CN110713589B - Anthracene diimide bromide and preparation and application of polymer thereof - Google Patents

Anthracene diimide bromide and preparation and application of polymer thereof Download PDF

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CN110713589B
CN110713589B CN201810768002.3A CN201810768002A CN110713589B CN 110713589 B CN110713589 B CN 110713589B CN 201810768002 A CN201810768002 A CN 201810768002A CN 110713589 B CN110713589 B CN 110713589B
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toluene
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李�灿
涂丹丹
郭鑫
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a synthesis method of anthracene diimide bromide isomers brominated at two different sites, an anthracene diimide high molecular material based on the two bromide isomers, and application thereof in the field of organic electronic devices. The selective control of the bromination of the anthracene diimide at different sites is realized by two synthetic methods of pre-bromination and post-bromination. The anthracene diimide high molecular material of the invention keeps the advantages of diimide six-membered rings of imide classical materials (such as naphthalene diimide and perylene diimide) on one hand, and expands the conjugation degree in the direction vertical to the diimide six-membered rings on the other hand, thereby avoiding the problem of increased steric hindrance caused by conjugation expansion. The controllable bromination of different substitution sites of the anthracene diimide provides a new construction unit for the design of n-type organic semiconductor materials, and also provides material support for the development of organic electronic devices such as organic field effect transistors, solar cells and the like.

Description

Anthracene diimide bromide and preparation and application of polymer thereof
Technical Field
The invention relates to the field of organic semiconductors, in particular to a preparation method of two anthracene diimide isomers brominated at different sites and macromolecules thereof, and the anthracene diimide isomers and the macromolecules thereof are applied to organic electronic devices.
Background
Organic semiconductors are widely used in organic electronic devices such as Organic Field Effect Transistors (OFETs) and organic solar cells (OPVs). Compared with a wide variety of p-type organic semiconductors, n-type organic semiconductors are of a single kind and have relatively slow development. At present, the widely applied n-type polymer materials mainly comprise Naphthalene Diimide (NDI) and Perylene Diimide (PDI) materials. The properties such as absorption, energy level, crystallinity and molecular configuration of the polymer can be adjusted by changing a copolymerization unit, adjusting the length of a solubilizing group, introducing a heteroatom (such as S, O, F, Se) for regulating and controlling intramolecular/intermolecular interaction and the like, but the properties of NDI and PDI polymers cannot be fundamentally changed. From the viewpoint of material type and performance, development of a novel n-type building block and a polymer material thereof is required.
The key point of developing n-type high polymer materials is that the conjugation degree is expanded, the LUMO/HOMO energy level is reduced, and good stability is achieved. However, the phenyl aromatic fused ring type imide materials have been slowly developed because of the great difficulty in synthesis. Based on the above, the invention discloses preparation methods of anthracene diimide bromide isomers with different site bromination and anthracene diimide high-molecular materials with different polymerization sites, which break through the difficult problems of substitution and selectivity of anthracene diimide at different sites, provide a new construction unit for the development of n-type organic semiconductor materials, and have great application prospects in organic electronic devices.
Disclosure of Invention
One of the purposes of the invention is to selectively brominate at two groups of symmetrical and substitutable sites of anthracene diimide to synthesize two anthracene diimide bromide isomers, and further synthesize a novel anthracene diimide high molecular material with different main chain conformations.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the anthracene diimide bromide isomer material with two kinds of anthracene diimide bromide at different sites is characterized in that the chemical structural formula is any one of the following formulas:
Figure BDA0001729522000000021
the symbols and indices in the formula have the following meanings:
R1,R2are the same or different and are each one of the structures shown below:
Figure BDA0001729522000000022
o, m, n, x and y are the same or different, and the value range is as follows: 50 is more than or equal to o, m, n, x and y are more than or equal to 0, and the optimal range is as follows: 15 is more than or equal to o, m, n, x and y are more than or equal to 6.
R3-R7Are identical or different and are each one of the following structural units:
Figure BDA0001729522000000023
the polymer of two anthracene diimide bromides is characterized in that one or more than two of the following chemical structural formulas are connected:
Figure BDA0001729522000000024
ar is one or more than two of the following structural units:
Figure BDA0001729522000000031
r 'and R' are the same or different and each is one of the structures shown below:
Figure BDA0001729522000000032
a, b, c, d and e are the same or different, and the value range is as follows: 50 is more than or equal to a, b, c, d and e is more than or equal to 0, and the optimal range is as follows: 15 is more than or equal to a, b, c, d, e is more than or equal to 6.
