CN111892696A - Dithienobenzene fused ring quinoxaline conjugated polymer and preparation method and application thereof - Google Patents

Dithienobenzene fused ring quinoxaline conjugated polymer and preparation method and application thereof Download PDF

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CN111892696A
CN111892696A CN202010714965.2A CN202010714965A CN111892696A CN 111892696 A CN111892696 A CN 111892696A CN 202010714965 A CN202010714965 A CN 202010714965A CN 111892696 A CN111892696 A CN 111892696A
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dithienobenzene
conjugated polymer
fused ring
quinoxaline conjugated
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张连杰
江海盈
陈军武
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South China University of Technology SCUT
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Abstract

The invention discloses a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method and application thereof. The invention firstly synthesizes
Figure DDA0002597827660000011
And then carrying out copolymerization reaction with a bi (trimethyltin) substituted heterocyclic compound to obtain the dithienobenzene fused ring quinoxaline conjugated polymer. The dithienobenzene condensed ring quinoxaline conjugated polymer has wide band gap and higher field-induced hole mobility, and can realize better absorption complementation and higher photoelectric conversion efficiency when being used in a non-fullerene thick film photoelectric functional device.

Description

Dithienobenzene fused ring quinoxaline conjugated polymer and preparation method and application thereof
Technical Field
The invention relates to a dithienobenzene fused ring quinoxaline conjugated polymer, a preparation method and application thereof, belonging to the technical field of photoelectron materials.
Background
The development of a novel green energy technology is one of important ways for solving the problems of energy shortage, environmental pollution and the like, and solar energy has the advantages of being green, renewable, wide in distribution, easy to obtain and the like, and has a wide application prospect. Therefore, the development of solar power generation technology is of great significance, and the development of solar cells is the most critical, wherein the development of new materials cannot be separated.
The polymer organic solar cell is a novel thin-film photovoltaic cell, has the advantages of all solid state, wide adjustable range of photovoltaic material properties, translucency realization, capability of being made into flexible cell devices, capability of being prepared in large area and at low cost and the like, and can be applied to places such as building external windows, automobile windshields and foldable curtains. In polymer organic solar cells, the active material is a key factor in determining the efficiency of the cell. At present, the main receptor of the active layer is generally a narrow-bandgap non-fullerene material, the donor material is generally a conjugated polymer, and the traditional donor material is generally a few conjugated polymers with narrow bandgap, but less conjugated polymers with wide bandgap, so that absorption complementation cannot be well formed to improve the utilization of solar spectrum.
Therefore, there is a need to develop a conjugated polymer having a wide band gap, good planarity, high field hole mobility, and high photoelectric conversion efficiency.
Disclosure of Invention
The invention aims to provide a dithienobenzene fused ring quinoxaline conjugated polymer, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a dithiophene fused ring quinoxaline conjugated polymer has a structural formula as follows:
Figure BDA0002597827640000011
in the formula, R1Is C8～C28Alkyl of R2Is C8～C28X is-H or-F, Y is-H or-F, M is
Figure BDA0002597827640000012
Fluorine substitution
Figure BDA0002597827640000013
Fluorine substitution
Figure BDA0002597827640000014
Fluorine substitution
Figure BDA0002597827640000015
N is an integer of 10 to 70.
Preferably, said R is1Is C8～C28Branched alkyl groups of (a).
Preferably, said R is2Is C8～C28Branched alkyl groups of (a).
Preferably, R in the dithienobenzene fused ring quinoxaline conjugated polymer1And R2The same group is taken.
Preferably, n is an integer of 30 to 55.
Preferably, the number average molecular weight of the dithienobenzene fused ring quinoxaline conjugated polymer is 19400-49000 g/mol.
Further preferably, the number average molecular weight of the dithienobenzene fused ring quinoxaline conjugated polymer is 21000-38500 g/mol.
Preferably, the hole mobility of the dithienobenzene condensed ring quinoxaline conjugated polymer is 0.01-0.10 cm2/(V·s)。
Further preferably, the hole mobility of the dithienobenzene fused ring quinoxaline conjugated polymer is 0.06-0.09 cm2/(V·s)。
The preparation method of the dithienobenzene fused ring quinoxaline conjugated polymer comprises the following steps:
1) converting the 2-alkylthiophene to a 2-alkyl-5-bromothiophene;
2) converting 2-alkyl-5-bromothiophene to 2-alkyl-4-bromothiophene;
3) conversion of 2-alkyl-4-bromothiophenes to
Figure BDA0002597827640000021
4) Will be provided with
Figure BDA0002597827640000022
Is converted into
Figure BDA0002597827640000023
5) Will be provided with
Figure BDA0002597827640000024
Is converted into
Figure BDA0002597827640000025
6) Will be provided with
Figure BDA0002597827640000026
And a bis (trimethyltin) -substituted heterocyclic compound Me3Sn-M-SnMe3And (4) carrying out copolymerization to obtain the dithienobenzene fused ring quinoxaline conjugated polymer.
