.8mg,0.055mmol), Pd 2 (dba) 3 (1.5mg,0.00165mmol,3 mol%) and P (o-Tol) 3 (5.05mg,0.0165mmol,30 mol%) was charged to an oven dried Schlenk tube equipped with a magnetic stirrer. The nitrogen was purged 3 times. Toluene (3mL) was added under a nitrogen atmosphere. The reaction was stirred at room temperature for 2 minutes and then heated at 130 ℃ for 24 hours. The reaction mixture was cooled to room temperature, poured into chlorobenzene (100mL) and heated to 150 ℃ until all solids were dissolved, then added dropwise to methanol. Then the sediment is sequentially treated with methanol and CH 2 Cl 2 、CHCl 3 And carrying out Soxhlet extraction on chlorobenzene. The chlorobenzene solution was then added dropwise to methanol, and the precipitate was collected and dried under vacuum overnight to give compound H as a red-brown solid (56.5mg, 76%).
The detection data of the compound H are as follows:
M n ＝68.8kDa，
Figure BDA0003253156830000162
the synthetic route of the compound H is as follows:
Figure BDA0003253156830000163
example 3
Synthesis of polymer receptor:
to an oven dried round bottom flask was added gamma-Br-BTIC (100mg, 0.0533mmol, 1.00equiv), 2, 5-bis (trimethylstannyl) thieno [3,2-b [ ]]Thiophene (28.0mg, 0.0533mmol), 1.00equiv) and Pd (PPh) 3 ) 2 Cl 2 (1.10mg, 0.000160mmol, 0.0300 equiv). The reaction flask was purged with nitrogen for 3 times, and toluene was added(5.30 mL). The reaction mixture was heated to 110 ℃ and refluxed for 48 hours. The mixture was added to MeOH (200mL) and the collected product was soxhlet extracted with MeOH, n-hexane, DCM. The polymer obtained from DCM was added to MeOH (200 mL). After filtration, the solid was collected and dried in vacuo to give compound I (92mg, 89%).
Wherein, the detection data of the compound I are as follows:
M n ＝10.6kDa，
Figure BDA0003253156830000171
the synthetic route of the compound I is as follows:
Figure BDA0003253156830000172
example 4
The preparation process of the full polymer photovoltaic device comprises the following steps:
the ITO-coated glass substrate was washed with deionized water, acetone, and isopropanol, respectively, once for 30 minutes, and dried in an oven at 80 ℃ for 12 hours before use. The ITO glass was then placed in UV ozone for 15 minutes and a PEDOT: PSS film was spin coated onto the ITO substrate, followed by heat treatment at 100 ℃ for 15 minutes and cooling to room temperature under vacuum. Reacting compound G or H: a mixture of Compound I (1:1wt/wt) was dissolved in chloroform solution, and a small amount of 1-CN (1.0%, v/v) was added to obtain a solution of 9mg/mL at room temperature. The active layer was spin-coated at 3000rpm for 45 seconds to obtain a blended film. The blended film was then annealed at 100 ℃ for 10 minutes. 0.5mg mL of -1 A methanol solution of PNDIT-F3N was spin coated on top of the active layer. Finally, a 100nm Ag layer was deposited by vacuum deposition in defined areas (0.045 cm) 2 )。
Example 5
The preparation process of the full polymer photovoltaic device comprises the following steps:
the ITO-coated glass substrate was washed with deionized water, acetone, and isopropanol, respectively, once for 30 minutes, and dried in an oven at 80 ℃ for 12 hours before use. Then IT will beThe O glass was placed in UV ozone for 15 minutes and a PEDOT: PSS film was spin coated onto the ITO substrate, followed by heat treatment at 100 ℃ for 15 minutes and cooling to room temperature under vacuum. Reacting compound G or H: a mixture of Compound I (1:1.2wt/wt) was dissolved in chloroform solution, and a small amount of 1-CN (1.0%, v/v) was added to obtain a solution of 9mg/mL at room temperature. The active layer was spin-coated at 3000rpm for 45 seconds to obtain a blended film. The blended film was then annealed at 100 ℃ for 10 minutes. 0.5mg mL of -1 A methanol solution of PNDIT-F3N was spin coated on top of the active layer. Finally, a 100nm Ag layer was deposited by vacuum deposition in defined areas (0.045 cm) 2 )。
Example 6
The preparation process of the full polymer photovoltaic device comprises the following steps:
the ITO-coated glass substrate was washed with deionized water, acetone, and isopropanol, respectively, once for 30 minutes, and dried in an oven at 80 ℃ for 12 hours before use. The ITO glass was then placed in UV ozone for 15 minutes and a PEDOT: PSS film was spin coated onto the ITO substrate, followed by heat treatment at 100 ℃ for 15 minutes and cooling to room temperature under vacuum. Reacting compound G or H: a mixture of Compound I (1:1.5wt/wt) was dissolved in chloroform solution, and a small amount of 1-CN (1.0%, v/v) was added to obtain a solution of 9mg/mL at room temperature. The active layer was spin-coated at 3000rpm for 45 seconds to obtain a blended film. The blended film was then annealed at 100 ℃ for 10 minutes. 0.5mg mL of -1 A methanol solution of PNDIT-F3N was spin coated on top of the active layer. Finally, a 100nm Ag layer was deposited by vacuum deposition in defined areas (0.045 cm) 2 )。
Example 7
The preparation process of the full polymer photovoltaic device comprises the following steps:
the ITO-coated glass substrate was washed with deionized water, acetone, and isopropanol, respectively, once for 30 minutes, and dried in an oven at 80 ℃ for 12 hours before use. The ITO glass was then placed in UV ozone for 15 minutes and a PEDOT: PSS film was spin coated onto the ITO substrate, followed by heat treatment at 100 ℃ for 15 minutes and cooling to room temperature under vacuum. Reacting compound G or H: a mixture of Compound I (1:1wt/wt) is dissolved in chloroform solution and a small amount of 1-CN (0.5%, v-v) to obtain a solution of 9mg/mL at room temperature. The active layer was spin-coated at 3000rpm for 45 seconds to obtain a blended film. The blended film was then annealed at 100 ℃ for 10 minutes. 0.5mg mL of -1 A methanol solution of PNDIT-F3N was spin coated on top of the active layer. Finally, a 100nm Ag layer was deposited by vacuum deposition in defined areas (0.045 cm) 2 )。
Example 8
The preparation of an all-polymer photovoltaic device was as follows (different solvent additive ratio from example 4):
the ITO-coated glass substrate was washed with deionized water, acetone, and isopropanol, respectively, once for 30 minutes, and dried in an oven at 80 ℃ for 12 hours before use. The ITO glass was then placed in UV ozone for 15 minutes and a PEDOT: PSS film was spin coated onto the ITO substrate, followed by heat treatment at 100 ℃ for 15 minutes and cooling to room temperature under vacuum. Reacting compound G or H: a mixture of Compound I (1:1wt/wt) was dissolved in chloroform solution, and a small amount of 1-CN (1.5%, v/v) was added to obtain a solution of 9mg/mL at room temperature. The active layer was spin-coated at 3000rpm for 45 seconds to obtain a blended film. The blended film was then annealed at 100 ℃ for 10 minutes. 0.5mg mL of -1 A methanol solution of PNDIT-F3N was spin coated on top of the active layer. Finally, a 100nm Ag layer was deposited by vacuum deposition in defined areas (0.045 cm) 2 )。
And (4) testing results:
(1) the polymers prepared in examples 1 to 3 were tested for their absorption spectra in the chlorobenzene solution and thin film state using a UV-visible spectrophotometer, in which the optical band gap of the polymer was determined using an empirical formula (E) g opt ＝1240/λ onset film ) Wherein λ is onset film FIG. 1 shows the absorption spectrum of the polymer-containing solution in diluted chlorobenzene in examples 1 to 3, and FIG. 2 shows the absorption spectrum of the polymer-containing solution in solid thin film in examples 1 to 3, as the absorption edge of the absorption spectrum of the polymer in the thin film.
The strongest absorption (. lamda.) of the polymers containing examples 1-3 was calculated by UV-visible absorption spectroscopy and empirical formula for optical band gap max sol And λ max film ) And optical bandgap (E) g opt ) The following:
example 1: lambda [ alpha ] max sol ＝564nm；λ max film ＝536nm；λ onset film ＝619nm；E g opt ＝2.00eV；
Example 2: lambda [ alpha ] max sol ＝569nm；λ max film ＝570nm；λ onset film ＝621nm；E g opt ＝2.00eV；
Example 3: lambda [ alpha ] max sol ＝762nm；λ max film ＝795nm；λ onset film ＝876nm；E g opt ＝1.42eV；
(2) Measurement of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) of the polymers prepared in examples 1-3, and bandgap (E) g ec ) And (4) calculating.