The invention also aims to provide application of the anthracene diimide high molecular material with different main chain conformations in an organic electronic device. Taking the polymer material A, F in examples 8 and 11 as an example, the polymer material is used as an active layer acceptor material of an organic solar cell, and PTB7-Th is used as a donor material, so as to prepare the organic solar cell.
The technical scheme for solving the technical problems is as follows: the preparation of anthracene diimide bromide isomer with different bromization sites and high molecular material and its application in organic electronic device are disclosed.
The terms:
"DBH" refers to 1,3-dibromo-5,5-dimethylhydantoin, named 1,3-dibromo-5,5-dimethylhydantoin in Chinese.
“P(o-tolyl)3", refers to tris (o-methylphenyl) phosphorus.
“Pd2(dba)3", refers to three (two benzylidene acetonates) dipalladium.
"PTB 7-Th" refers to poly [ [4,8-bis [5- (2-ethylhexyl) -2-thienyl ] benzol [1,2-b:4,5-b0] dithiophene-2,6-diyl ] [2- [ [ (2-ethylhexyl) oxy ] carbonyl ] -3-fluorothieno [3,4-b ] thiophene ] ].
The invention has the beneficial effects that:
1. according to the preparation method of the anthracene diimide bromide isomer, the bromination sites can be selectively controlled by the methods of pre-bromination and post-bromination. The two groups of symmetrical and bromine substitutable positions provide multiple possibilities for synthesizing the anthracene diimide material.
2. The anthracene diimide high-molecular material provided by the invention has the advantages that the reaction at different sites can be accurately controlled, so that the molecular configuration, crystallinity, energy level and other physical and chemical properties of the anthracene diimide high-molecular material are easy to regulate and control.
3. The synthesis of the anthracene diimide of the novel organic semiconductor electron-pulling construction unit can greatly enrich the variety of n-type organic semiconductors and has wide application prospect in organic electronic devices.
Drawings
FIG. 1 shows the UV-VIS absorption spectra of the methylene chloride solutions of examples 1 and 4.
FIG. 2 shows cyclic voltammograms of example 8 and example 11.
FIG. 3 shows the UV-VIS absorption spectra of examples 8 and 11.
Fig. 4 is an organic solar cell inverted device structure described in example 14.
Fig. 5 is a current density-voltage curve for devices prepared as the organic solar cell acceptor material of example 8 and example 11.
Detailed description of the invention
The following examples illustrate the present invention in more detail, but are not intended to limit the invention thereto.
The procedure for the synthesis of the intermediate compounds required in the synthesis examples is as follows:
synthesis of Compound 6:
12.2467g (24.8mmol) of Compound 5 and 70mL of dehydrated ether were stirred at room temperature for 0.5 hour under an argon atmosphere, 31.7mL (50.84mmol) of a 1.6M n-butyllithium n-hexane solution was slowly added thereto at 0 ℃, the mixture was stirred at room temperature for 2 hours after completion of the addition, an excess of dry ice was added to the mixture, water was added to the mixture after completion of the reaction, the organic phase was separated, the aqueous phase was made acidic with 6M hydrochloric acid solution, and the mixture was stirred for 1 hour and then filtered to obtain Compound 6 (yield > 90%).