Preferably, the preparation method of the dithienobenzene fused ring quinoxaline conjugated polymer comprises the following steps:
1) carrying out the reaction of 2-alkylthiophene and N-bromosuccinimide to obtain 2-alkyl-5-bromothiophene;
2) carrying out the reaction of 2-alkyl-5-bromothiophene and lithium diisopropylamide to obtain 2-alkyl-4-bromothiophene;
3) carrying out the reaction of 2-alkyl-4-bromothiophene and 1, 4-dimethylpiperazine-2, 3-dione to obtain
Figure BDA0002597827640000031
4) To carry out
Figure BDA0002597827640000032
To obtain a cyclization reaction
Figure BDA0002597827640000033
5) To carry out
Figure BDA0002597827640000034
And
Figure BDA0002597827640000035
by reaction of (A) to obtain
Figure BDA0002597827640000036
6) To carry outAnd a bis (trimethyltin) -substituted heterocyclic compound Me3Sn-M-SnMe3To obtain the dithienobenzene fused ring quinoxaline conjugated polymer.
A solar cell comprises an anode, a hole transport layer, an active material layer, an electron transport layer and a cathode which are sequentially stacked; the active material layer comprises an electron donor and an electron acceptor, wherein the electron donor is the dithienobenzene fused ring quinoxaline conjugated polymer.
Preferably, the electron acceptor is a non-fullerene acceptor material.
A transistor comprising the above dithienobenzene-fused ring quinoxaline conjugated polymer.
The invention has the beneficial effects that: the dithienobenzene condensed ring quinoxaline conjugated polymer has wide band gap and higher field-induced hole mobility, and can realize better absorption complementation and higher photoelectric conversion efficiency when being used in a non-fullerene thick film photoelectric functional device.
Drawings
Fig. 1 is a synthesis scheme of a dithienobenzene fused ring quinoxaline conjugated polymer of the present invention.
FIG. 2 is a NMR spectrum of 2- (2-ethylhexyl) -5-bromothiophene in example 1.
FIG. 3 is a NMR chart of 2- (2-ethylhexyl) -4-bromothiophene in example 1.
FIG. 4 is a NMR spectrum of bis [2- (2-ethylhexyl) thiophen-4-yl ] ethane-1, 2-dione in example 1.
FIG. 5 is a NMR spectrum of 2, 7-bis (2-ethylhexyl) benzodithiophene-4, 5-dione in example 1.
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-ethylhexyl) dithienophenoloxazine in example 1.
Detailed Description
The synthetic route of the dithienobenzene fused ring quinoxaline conjugated polymer is shown in figure 1.
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 2- (2-ethylhexyl) -5-bromothiophene: adding 30mmol of 2- (2-ethylhexyl) thiophene into 35mL of anhydrous Tetrahydrofuran (THF), stirring for dissolving, adding 30mmol of N-bromosuccinimide (NBS), stirring for reacting for 3h, adding saturated sodium sulfite solution for terminating the reaction, extracting with N-hexane, drying the organic phase with anhydrous magnesium sulfate, removing the solvent, and separating and purifying with silica gel chromatographic column to obtain 28mmol of 2- (2-ethylhexyl) -5-bromothiophene (yellow liquid, yield 93.3%, nuclear magnetic resonance hydrogen spectrum shown in figure 2), wherein the reaction formula is as follows:
Figure BDA0002597827640000041
2) preparation of 2- (2-ethylhexyl) -4-bromothiophene: 26mmol of 2- (2-ethylhexyl) -5-bromothiophene is dropwise added into 30mmol of Lithium Diisopropylamide (LDA) to react for 12h, then distilled water is added to quench the reaction, dichloromethane is used for extraction, anhydrous magnesium sulfate is used for drying an organic phase, a solvent is removed, and silica gel chromatographic column is used for separation and purification to obtain 23.3mmol of 2- (2-ethylhexyl) -4-bromothiophene (light yellow liquid, the yield is 89.6%, and a nuclear magnetic resonance hydrogen spectrum diagram is shown in figure 3), wherein the reaction formula is as follows:
Figure BDA0002597827640000042
3) preparation of bis [2- (2-ethylhexyl) thiophen-4-yl ] ethane-1, 2-dione: dropwise adding 20mmol of 2- (2-ethylhexyl) -4-bromothiophene into 20mmol of n-butyllithium (BuLi), reacting for 2 hours after the addition, adding 10mmol of 1, 4-dimethylpiperazine-2, 3-dione, adding distilled water, quenching, extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, removing the solvent, and separating and purifying with a silica gel chromatographic column to obtain 7.6mmol of bis [2- (2-ethylhexyl) thiophen-4-yl ] ethane-1, 2-dione (pale yellow liquid, yield 76.0%, nuclear magnetic resonance hydrogen spectrum shown in figure 4), wherein the reaction formula is as follows:
Figure BDA0002597827640000051
4) preparation of 2, 7-bis (2-ethylhexyl) benzodithiophene-4, 5-dione: adding 6mmol of bis [2- (2-ethylhexyl) thiophen-4-yl ] ethane-1, 2-diketone into 20mL of dichloromethane under the protection of nitrogen, stirring for dispersion, adding 7.2mmol of ferric trichloride, reacting for 5h, adding distilled water for quenching reaction, extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, removing the solvent, and separating and purifying by a silica gel chromatographic column to obtain 4.5mmol of 2, 7-bis (2-ethylhexyl) benzodithiophene-4, 5-diketone (yellow brown liquid, the yield is 75.0%, the nuclear magnetic resonance hydrogen spectrum is shown in figure 5), wherein the reaction formula is as follows:
Figure BDA0002597827640000052