The polymers prepared in examples 1 to 3 were each dissolved in chlorobenzene to prepare a solution having a concentration of 6mg/mL, and the solution was dropped onto a working electrode (dropping diameter: 2 mm). Use of 0.1M Bu 4 NPF 6 The acetonitrile solution is used as electrolyte, platinum wire is used as counter electrode, Ag/Ag + As reference electrode, ferrocene was the standard. Measuring the oxidation-reduction potential by electrochemical cyclic voltammetry, and calculating the Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO) and band gap (E) g ec )。
Among them, the electrochemical cyclic voltammograms of the polymers prepared in examples 1 to 3 are shown in FIG. 3.
Wherein, the calculation formulas of the HOMO and the LUMO of the polymer are as follows:
E HOMO ＝-E ox +[(-4.8)+0.044](eV)
E LUMO ＝-E red +[(-4.8)+0.044](eV)
wherein E is ox And E red To measure the resulting redox potential. The Highest Occupied Molecular Orbital (HOMO) and lowest unoccupied molecular orbital (HOMO) of the polymers prepared in examples 1-3 were obtainedMolecular Orbital (LUMO) and band gap (E) g ec ) The following were used:
example 1: e HOMO ＝-5.57eV；E LOMO ＝-3.57eV；E g ec ＝2.00eV；
Example 2: e HOMO ＝-5.60eV；E LOMO ＝-3.60eV；E g ec ＝2.00eV；
Example 3: e HOMO ＝-5.67eV；E LOMO ＝-4.25eV；E g ec ＝1.42eV；
(3) Example 4 all-polymer solar cell in a glove box filled with nitrogen using an AAA grade solar simulator AM 1.5G (100 mW/cm) 2 ) The open circuit voltage (V) of the device of example 4 was tested at OC ) Short-circuit current (J) SC ) Fill Factor (FF), and energy conversion efficiency (PCE). Fig. 4 is a J (current power) -V (voltage) graph of the device of example 4, and table 1 shows the open circuit voltage, short circuit current, fill factor and energy conversion efficiency of the device of example 4.
TABLE 1
Figure BDA0003253156830000211
(5) The external quantum conversion efficiency of the device of example 4 was tested:
to further understand the effect of molecular trimming on the performance of the all-polymer solar cell, the external quantum efficiency curve of the polymer photovoltaic device of example 4 was tested using DSR 100UV-B of the beijing zhuliham optical instrument, as shown in figure 5. Both polymer-based devices exhibit a broad range of photoresponses from 300 to 900nm, resulting from complementary absorption between the corresponding polymer donor and acceptor.
In conclusion, the invention constructs a polymer donor structure containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, the molecular structure of the polymer donor is finely adjusted to enable the polymer donor structure to be more matched with a polymer acceptor in the aspects of absorption spectrum and energy level, and simultaneously, the appearance favorable for carrier transmission is formed, so that the full polymer solar cell with higher photoelectric conversion efficiency is realized.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.

Claims (9)

1. Containing dithiophene [3,2-f:2',3' -h]A polymer of quinoxaline units, characterized in that the polymer contains dithiophene [3,2-f:2',3' -h]The general formula of the molecular structure of the polymer of the quinoxaline unit is
Figure FDA0003800905130000011
Wherein when R is 2 When the alkyl group is a straight-chain alkyl or branched-chain alkyl group having 4 to 20 carbon atoms, R 1 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is hydrogen or methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S, Y is O or S; when R is 2 When it is hydrogen, R 1 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is hydrogen or methyl or other alkyl chain, n is a natural number greater than or equal to 5, X is O or S, and Y is Se.
2. The polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units according to claim 1, wherein the number average molecular weight of the polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units is 38000-100000, the weight average molecular weight is 60000-500000, and the dispersity is 1.8-4.3.