The synthetic route is as follows:
Figure BDA0001729522000000051
example 1
1.8188g (6mmol) of Compound 1 and 4.8043g (36mmol) of aluminum chloride were dissolved in 80mL of anhydrous o-dichlorobenzene under an argon atmosphere, and stirred at room temperature for 15 minutes, then 29.1204g (0.09mol) of Compound 2a was added, and the mixture was refluxed at 180 ℃ for 12 hours, and the solvent was distilled off under reduced pressure to obtain Compound 3a by column separation. After 1g (2.06mmol) of compound 3a was dissolved in 8mL of concentrated sulfuric acid and stirred at 60 ℃ for 4 hours, the brominating reagent DBH 5.8907g (20.6mmol) was added in portions and reacted for 15 hours, and the reaction solution was diluted with water and extracted with dichloromethane, dried, filtered, and subjected to column separation to obtain red compound 4 a.1H NMR(400MHz,CDCl3)：δ＝10.54(s,2H), 8.88(s,2H),4.21(t,J＝7.3Hz,4H),2.06-2.02(m,2H),1.42-1.22(m,60Hz),0.86(t, J＝7.0Hz,12H)ppm，13C NMR(101MHz,CDCl3): δ is 163.90,162.17,137.15,131.19, 127.76,125.98,123.88,77.33,54.62,45.25,36.50,31.91,31.88,31.65,31.31,30.04, 29.70,29.65,29.62,29.56,29.34,29.30,28.40,26.41,25.04,22.66,14.12 ppm. The ultraviolet visible absorption is shown in figure 1 (the wavelength of the maximum absorption position of the ultraviolet visible absorption is respectively 401nm, 422nm, 462nm and 494nm), and the specific synthetic route is as follows:
Figure BDA0001729522000000052
example 2
1.8188g (6mmol) of Compound 1 and 4.8043g (36mmol) of aluminum chloride were dissolved in 80mL of anhydrous o-bis under an argon atmosphereChlorobenzene was stirred at room temperature for 15 minutes, then 11.4471g (0.09mol) of Compound 2b was added, the mixture was refluxed at 180 ℃ for 12 hours, the reagent was distilled off under reduced pressure, and the compound 3b was isolated by column chromatography. After 1g (2.06mmol) of compound 3b was dissolved in 8mL of concentrated sulfuric acid and stirred at 50 ℃ for 4 hours, 0.8835g (3.09mmol) of DBH as a brominating reagent was added in portions and reacted for 10 hours, and the reaction solution was diluted with water and extracted with dichloromethane, dried, filtered, and subjected to column separation to obtain red compound 4 b.1HNMR(400MHz,CDCl3) δ 10.60(s,2H),8.90(s,2H), 4.27(t, J7.68 Hz,4H),1.81-1.77(m,4H),1.37-1.25(m,10Hz),0.93(t, J7.0 Hz,6H) ppm. The specific synthetic route is as follows:
Figure BDA0001729522000000061
example 3
1.8188g (6mmol) of Compound 1 and 4.8043g (36mmol) of aluminum chloride were dissolved in 80mL of anhydrous o-dichlorobenzene under an argon atmosphere, stirred at room temperature for 15 minutes, then 19.0215g (0.09mol) of Compound 2c was added, reflux was carried out at 180 ℃ for 12 hours, the reagents were distilled off under reduced pressure, and the compound 3c was isolated by column chromatography. After 1g (2.06mmol) of compound 3c was dissolved in 8mL of concentrated sulfuric acid and stirred at 50 ℃ for 4 hours, 2.3563g (8.24mmol) of DBH as a brominating reagent was added in portions and reacted for 10 hours, and the reaction solution was diluted with water and extracted with dichloromethane, dried, filtered, and subjected to column separation to obtain red compound 4 c. The specific synthetic route is as follows:
Figure BDA0001729522000000062
example 4
2.5442g (6mmol) of Compound 6 was added to 20mL of thionyl chloride, refluxed for 2 hours, and then excess thionyl chloride was distilled off to give Compound 7, Compound 7 and 4.8043g (36mmol) of aluminum trioxide were dissolved in 80mL of anhydrous o-dichlorobenzene under an anhydrous and oxygen-free argon atmosphere, stirred at room temperature for 10 minutes, then 29.1204g (0.09mol) of Compound 2a was added, reacted at 180 ℃ for 12 hours, and then o-dichlorobenzene was distilled under reduced pressure to give Compound 7The residue was taken up in dichloromethane and the column separated to give the yellow compound 8 a.1H NMR(400 MHz,CDCl3)δ10.09(d,J＝9.8Hz,2H),7.95(d,J＝9.8Hz,2H),4.25(t,J＝7.4Hz,4H), 2.07-2.04(m,2H),1.42-1.21(m,60Hz),0.86(t,J＝7.4Hz,12H)ppm。13C NMR(101 MHz,CDCl3)：δ＝163.60,161.35,142.66,140.97,134.57,133.42,129.68,55.42, 49.29,45.36,38.38,36.53,31.91,31.88,31.68,30.07,29.65,29.62,29.59,29.54,29.34, 29.31,26.38,22.68,22.66,20.12,14.11ppm。13C NMR (101MHz, CDCl 3): δ is 163.90,162.17,137.15,131.19,127.76,125.98,123.88, 77.33,54.62,45.25,36.50,31.91,31.88,31.65,31.31,30.04, 29.70,29.65,29.62,29.56,29.34,29.30,28.40,26.41,25.04,22.66,14.12 ppm. The ultraviolet-visible absorption is shown in fig. 1, and the wavelengths of the maximum absorption positions of the ultraviolet-visible absorption are respectively as follows: 396nm, 416nm, 442nm, 471 nm. The specific synthetic route is as follows:
Figure BDA0001729522000000071
example 5
2.5442g (6mmol) of compound 6 was added to 20mL of thionyl chloride, refluxed for 2 hours, and then excess thionyl chloride was distilled off to give compound 7, 4.8043g (36mmol) of aluminum trioxide were dissolved in 80mL of anhydrous o-dichlorobenzene under an atmosphere of anhydrous and oxygen-free argon, stirred at room temperature for 10 minutes, then 11.4471g (0.09mol) of compound 2b was added, reacted at 180 ℃ for 12 hours, then o-dichlorobenzene was distilled off under reduced pressure, the residue was dissolved in dichloromethane, and column separation gave yellow compound 8 b.1HNMR(400MHz, CDCl3) δ 10.16(d, J9.7 Hz,2H),7.96(d, J9.7 Hz,2H),4.29(t, J7.6 Hz,4H), 1.83-1.77(m,4H),1.48-1.37(m,10Hz),0.93(t, J6.9 Hz,6H) ppm. The specific synthetic route is as follows:
Figure BDA0001729522000000081
example 6
2.5442g (6mmol) of compound 6 was added to 20mL of thionyl chloride, refluxed for 2 hours, and then excess thionyl chloride was distilled off to give compound 7, 4.8043g (36mmol) of aluminum trioxide were dissolved in 80mL of anhydrous o-dichlorobenzene under an atmosphere of anhydrous and oxygen-free argon, stirred at room temperature for 10 minutes, then 19.0215g (0.09mol) of compound 2c was added, reacted at 180 ℃ for 12 hours, then o-dichlorobenzene was distilled off under reduced pressure, the residue was dissolved in dichloromethane, and a yellow compound 8c was obtained after column separation.1HNMR(400MHz, CDCl3)δ10.17(d,J＝9.8Hz,2H),7.96(d,J＝9.8Hz,2H),4.29(t,J＝7.6Hz,4H), 1.82-1.77(m,4H),1.54-1.26(m,36H),0.89(t,J＝6.7Hz,6H)ppm。13C NMR (101MHz, CDCl 3): δ 186.68,163.18,150.11,142.79,134.60,129.71,118.32,41.64,31.93, 29.66,29.64,29.60,29.36,28.04,27.25,22.70,14.13 ppm. The specific synthetic route is as follows:
Figure BDA0001729522000000082
example 7
2.5442g (6mmol) of compound 6 was added to 20mL of thionyl chloride, refluxed for 2 hours, and then excess thionyl chloride was distilled off to obtain compound 7, 4.8043g (36mmol) of aluminum trioxide were dissolved in 80mL of anhydrous o-dichlorobenzene under an atmosphere of anhydrous and oxygen-free argon, stirred at normal temperature for 10 minutes, then 13.9716g (0.09mol) of compound 2d was added, reacted at 180 ℃ for 12 hours, then o-dichlorobenzene was distilled out under reduced pressure, the residue was dissolved in dichloromethane, and column separation was performed to obtain yellow compound 8 d.1H NMR (400MHz,CDCl3) δ 10.10(d, J9.8 Hz,2H),7.96(d, J9.8 Hz,2H),4.25(t, J7.4 Hz,4H), 2.07-2.02(m,2H),1.42-1.21(m,16Hz),0.86(t, J7.4 Hz,12H) ppm. The specific synthetic route is as follows:
Figure BDA0001729522000000091
example 8
Synthesis of Polymer A
Under argon atmosphere, compounds 4a, 5-bistrimethylstannyl-2, 2' -bithiophene and Pd2(dba)3、 P(o-tolyl)3The molar ratio is as follows: 1:1:0.04: 0.08 and toluene are mixed and stirred, reacted for 1 day at 110 ℃, and then bromobenzene is added for end capping. After the reaction, the reaction solution was precipitated with a mixed solvent of dilute hydrochloric acid (1 mol/l)/methanol (volume ratio 1:8), filtered, extracted with acetone, n-hexane, and chloroform in this order with a Soxhlet extractor, and then precipitated with methanol to obtain Polymer A. The cyclic voltammetry curves and the uv-vis absorption spectra are shown in fig. 2 and 3, and the LUMO and HOMO of polymer a measured by cyclic voltammetry were-4.02 eV and-5.43 eV, respectively. The maximum absorption peaks of polymer a were respectively: 444nm and 740 nm. The degree of polymerization PDI was 2.28. The synthetic route is as follows:
Figure BDA0001729522000000092
example 9
Synthesis of Polymer B