5) preparation of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-ethylhexyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-ethylhexyl) benzodithiophene-4, 5-dione and 3.5mmol of 3, 6-dibromo-4, 5-difluoro-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred for reaction for 24 hours, and then distilled water was added to quench the reaction, the mixture was extracted with dichloromethane, washed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and the mixture was purified by silica gel column chromatography to obtain 2.86mmol of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-ethylhexyl) dithienophenoloxazine (orange solid, yield 81.7%, nuclear magnetic resonance hydrogen spectrum shown in FIG. 6) having the following reaction formula:
Figure BDA0002597827640000053
6) preparation of Polymer PDTQ-1: under the protection of argon, 0.2mmol of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-ethylhexyl) dithieno-phenazine, 0.2mmol of 2, 5-bis (trimethyltin) thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, the mixed solution is purged with argon for 15min, then the mixed solution is heated to 110 ℃ for reaction for 72h, then the reaction solution is cooled to room temperature and dripped into methanol, the precipitate is collected, soxhlet extraction is carried out by sequentially using methanol, acetone, ethyl acetate and chloroform, then the chloroform extract is concentrated and precipitated again in methanol, and vacuum drying is carried out to obtain a polymer PDTQ-1 (black solid), the molecular weight (GPC, THF, 60 ℃): mn is 8500g/mol, Mw/Mn is 2.5, and the reaction formula is as follows:
Figure BDA0002597827640000061
example 2:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 8, 11-dibromo-9-fluoro-2, 5-bis (2-ethylhexyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-ethylhexyl) benzodithiophene-4, 5-dione (preparation method reference example 1) and 3.5mmol of 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred for reaction for 24 hours, then distilled water was added to quench the reaction, extracted with dichloromethane, washed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and separated and purified by a silica gel column chromatography to obtain 2.82mmol of 8, 11-dibromo-9-fluoro-2, 5-bis (2-ethylhexyl) dithienophenoloxazine (orange solid, yield 80.6%), MS (EI) m/z: 692 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000062
2) preparation of Polymer PDTQ-2: under the protection of argon, 0.2mmol of 8, 11-dibromo-9-fluoro-2, 5-bis (2-ethylhexyl) dithieno-phenazine, 0.2mmol of 2, 5-bis (trimethyltin) thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, the mixed solution is purged with argon for 15min, then the mixed solution is heated to 110 ℃ for reaction for 72h, then the reaction solution is cooled to room temperature and dripped into methanol, the precipitate is collected, soxhlet extraction is carried out by sequentially using methanol, acetone, ethyl acetate and chloroform, then the chloroform extract is concentrated and precipitated again in methanol, and vacuum drying is carried out to obtain polymer PDTQ-2 (black solid), the molecular weight (GPC, THF, 60 ℃): 7800g/mol Mn, 3.1 Mw/Mn) is:
Figure BDA0002597827640000063
example 3:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 8, 11-dibromo-2, 5-bis (2-ethylhexyl) dithienophenolazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-ethylhexyl) benzodithiophene-4, 5-dione (preparation method reference example 1) and 3.5mmol of 3, 6-dibromo-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred to react for 24 hours, and then distilled water was added to quench the reaction, followed by extraction with dichloromethane, washing with an aqueous ammonium chloride solution, drying of the organic phase with anhydrous magnesium sulfate, removal of the solvent, and separation and purification with a silica gel column to obtain 2.9mmol of 8, 11-dibromo-2, 5-bis (2-ethylhexyl) dithienophenoloxazine (orange solid, yield 82.9%), MS EI) m/z: 674 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000071
2) preparation of Polymer PDTQ-3: under the protection of argon, 0.2mmol of 8, 11-dibromo-2, 5-bis (2-ethylhexyl) dithienophenolizine, 0.2mmol of 2, 5-bis (trimethyltin) thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, the mixed solution is firstly purged with argon for 15min, then the mixed solution is heated to 110 ℃ for reaction for 72h, then the reaction solution is cooled to room temperature and dripped into methanol, the precipitate is collected, soxhlet extraction is carried out by sequentially using methanol, acetone, ethyl acetate and chloroform, then the chloroform extract is concentrated and precipitated again in methanol, and vacuum drying is carried out to obtain a polymer PDTQ-3 (black solid), the molecular weight (GPC, THF, 60 ℃): the Mn is 8700g/mol, the Mw/Mn is 2.8, and the reaction formula is as follows:
Figure BDA0002597827640000072
example 4:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 2- (2-hexyldecyl) -5-bromothiophene: 30mmol of 2- (2-hexyldecyl) thiophene was added to 35mL of anhydrous Tetrahydrofuran (THF), and dissolved by stirring, 30mmol of N-bromosuccinimide (NBS) was added, and the reaction was stirred for 3 hours, and then a saturated sodium sulfite solution was added to terminate the reaction, and extraction was performed with N-hexane, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and separation and purification was performed by silica gel chromatography to obtain 27.1mmol of 2- (2-hexyldecyl) -5-bromothiophene (yellow liquid, yield 90.2%) represented by the following formula:
Figure BDA0002597827640000081
2) preparation of 2- (2-hexyldecyl) -4-bromothiophene: 26mmol of 2- (2-hexyldecyl) -5-bromothiophene is dropwise added into 30mmol of Lithium Diisopropylamide (LDA) to react for 12h, then distilled water is added to quench the reaction, dichloromethane is used for extraction, anhydrous magnesium sulfate is used for drying an organic phase, a solvent is removed, and silica gel chromatography is used for separation and purification to obtain 22.7mmol of 2- (2-hexyldecyl) -4-bromothiophene (light yellow liquid, the yield is 87.2 percent), and the reaction formula is as follows:
Figure BDA0002597827640000082
3) preparation of bis [2- (2-hexyldecyl) thiophen-4-yl ] ethane-1, 2-dione: dropwise adding 20mmol of 2- (2-hexyldecyl) -4-bromothiophene into 20mmol of n-butyllithium (BuLi), reacting for 2 hours after the addition, adding 10mmol of 1, 4-dimethylpiperazine-2, 3-dione, adding distilled water, quenching, extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, removing the solvent, and purifying by silica gel chromatography to obtain 15.1mmol of bis [2- (2-hexyldecyl) thiophen-4-yl ] ethane-1, 2-dione (pale yellow liquid, yield 75.3%), wherein:
Figure BDA0002597827640000083
4) preparation of 2, 7-bis (2-hexyldecyl) benzodithiophene-4, 5-dione: under the protection of nitrogen, 6mmol of bis [2- (2-hexyldecyl) thiophen-4-yl ] ethane-1, 2-dione is added into 20mL of dichloromethane, stirred and dispersed, 7.2mmol of ferric trichloride is added, the reaction is carried out for 5h, then distilled water is added for quenching, the dichloromethane is used for extraction, the organic phase is dried by anhydrous magnesium sulfate, the solvent is removed, and silica gel chromatographic column separation and purification are carried out to obtain 4.4mmol of 2, 7-bis (2-hexyldecyl) benzodithiophene-4, 5-dione (yellow brown liquid, the yield is 73.3 percent), and the reaction formula is as follows:
Figure BDA0002597827640000084
5) preparation of 8, 11-dibromo-2, 5-bis (2-hexyldecyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-hexyldecyl) benzodithiophene-4, 5-dione and 3.5mmol of 3, 6-dibromo-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred for reaction for 24 hours, then distilled water was added to quench the reaction, extraction was performed with methylene chloride, washing was performed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and separation and purification were performed by silica gel chromatography to obtain 2.85mmol of 8, 11-dibromo-2, 5-bis (2-hexyldecyl) dithienophenoxazine (orange solid, yield 81.4%), MS (EI) m/z: 898 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000091
6) preparation of Polymer PDTQ-4: under the protection of argon, 0.2mmol of 8, 11-dibromo-2, 5-bis (2-hexyldecyl) dithienophenolizine, 0.2mmol of 2, 5-bis (trimethyltin) thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, the mixed solution is firstly purged with argon for 15min, then the mixed solution is heated to 110 ℃ for reaction for 72h, then the reaction solution is cooled to room temperature and dripped into methanol, the precipitate is collected, soxhlet extraction is carried out by sequentially using methanol, acetone, ethyl acetate and chloroform, then the chloroform extract is concentrated and precipitated again in methanol, and vacuum drying is carried out to obtain a polymer PDTQ-4 (black solid), the molecular weight (GPC, THF, 60 ℃): 11200g/mol, 2.2 Mw/Mn, and the reaction formula is:
Figure BDA0002597827640000092
example 5:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 8, 11-dibromo-9-fluoro-2, 5-bis (2-hexyldecyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-hexyldecyl) benzodithiophene-4, 5-dione (preparation method reference example 4) and 3.5mmol of 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred to react for 24 hours, then distilled water was added to quench the reaction, extracted with dichloromethane, washed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and separated and purified by a silica gel column chromatography to obtain 2.83mmol of 8, 11-dibromo-9-fluoro-2, 5-bis (2-hexyldecyl) dithienophenoxazine (orange solid, yield 80.8%), MS (EI) m/z: 916 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000093
2) preparation of Polymer PDTQ-5: under the protection of argon, 0.2mmol of 8, 11-dibromo-9-fluoro-2, 5-bis (2-hexyldecyl) dithienophenoxazine, 0.2mmol of 5,5 '-bistrimethyltin-2, 2' -bithiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene were mixed, the mixed solution was purged with argon for 15min, the mixed solution was heated to 110 ℃ and reacted for 72 hours, the reaction solution was cooled to room temperature and dropped into methanol, the precipitate was collected, soxhlet extraction was performed with methanol, acetone, ethyl acetate and chloroform in this order, the chloroform extract was concentrated and precipitated again in methanol, and vacuum drying was performed to obtain polymer PDTQ-5 (black solid), molecular weight (GPC, THF, 60 ℃): mn is 9800g/mol, Mw/Mn is 2.7, and the reaction formula is as follows:
Figure BDA0002597827640000101
example 6:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-hexyldecyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-hexyldecyl) benzodithiophene-4, 5-dione (preparation method reference example 4) and 3.5mmol of 3, 6-dibromo-4, 5-difluoro-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred to react for 24 hours, then distilled water was added to quench the reaction, extracted with dichloromethane, washed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and purified by silica gel chromatography to obtain 2.86mmol of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-hexyldecyl) dithienophenoxazine (orange solid, yield 81.8%), MS (EI)/z: 934 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000102