3. The dithiophene [3,2-f:2',3' -h ] quinoxaline unit-containing polymer according to claim 1, wherein the dithiophene [3,2-f:2',3' -h ] quinoxaline unit-containing polymer is of one of the following structural formulae:
Figure FDA0003800905130000012
4. a method for preparing a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, comprising the steps of:
s11: will be provided with
Figure FDA0003800905130000021
Reacting in ethanol to generate a molecular structure of
Figure FDA0003800905130000022
A first intermediate of (1), R 3 Is methyl or other alkyl chain;
s12: dissolving the first intermediate in CH 3 Cl and acetic acid, then adding NBS for reaction to generate a molecular structure of
Figure FDA0003800905130000023
A second intermediate of (a);
s13: reacting the second intermediate in Pd (Ph) 3 P) 4 Under the catalysis of (2), adding into a nitrogen atmosphere
Figure FDA0003800905130000024
Toluene and DMF react to generate a molecular structure of
Figure FDA0003800905130000025
When R is a third intermediate of 2 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain; y is O or S; when R is 2 When it is hydrogen, R 3 Is methyl or other alkyl chain, Y is Se;
s14: dissolving the third intermediate in THF, adding NBS for reaction to generate a molecular structure of
Figure FDA0003800905130000026
A fourth intermediate of (4);
s15: reacting said fourth intermediate with
Figure FDA0003800905130000027
In Pd 2 (dba) 3 、P(o-Tol) 3 Adding toluene to react under a catalytic system and a nitrogen atmosphere to prepare a mixture, and performing Soxhlet extraction on the mixture to obtain a compound with a molecular structural formula
Figure FDA0003800905130000031
Wherein when R is 2 When the alkyl group is a straight-chain alkyl or branched-chain alkyl group having 4 to 20 carbon atoms, R 1 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain, n is a natural number which is more than or equal to 5, X is O or S, and Y is O or S; when R is 2 When it is hydrogen, R 1 Is a straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, R 3 Is methyl or other alkyl chain, n is a natural number which is more than or equal to 5, X is O or S, and Y is Se.
5. The method for producing a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units according to claim 4, wherein the step of post-treating the reaction mixture in step S15 comprises:
s151: pouring the reaction mixture into chlorobenzene, and heating until all solids are dissolved to obtain a solution a;
s152: dropwise adding the solution a into methanol to obtain a precipitate a;
s153: sequentially using methanol and CH for the sediment a 2 Cl 2 、CHCl 3 Performing Soxhlet extraction on chlorobenzene to obtain a solution b;
s154: and dropwise adding the solution b into methanol to obtain a sediment b, and drying the sediment b to obtain the polymer.
6. A method for preparing a polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline units, comprising the steps of:
s21: will be provided with
Figure FDA0003800905130000032
Adding into THF solution, adding LiAlH under nitrogen atmosphere 4 The molecular structural formula of the reaction product is
Figure FDA0003800905130000041
Wherein R is 2 Is straight-chain alkyl or branched-chain alkyl of 4-20 carbon atoms, Y is O or S, when R is 2 Y is Se when hydrogen is present;
s22: dissolving the first intermediate product in CHCl 3 Adding 1, 4-dioxane-2, 3-diol into acetic acid to react to produce the product with molecular structural formula
Figure FDA0003800905130000042
A second intermediate product of (a);
s23: dissolving the second intermediate product in THF, adding NBS for reaction to generate a molecular structural formula of
Figure FDA0003800905130000043
A third intermediate product of (a);
s24: the third intermediate product and
Figure FDA0003800905130000044
in Pd 2 (dba) 3 、P(o-Tol) 3 Under the catalysis, toluene is added in a nitrogen atmosphere for reaction to generate a molecular structural formula of
Figure FDA0003800905130000045
Wherein when R is 2 When the alkyl group is a straight-chain alkyl or branched-chain alkyl group having 4 to 20 carbon atoms, R 1 Is straight-chain alkyl or branched-chain alkyl with 4-20 carbon atoms, n is a natural number which is more than or equal to 5, X is O or S, and Y is O or S; when R is 2 When it is hydrogen, R 1 Is straight-chain alkyl or branched-chain alkyl with 4-20 carbon atoms, n is a natural number which is more than or equal to 5, X is O or S, Y is Se, and the polymer is also subjected to Soxhlet extraction.
7. An all-polymer photovoltaic device comprising an active layer comprising a polymer electron donor and a polymer electron acceptor, wherein the polymer electron donor is the polymer containing a dithieno [3,2-f:2',3' -h ] quinoxaline unit according to any one of claims 1 to 3, or the polymer containing a dithieno [3,2-f:2',3' -h ] quinoxaline unit prepared by the preparation method according to any one of claims 4 to 6.
8. The all-polymer photovoltaic device according to claim 7, wherein the molecular structural formula of the polymer electron acceptor is:
Figure FDA0003800905130000051
wherein n is a natural number greater than or equal to 5.
9. The all-polymer photovoltaic device according to claim 8, wherein the mass ratio of the polymer electron donor to the polymer electron acceptor is 1: 1-2.
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