Under argon atmosphere, compounds 4a, 2, 5-bis (trimethylstannyl) thiophene and Pd2(dba)3、P(o-tolyl)3The molar ratio is as follows: 1:1:0.04: 0.08 and toluene are mixed and stirred, reacted for 1 day at 110 ℃, and then bromobenzene is added for end capping. After the reaction, the reaction mixture was precipitated with a mixed solvent of dilute hydrochloric acid (1 mol/l)/methanol (volume ratio 1:8), filtered, extracted with acetone, n-hexane, and chloroform in this order with a soxhlet extractor, and then precipitated with methanol to obtain polymer B having a degree of polymerization PDI of 2.15. The synthetic route is as follows:
Figure BDA0001729522000000101
example 10
Synthesis of Polymer E
Under argon atmosphere, compounds 4c, (3, 3-twenty-two-radical-2, 2-bithiophene-5, 5-two-radical) bi (trimethyl tin) and Pd2(dba)3、P(o-tolyl)3The molar ratio is as follows: 1:1:0.04: 0.08 and toluene are mixed and stirred, reacted for 1 day at 110 ℃, and then bromobenzene is added for end capping. After the reaction, the reaction solution was precipitated with a mixed solvent of dilute hydrochloric acid (1 mol/l)/methanol (volume ratio 1:8), filtered, extracted with acetone, n-hexane, and chloroform in this order with a Soxhlet extractor, and then precipitated with methanol to obtain Polymer E. The synthetic route is as follows:
Figure BDA0001729522000000102
example 11
Synthesis of Polymer F
Under argon atmosphere, compounds 8a, 5-bistrimethylstannyl-2, 2' -bithiophene and Pd2(dba)3、 P(o-tolyl)3The molar ratio is as follows: 1:1:0.04: 0.08 and toluene are mixed and stirred, reacted for 1 day at 110 ℃, and then bromobenzene is added for end capping. After the reaction is finished, the reaction solution is settled by using a mixed solvent of diluted hydrochloric acid (1 mol/L)/methanol (volume ratio is 1:8), filtered, extracted by using a Soxhlet extractor sequentially using acetone, normal hexane and chloroform reagents, and then settled by using methanol to obtain a polymer F. The cyclic voltammetry curves and the uv-vis absorption spectra are shown in fig. 2 and 3, and the LUMO of polymer F measured by cyclic voltammetry is-4.06 eV and the HOMO is-5.44 eV. The maximum absorption peaks of polymer a were respectively: 411nm, 477nm and 700 nm. The synthetic route is as follows:
Figure BDA0001729522000000111
example 12
Synthesis of Polymer G
Under argon atmosphere, compounds 8a, 2, 5-bis (trimethylstannyl) thiophene and Pd2(dba)3、P(o-tolyl)3The molar ratio is as follows: 1:1:0.04: 0.08 and toluene are mixed and stirred, reacted for 1 day at 110 ℃, and then bromobenzene is added for end capping. After the reaction is finished, the reaction solution is mixed with a mixed solvent of diluted hydrochloric acid (1 mol/L)/methanol (volume ratio is 1:8)The mixture was precipitated, filtered, extracted with acetone, n-hexane, and chloroform in this order using a soxhlet extractor, and then precipitated with methanol to obtain polymer G having a degree of polymerization PDI of 3.75. The synthetic route is as follows:
Figure BDA0001729522000000112
example 13
Synthesis of Polymer J
Under argon atmosphere, compounds 8c, (3, 3-twenty-two-radical-2, 2-bithiophene-5, 5-two-radical) bi (trimethyl tin) and Pd2(dba)3、P(o-tolyl)3The molar ratio is as follows: 1:1:0.04: 0.08 and toluene are mixed and stirred, reacted for 1 day at 110 ℃, and then bromobenzene is added for end capping. After the reaction is finished, the reaction solution is settled by using a mixed solvent of dilute hydrochloric acid (1 mol/L)/methanol (volume ratio is 1:8), filtered, extracted by using a Soxhlet extractor sequentially using acetone, normal hexane and chloroform reagents, and then settled by using methanol to obtain a polymer J. The synthetic route is as follows:
Figure BDA0001729522000000121
example 14
The anthracene diimide macromolecule is used as an acceptor material in the application of the organic solar cell.
An organic solar cell device with an inverted structure is shown in figure 4, and each layer sequentially comprises a glass substrate/ITO cathode 1, a ZnO layer 2, an active layer 3 consisting of a donor material, namely an anthracene diimide high polymer material, and a hole transport layer MoO 34 and Ag electrodes 5.