2) preparation of Polymer PDTQ-6: under the protection of argon, 0.2mmol of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-hexyldecyl) dithieno-phenazine, 0.2mmol of 2, 5-bis (trimethyltin) -thieno [3,2-b ] thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, argon is firstly used for purging the mixed solution for 15min, then the mixed solution is heated to 110 ℃, reaction is carried out for 72h, then the reaction solution is cooled to room temperature and is dripped into methanol, collecting precipitate, sequentially performing Soxhlet extraction with methanol, acetone, ethyl acetate and chloroform, concentrating chloroform extract, precipitating again in methanol, and vacuum drying to obtain polymer PDTQ-6 (black solid) with molecular weight (GPC, THF, 60 deg.C): mn is 9900g/mol, Mw/Mn is 2.9, and the reaction formula is as follows:
Figure BDA0002597827640000111
example 7:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 2- (2-dodecylhexadecyl-hexadecyl) -5-bromothiophene: adding 30mmol of 2- (2-dodecyl hexadecyl) thiophene into 35mL of anhydrous Tetrahydrofuran (THF), stirring for dissolving, adding 30mmol of N-bromosuccinimide (NBS), stirring for reacting for 3 hours, adding saturated sodium sulfite solution for terminating the reaction, extracting with N-hexane, drying an organic phase with anhydrous magnesium sulfate, removing the solvent, and separating and purifying by using a silica gel chromatographic column to obtain 26.9mmol of 2- (2-dodecyl hexadecyl) -5-bromothiophene (yellow liquid, yield 89.7 percent), wherein the reaction formula is as follows:
Figure BDA0002597827640000112
2) preparation of 2- (2-dodecylhexadecyl-4-bromothiophene: 26mmol of 2- (2-dodecyl hexadecyl) -5-bromothiophene is dropwise added into 30mmol of Lithium Diisopropylamide (LDA) to react for 12 hours, distilled water is added to quench the reaction, dichloromethane is used for extraction, anhydrous magnesium sulfate is used for drying an organic phase, a solvent is removed, and silica gel chromatographic column is used for separation and purification to obtain 22.2mmol of 2- (2-dodecyl hexadecyl) -4-bromothiophene (light yellow liquid, the yield is 85.3 percent), and the reaction formula is as follows:
Figure BDA0002597827640000113
3) preparation of bis [2- (2-dodecylhexadecyl) thiophen-4-yl ] ethane-1, 2-dione: dropwise adding 20mmol of 2- (2-dodecyl hexadecyl) -4-bromothiophene into 20mmol of n-butyl lithium (BuLi), reacting for 2 hours after the addition is finished, adding 10mmol of 1, 4-dimethylpiperazine-2, 3-dione, adding distilled water, quenching, extracting with dichloromethane, drying an organic phase with anhydrous magnesium sulfate, removing the solvent, and separating and purifying by using a silica gel chromatographic column to obtain 14.6mmol of bis [2- (2-dodecyl hexadecyl) thiophene-4-yl ] ethane-1, 2-dione (light yellow liquid, yield 72.9 percent), wherein the reaction formula is as follows:
Figure BDA0002597827640000114
4) preparation of 2, 7-bis (2-dodecylhexadecyl) benzodithiophene-4, 5-dione: adding 6mmol of bis [2- (2-dodecyl hexadecyl) thiophene-4-yl ] ethane-1, 2-diketone into 20mL of dichloromethane under the protection of nitrogen, stirring for dispersing, adding 7.2mmol of ferric trichloride, reacting for 5 hours, adding distilled water for quenching reaction, extracting with dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, removing a solvent, and separating and purifying by using a silica gel chromatographic column to obtain 4.3mmol of 2, 7-bis (2-dodecyl hexadecyl) benzodithiophene-4, 5-diketone (yellow brown liquid, the yield is 71.4 percent):
Figure BDA0002597827640000121
5) preparation of 8, 11-dibromo-2, 5-bis (2-dodecylhexadecyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-dodecylhexadecyl) benzodithiophene-4, 5-dione and 3.5mmol of 3, 6-dibromo-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred to react for 24 hours, then distilled water was added to quench the reaction, extraction was performed with dichloromethane, washing was performed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and separation and purification were performed with a silica gel column to obtain 2.81mmol of 8, 11-dibromo-2, 5-bis (2-dodecylhexadecyl) dithienophenozine (orange solid, yield 80.2%), MS EI) m/z: 1234 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000122
6) preparation of Polymer PDTQ-7: under the protection of argon, 0.2mmol of 8, 11-dibromo-2, 5-bis (2-dodecylhexadecyl) dithieno-phenazine, 0.2mmol of 2, 5-bis (trimethyltin) -thieno [3,2-b ] thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene were mixed, the mixed solution was purged with argon gas for 15min, the mixed solution was heated to 110 ℃ and reacted for 72 hours, the reaction solution was cooled to room temperature and dropped into methanol, the precipitate was collected, soxhlet extraction was performed with methanol, acetone, ethyl acetate and chloroform in this order, the chloroform extract was concentrated and precipitated again in methanol, and vacuum drying was performed to obtain polymer PDTQ-7 (black solid), molecular weight (GPC, THF, 60 ℃): mn is 7900g/mol, Mw/Mn is 3.2, and the reaction formula is:
Figure BDA0002597827640000123
example 8:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 8, 11-dibromo-9-fluoro-2, 5-bis (2-dodecylhexadecyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-dodecylhexadecyl) benzodithiophene-4, 5-dione (preparation method reference example 7) and 3.5mmol of 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heated to 80 ℃ and stirred for reaction for 24 hours, then distilled water was added to quench the reaction, extracted with dichloromethane, washed with an aqueous ammonium chloride solution, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed, and the mixture was purified by silica gel column chromatography to obtain 2.89mmol of 8, 11-dibromo-9-fluoro-2, 5-bis (2-dodecylhexadecyl) dithienophenoxazine (orange solid) in 82.6% yield, MS (EI) m/z: 1252 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000131
2) preparation of Polymer PDTQ-8: under the protection of argon, 0.2mmol of 8, 11-dibromo-9-fluoro-2, 5-bis (2-dodecylhexadecyl) dithieno-phenazine, 0.2mmol of 2, 5-bis (trimethyltin) -3, 6-difluoro-thieno [3,2-b ] thiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, the mixed solution is firstly purged by argon for 15min, then the mixed solution is heated to 110 ℃, reacted for 72h, then the reaction solution is cooled to room temperature and dripped into methanol, precipitate is collected, soxhlet extraction is carried out by methanol, acetone, ethyl acetate and chloroform in turn, the chloroform extract is concentrated and then precipitated again in methanol, vacuum drying is carried out, and the polymer PDTQ-8 (black solid) is obtained, molecular weight (GPC, THF, 60 ℃ C.): 7600g/mol Mn/Mn 3.3, and the reaction formula is:
Figure BDA0002597827640000132
example 9:
a dithienobenzene fused ring quinoxaline conjugated polymer and a preparation method thereof comprise the following steps:
1) preparation of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-dodecylhexadecyl) dithienophenoloxazine: under the protection of nitrogen, 3.5mmol of 2, 7-bis (2-dodecylhexadecyl hexadecyl) benzodithiophene-4, 5-dione (preparation method reference example 7) and 3.5mmol of 3, 6-dibromo-4, 5-difluoro-1, 2-phenylenediamine were mixed and dispersed in 30mL of acetic acid, heating to 80 ℃ and stirring for reaction for 24h, adding distilled water to quench the reaction, extracting with dichloromethane, washing with an aqueous ammonium chloride solution, drying the organic phase with anhydrous magnesium sulfate, removing the solvent, and purifying by silica gel chromatography to obtain 2.8mmol of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-dodecylhexadecyl) dithienophenoloxazine (orange solid, yield 80.0%), ms (ei) m/z: 1270 (M)+) The reaction formula is as follows:
Figure BDA0002597827640000141
2) preparation of Polymer PDTQ-9: under the protection of argon, 0.2mmol of 8, 11-dibromo-9, 10-difluoro-2, 5-bis (2-dodecylhexadecyl) dithieno-phenazine, 0.2mmol of 3,3' -difluoro-5, 5' -bistrimethyltin-2, 2' -bithiophene, 6mg of tris (dibenzylideneacetone) dipalladium, 12mg of tris (o-methylphenyl) phosphorus and 8mL of anhydrous toluene are mixed, the mixed solution is firstly purged by argon, then the mixed solution is heated to 110 ℃, reacted for 72 hours, then the reaction solution is cooled to room temperature and dripped into methanol, the precipitate is collected, soxhlet extraction is carried out by methanol, acetone, ethyl acetate and chloroform in turn, then the chloroform extract is concentrated and precipitated again in methanol, vacuum drying is carried out to obtain a polymer PDTQ-9 (black solid), molecular weight (GPC, THF, 60 ℃ C.): mn is 8300g/mol, Mw/Mn is 3.5, and the reaction formula is as follows:
Figure BDA0002597827640000142
and (3) performance testing:
1) preparation and performance of solar cell:
the manufacturing process of the solar cell comprises the following steps: using ITO glass cleaned in advance as a cathode, spin-coating a layer of PEDOT (40 nm) and PSS (PSS) as a cathode buffer layer on the ITO glass, vacuum-drying, then spin-coating a 130nm photovoltaic active layer (bithiophene fused ring quinoxaline conjugated polymer: acceptor material ITIC (1: 1, mass ratio), drying at 70 ℃ for 10min, and continuously spin-coating a layer of PFN (conjugated polymer [9, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl aminopropyl) fluorene) with the thickness of 10nm]) As anode modifying layer, vacuum evaporating 100nm Al metal anode, applying negative bias between ITO and Al metal electrode at 100mW/cm2AM1.5 of (2) was measured under irradiation of simulated sunlight for cell characteristics.
And (3) testing results:
the open-circuit voltage of the solar cell containing the polymer PDTQ-1 is 0.89V, and the short-circuit current is 17.23mA/cm2The filling factor is 67.5%, and the energy conversion efficiency is 10.35%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-2 is 0.87V, and the short-circuit current is 13.21mA/cm2The filling factor is 58.23 percent, and the energy conversion efficiency is 6.69 percent;
the open-circuit voltage of the solar cell containing the polymer PDTQ-3 is 0.80V, and the short-circuit current is 8.72mA/cm2The filling factor is 51.45%, and the energy conversion efficiency is 3.59%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-4 is 0.82V, and the short-circuit current is 9.35mA/cm2The filling factor is 50.62%, and the energy conversion efficiency is 3.88%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-5 is 0.85V, and the short-circuit current is 15.86mA/cm2The filling factor is 54.33%, and the energy conversion efficiency is 7.32%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-6 is 0.86V, and the short-circuit current is 17.23mA/cm2The filling factor is 63.75%, and the energy conversion efficiency is 9.44%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-7 is 0.81V, and the short-circuit current is 7.95mA/cm2The filling factor is 59.73%, and the energy conversion efficiency is 3.85%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-8 is 0.91V, and the short-circuit current is 6.78mA/cm2The filling factor is 52.13%, and the energy conversion efficiency is 3.22%;
the open-circuit voltage of the solar cell containing the polymer PDTQ-9 is 0.92V, and the short-circuit current is 9.77mA/cm2The fill factor was 51.83%, and the energy conversion efficiency was 4.66%.