The preparation process of the organic solar cell device comprises the following steps:
(1) cleaning the ITO glass: and (3) sequentially carrying out ultrasonic treatment on the ITO film for 15-20 minutes by using deionized water, acetone, ethanol, isopropanol and ethanol, blowing the residual ethanol on the ITO film by using nitrogen flow, and carrying out ultraviolet-ozone treatment for 20 minutes.
(2) Preparing an electron transport layer ZnO: preparing 0.45 mol/L2-methoxy ethanol solution of zinc acetate dihydrate, stirring for 2 hours at 70 ℃, dropwise adding ethanolamine with equal molar amount, continuing stirring for 2 hours, and then stirring for 10 hours at normal temperature. The prepared ZnO precursor solution is spin-coated (3000 r/min) on ITO, and annealing is carried out for 1 hour at 200 ℃ in the air.
(3) Preparation of the active layer: PTB7-Th with a total concentration of 12mg/mL, a mixed solution of example 8-1: 2 (mass ratio) and PTB7-Th with a total concentration of 12mg/mL, a mixed solution of example 11-1: 2 (mass ratio) were prepared, and the prepared solutions were each spin-coated (1000 rpm) on a ZnO film, and placed under a certain degree of vacuum (8-10)-4-4*10-4Pa) to evaporate off the residual reagent of the active layer.
(4) Preparation of hole transport layer and electrode: transferring the sample coated with the active layer to a vacuum evaporation chamber, and keeping the vacuum degree below 4 x 10-4Evaporating 8nm MoO in Pa atmosphere3And 100nm of Ag.
Taking the anthracene diimide polymers prepared in examples 8 and 11 as the acceptor material of the active layer of the organic solar cell and the donor material PTB7-Th commonly used in organic solar cells as an example, the structure of the organic solar trans-cell device is as follows: ITO/ZnO/PTB7-Th anthracene diimide high-molecular material/MoO3and/Ag. The organic solar cell prepared above was subjected to I-V test, and the specific results are shown in table 1.
Table 1 performance parameters device results for devices prepared as organic solar cell receptor materials example 8 and example 11
Figure BDA0001729522000000131
It will be readily understood by those skilled in the art that various modifications or changes in form may be made to the present invention without departing from the synthesis and use of the materials disclosed in the foregoing specification, and such changes are to be considered as included within the scope of the present invention. Therefore, the above-mentioned embodiments are merely examples for illustrating the details of the present invention, and do not limit the scope of the present invention. Variations or modifications of the materials thus far introduced are within the scope of the present invention.

Claims (12)

1. The anthracene diimide bromide is an anthracene diimide bromide isomer material obtained by brominating different sites of two kinds of anthracene diimides, and is characterized in that the chemical structural formula of the anthracene diimide bromide isomer material is any one of the following general formulas:
Figure 188608DEST_PATH_IMAGE001
the symbols and indices in the formula have the following meanings:
R1, R2are the same or different and are each one of the structures shown below:
Figure 818785DEST_PATH_IMAGE002
o, m, n, x and y are the same or different, and the value range is as follows: 50 is more than or equal to o, m, n, x and y are more than or equal to 0;
R3-R7are identical or different and are each one of the following structural units:
Figure 466935DEST_PATH_IMAGE003
Figure 7638DEST_PATH_IMAGE004
Figure 57634DEST_PATH_IMAGE005
。
2. the anthracene diimide bromide according to claim 1, wherein: o, m, n, x and y are the same or different, and the value range is as follows: 15 is more than or equal to o, m, n, x and y are more than or equal to 6.
3. The polymer of anthracene diimide bromide according to claim 1, wherein the general chemical formula of the polymer is formed by connecting one or more than two of the following structural formulas:
Figure 596062DEST_PATH_IMAGE006
ar is one or more than two of the following structural units:
Figure 590563DEST_PATH_IMAGE007
Figure 872640DEST_PATH_IMAGE008
Figure 511563DEST_PATH_IMAGE009
r 'and R' are the same or different and each is one of the structures shown below:
Figure 814368DEST_PATH_IMAGE010
a, b, c, d and e are the same or different, and the value range is as follows: 50 is more than or equal to a, b, c, d, e and more than or equal to 0.