2) Preparation and performance of the transistor:
the manufacturing process of the transistor comprises the following steps: the method is characterized in that an upper contact geometric structure is adopted, silver is used as a source electrode and a drain electrode, highly doped n-type silicon and silicon dioxide generated by thermal growth are respectively used as a substrate and a grid insulating layer, n-octyl trichlorosilane is used as a surface modifier of a grid electrode, 11mg/mL of xylene solution of a dithienobenzene condensed ring quinoxaline conjugated polymer is spun into a polymer film with the thickness of 50nm on a spin coater under the condition of 2500rmp, then the polymer film is dried at 110 ℃ for 10min, a silver film with the thickness of 50nm is evaporated in vacuum to be used as the source electrode and the drain electrode, the ratio of the width to the length of a transistor is 100:1, and then a probe workstation and an Agilent 4155C semiconductor analyzer are used for characterization.
And (3) testing results:
the field mobility of the organic field effect transistors containing the polymers PDTQ-1 to PDTQ-9 was 0.07cm in this order2/(V·s)、0.09cm2/(V·s)、0.10cm2/(V·s)、0.06cm2/(V·s)、0.08cm2/(V·s)、0.10cm2/(V·s)、0.05cm2/(V·s)、0.02cm2V.s and 0.01cm2/(V·s)。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A dithiophene fused ring quinoxaline conjugated polymer is characterized in that: the structural formula is as follows:
Figure FDA0002597827630000011
in the formula, R1Is C8～C28Alkyl of R2Is C8～C28X is-H or-F, Y is-H or-F, M is
Figure FDA0002597827630000012
Fluorine substitution
Figure FDA0002597827630000013
Fluorine substitution
Figure FDA0002597827630000014
Figure FDA0002597827630000015
Fluorine substitution
Figure FDA0002597827630000016
N is an integer of 10 to 70.
2. The dithienobenzene fused ring quinoxaline conjugated polymer of claim 1, wherein: the R is1Is C8～C28Branched alkyl groups of (a).
3. The dithienobenzene fused ring quinoxaline conjugated polymer of claim 2, wherein: the R is2Is C8～C28Branched alkyl groups of (a).
4. The dithienobenzene-fused ring quinoxaline conjugated polymer according to any one of claims 1 to 3, wherein: the number average molecular weight of the dithienobenzene fused ring quinoxaline conjugated polymer is 19400-49000 g/mol.
5. The dithienobenzene-fused ring quinoxaline conjugated polymer according to any one of claims 1 to 3, wherein: the hole mobility of the dithienobenzene fused ring quinoxaline conjugated polymer is 0.01-0.10 cm2/(V·s)。
6. The method for producing a dithienobenzene-fused ring quinoxaline conjugated polymer according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
1) converting the 2-alkylthiophene to a 2-alkyl-5-bromothiophene;
2) converting 2-alkyl-5-bromothiophene to 2-alkyl-4-bromothiophene;
3) conversion of 2-alkyl-4-bromothiophenes to
Figure FDA0002597827630000017
4) Will be provided with
Figure FDA0002597827630000018
Is converted into
Figure FDA0002597827630000019
5) Will be provided with
Figure FDA0002597827630000021
Is converted into
Figure FDA0002597827630000022
6) Will be provided with
Figure FDA0002597827630000023
And a bis (trimethyltin) -substituted heterocyclic compound Me3Sn-M-SnMe3And (4) carrying out copolymerization to obtain the dithienobenzene fused ring quinoxaline conjugated polymer.
7. The method of claim 6, wherein: the method comprises the following steps:
1) carrying out the reaction of 2-alkylthiophene and N-bromosuccinimide to obtain 2-alkyl-5-bromothiophene;
2) carrying out the reaction of 2-alkyl-5-bromothiophene and lithium diisopropylamide to obtain 2-alkyl-4-bromothiophene;
3) carrying out the reaction of 2-alkyl-4-bromothiophene and 1, 4-dimethylpiperazine-2, 3-dione to obtain
Figure FDA0002597827630000024
4) To carry out
Figure FDA0002597827630000025
To obtain a cyclization reaction
Figure FDA0002597827630000026
5) To carry out
Figure FDA0002597827630000027
By reaction of (A) to obtain
Figure FDA0002597827630000028
6) To carry out
Figure FDA0002597827630000029
And a bis (trimethyltin) -substituted heterocyclic compound Me3Sn-M-SnMe3To obtain the dithienobenzene fused ring quinoxaline conjugated polymer.
8. A solar cell, characterized by: the anode, the hole transport layer, the active material layer, the electron transport layer and the cathode are sequentially stacked; the active material layer comprises an electron donor and an electron acceptor, wherein the electron donor is the dithienobenzene fused ring quinoxaline conjugated polymer according to any one of claims 1 to 5.
9. The solar cell according to claim 8, characterized in that: the electron acceptor is a non-fullerene acceptor material.