4. A method for producing the anthracene imide bromide according to claim 1,
the preparation process of the 3,7-2Br-ADI compound with 3, 7-site bromination of anthracene diimide comprises the following steps:
(1) adding the compound 1 and aluminum chloride into a reaction bottle under argon atmosphere, adding anhydrous o-dichlorobenzene, stirring at room temperature for 10-20 minutes, then adding the compound 2, stirring at 150-oC, refluxing for 12 to 24 hours,distilling under reduced pressure to remove the reagent, and separating by a column to obtain a compound 3;
(2) concentrated sulfuric acid solution of compound 3 at 50-80 deg.CoStirring for 3-6 hours at C, adding a brominating reagent 1,3-dibromo-5,5-Dimethylhydantoin (DBH), reacting for 8-48 hours, diluting the reaction solution with water, extracting with dichloromethane, drying, filtering, and separating by a column to obtain a compound 4, namely 3,7-2 Br-ADI;
compound 1: aluminum chloride: the molar ratio of the compound 2 is 1:5:8-1:7: 20;
compound 3: the molar ratio of the 1,3-dibromo-5,5-dimethylhydantoin is 1:1.5-1: 15;
Figure 968269DEST_PATH_IMAGE011
r in compound 2 and compound 3 and R in claim 11Or R2The same;
the preparation process of the compound 2,6-2Br-ADI with 2, 6-site bromination of anthracene diimide comprises the following steps:
(1) under an argon atmosphere, at 0oDropwise adding n-butyllithium into the anhydrous ether solution of the compound 5, stirring at room temperature for more than 1 hour, adding dry ice, separating out a water phase after the reaction is finished, acidifying, washing and filtering to obtain a solid compound 6;
(2) adding thionyl chloride into the compound 6, refluxing for 2 hours, and distilling at normal pressure to obtain a compound 7;
(3) adding the compound 7 and aluminum chloride into a reaction bottle under argon atmosphere, adding anhydrous o-dichlorobenzene, stirring at room temperature for 10-20 minutes, then adding the compound 2, and reacting at 150-oRefluxing for 12-24 hr under C, distilling under reduced pressure to remove solvent, and separating with column to obtain compound 8, i.e. 2,6-2 Br-ADI;
compound 5: the molar ratio of n-butyllithium is 1: 2.2;
compound 6: the mol ratio of the thionyl chloride is 1:5-1: 15;
compound 7: aluminum chloride: the compound 2 has a molar ratio of 1:5:8-1:7: 20;
Figure 257299DEST_PATH_IMAGE012
。
5. a process for preparing a polymer according to claim 3,
preparation of polymer PADI-3,7-Ar polymerized in 3, 7-position of anthracene diimide:
under argon atmosphere, compounds of 4,5 '-bis (trimethylstannyl) -2,2' -bithiophene and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.03-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer A; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, the compounds 4,2, 5-bis (trimethylstannyl) thiophene and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.04-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer B; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, the compounds 4,2, 5-bis (trimethylstannyl) selenophene and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.04-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, the reaction solution is settled by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L,filtering, sequentially extracting with acetone, n-hexane, chloroform and/or toluene with a Soxhlet extractor, and settling with methanol to obtain polymer C; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, compound 4, (3,3 '-difluoro- [2,2' -bithiophene)]-5,5' -diyl) bis (trimethyltin), Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1: (0.04-0.06): (0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer D; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, compound 4, (3, 3-twenty-two-radical-2, 2-bithiophene-5, 5-two-radical) bi (trimethyl tin) and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1: (0.04-0.06): (0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling a diluted hydrochloric acid/methanol mixed solvent with the reaction molar concentration of 1-2 mol/L, filtering, sequentially extracting with acetone, n-hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling with methanol to obtain a polymer E, wherein the volume ratio of the diluted hydrochloric acid/methanol is 1:5-1: 10; the compound 4 is the compound 4 prepared in claim 4.
6. A process for preparing a polymer according to claim 3,
preparation of polymer PADI-2,6-Ar polymerized at 2, 6-position of anthracene diimide:
under argon atmosphere, compounds 8, 5 '-bis (trimethyltin) base-2, 2' -bithiophene and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.04-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane and chloroform by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer F; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, the compounds 8, 2, 5-bis (trimethylstannyl) thiophene and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.04-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer G; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, the compounds 8, 2, 5-bis (trimethylstannyl) selenophene and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.04-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer H; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, compound 8, (3,3 '-difluoro- [2,2' -bithiophene)]-5,5' -diyl) bis (trimethyltin), Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1 (0.04-0.06): 0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, the reaction solution is settled by using a mixed solvent of dilute hydrochloric acid/methanol with the molar concentration of 1-2 mol/L, filtered, and sequentially extracted by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractorExtracting, and then settling with methanol to obtain a polymer I; the volume ratio of the dilute hydrochloric acid to the methanol is 1:5-1: 10;
or, under argon atmosphere, compound 8, (3, 3-twenty-two-radical-2, 2-bithiophene-5, 5-two-radical) bi (trimethyl tin) and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1: (0.04-0.06): (0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer J, wherein the volume ratio of the diluted hydrochloric acid/methanol is 1:5-1: 10;
the compound 8 is the compound 8 prepared in claim 4.
7. A process for preparing a polymer according to claim 3,
preparing a random copolymer polymer by mixing and copolymerizing two anthracene diimides:
under argon atmosphere, compound 4 and compound 8, a tin salt, Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1: (0.04-0.06): (0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, the reaction solution is settled by using a mixed solvent of dilute hydrochloric acid/methanol with the molar concentration of 1-2 mol/L, filtered, extracted by using a Soxhlet extractor sequentially using acetone, normal hexane, chloroform and/or toluene, and then settled by using methanol to obtain a macromolecule, wherein the molar ratio of a compound 4 to a compound 8 is as follows: 0.01:0.99-0.99:0.01, the volume ratio of the dilute hydrochloric acid/methanol is 1:5-1:10, and the tin salt is 5,5 '-bis (trimethyl tin) -2,2' -bithiophene or 2, 5-bis (trimethyl tin base) thiophene; the compounds 4 and 8 are the compounds 4 and 8 prepared in claim 4.
8. A process for preparing a polymer according to claim 3,
preparing a random copolymer polymer by polymerizing anthracene diimide and two tin salts:
under argon atmosphere, compound 4 or compound 8, two different tin salts and Pd2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1: (0.04-0.06): (0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and then adding bromobenzene for end capping; after the reaction is finished, settling the reaction solution by using a dilute hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, extracting by using acetone, normal hexane, chloroform and/or toluene in sequence by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer, wherein the volume ratio of the dilute hydrochloric acid/methanol is 1:5-1:10, the tin salt is 5,5 '-bis (trimethyltin) -2,2' -bithiophene, 2, 5-bis (trimethyltin) thiophene, (3, 3-twenty-2, 2-bithiophene-5, 5-diyl) bis (trimethyltin) or 2, 5-bis (trimethyltin) selenophene, and the minimum molar content of each tin salt in the two tin salts is not lower than 1%; the compounds 4 and 8 are the compounds 4 and 8 prepared in claim 4.
9. The method for producing a polymer according to claim 3,
preparing a random copolymer polymer polymerized by anthracene diimide and three or more tin salts:
under the argon atmosphere, the compound 4 or the compound 8, three or more tin salts are prepared, wherein the tin salts are 5,5 '-bis (trimethylstannyl) -2,2' -bithiophene, 2, 5-bis (trimethylstannyl) thiophene, (3, 3-twenty-two-yl-2, 2-bithiophene-5, 5-two-yl) bis (trimethyltin) and 2, 5-bis (trimethylstannyl) selenophene, 5,5 '-bis (trimethylstannyl) -2,2' -diselenophene, 2, 5-bis (trimethylstannyl) chrysene, or (3, 3-docosyl-2, 2-diselenophene-5, 5-diyl) bis (trimethyltin), the minimum molar content of each tin salt in all tin salts being not less than 1%, tin salt, Pd.2(dba)3The tri (o-methylphenyl) phosphine comprises the following components in sequence by mol ratio: 1:1: (0.04-0.06): (0.07-0.09), mixing with toluene, stirring, polymerizing by stille at 90-110oReacting for 1-2 days under C, and addingAdding bromobenzene for end capping, after the reaction is finished, settling reaction liquid by using a diluted hydrochloric acid/methanol mixed solvent with the molar concentration of 1-2 mol/L, filtering, sequentially extracting by using acetone, normal hexane, chloroform and/or toluene by using a Soxhlet extractor, and then settling by using methanol to obtain a polymer, wherein the volume ratio of the diluted hydrochloric acid/methanol is 1:5-1: 10; the compounds 4 and 8 are the compounds 4 and 8 prepared in claim 4.
10. Use of a polymer according to claim 3 as an n-type semiconductor material in a field effect transistor.
11. Use of a polymer according to claim 3 as n-type acceptor material and/or electron transport material in an organic solar cell device.
12. Use of a polymer according to claim 3 as an electron transport material and/or a passivating agent in a perovskite solar cell device.
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