10. A transistor, characterized by: comprising the dithienobenzene-fused ring quinoxaline conjugated polymer according to any one of claims 1 to 5.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316216A (en) * 2021-11-17 2022-04-12 厦门华厦学院 Symmetric polymer based on dithienoquinoxaline-containing matrix as center and flexible electrochromic device
CN114349766A (en) * 2021-12-20 2022-04-15 淮阴工学院 D-A-D type organic semiconductor material and preparation method and application thereof
CN115386068A (en) * 2022-08-18 2022-11-25 东华大学 Conjugated polymer material containing benzodithiophene-4, 5-diketone and preparation method and application thereof

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918135A (en) * 2004-01-13 2007-02-21 日产化学工业株式会社 Aminoquinoxaline compound, polyaminoquinoxaline compound, and use thereof
CN102050794A (en) * 2009-11-09 2011-05-11 财团法人工业技术研究院 Quinoxalin derivative and organic LED (Light-Emitting Diode) containing same
CN102124044A (en) * 2008-08-18 2011-07-13 默克专利股份有限公司 Indacenodithiophene and indacenodiselenophene polymers and their use as organic semiconductors
CN102159617A (en) * 2008-09-19 2011-08-17 默克专利股份有限公司 Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors
CN102286140A (en) * 2010-06-18 2011-12-21 海洋王照明科技股份有限公司 Perylene tetracarboxylic diimide copolymer containing dithieno quinoxaline unit as well as preparation method and application thereof
CN102816301A (en) * 2012-08-30 2012-12-12 西安近代化学研究所 Dithiophene ring-fused germanium pentadiene-fluoroquinoxaline conjugated polymer
CN103360580A (en) * 2012-03-28 2013-10-23 株式会社东芝 Organic compound and solar cell using the same
US20140318628A1 (en) * 2013-04-30 2014-10-30 Advent Technologies Inc. Conjugated Polymers Containing Fused Electron Rich and Electron Poor Units, Preparation, Method and Uses
WO2016071140A1 (en) * 2014-11-04 2016-05-12 Basf Se Phenacene compounds for organic electronics
CN105906788A (en) * 2016-06-12 2016-08-31 南京邮电大学 Polymer of phenazine structure and preparation method and application thereof
CN106104836A (en) * 2014-02-20 2016-11-09 创新实验室有限公司 Conjugated polymer
CN106905306A (en) * 2017-01-12 2017-06-30 中南大学 Hexafluoro quinoxaline compounds and hexafluoro quinoxaline copolymer and application
KR20170106802A (en) * 2016-03-14 2017-09-22 건국대학교 산학협력단 Phenazine derivatives with the extended conjugated structure and applied to the organic photovoltaic polymers
CN108250222A (en) * 2018-01-30 2018-07-06 常州大学 (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials
WO2018131766A1 (en) * 2017-01-10 2018-07-19 건국대학교 산학협력단 Phenazine derivative having increased solubility, and polymer for organic photovoltaic conversion device, using same
KR20190086210A (en) * 2018-01-12 2019-07-22 주식회사 엘지화학 Heterocyclic compound and organic photovoltaic device comprising the same

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918135A (en) * 2004-01-13 2007-02-21 日产化学工业株式会社 Aminoquinoxaline compound, polyaminoquinoxaline compound, and use thereof
CN102124044A (en) * 2008-08-18 2011-07-13 默克专利股份有限公司 Indacenodithiophene and indacenodiselenophene polymers and their use as organic semiconductors
CN102159617A (en) * 2008-09-19 2011-08-17 默克专利股份有限公司 Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors
CN102050794A (en) * 2009-11-09 2011-05-11 财团法人工业技术研究院 Quinoxalin derivative and organic LED (Light-Emitting Diode) containing same
CN102286140A (en) * 2010-06-18 2011-12-21 海洋王照明科技股份有限公司 Perylene tetracarboxylic diimide copolymer containing dithieno quinoxaline unit as well as preparation method and application thereof
CN103360580A (en) * 2012-03-28 2013-10-23 株式会社东芝 Organic compound and solar cell using the same
CN102816301A (en) * 2012-08-30 2012-12-12 西安近代化学研究所 Dithiophene ring-fused germanium pentadiene-fluoroquinoxaline conjugated polymer
US20140318628A1 (en) * 2013-04-30 2014-10-30 Advent Technologies Inc. Conjugated Polymers Containing Fused Electron Rich and Electron Poor Units, Preparation, Method and Uses
CN106104836A (en) * 2014-02-20 2016-11-09 创新实验室有限公司 Conjugated polymer
WO2016071140A1 (en) * 2014-11-04 2016-05-12 Basf Se Phenacene compounds for organic electronics
KR20170106802A (en) * 2016-03-14 2017-09-22 건국대학교 산학협력단 Phenazine derivatives with the extended conjugated structure and applied to the organic photovoltaic polymers
CN105906788A (en) * 2016-06-12 2016-08-31 南京邮电大学 Polymer of phenazine structure and preparation method and application thereof
WO2018131766A1 (en) * 2017-01-10 2018-07-19 건국대학교 산학협력단 Phenazine derivative having increased solubility, and polymer for organic photovoltaic conversion device, using same
CN106905306A (en) * 2017-01-12 2017-06-30 中南大学 Hexafluoro quinoxaline compounds and hexafluoro quinoxaline copolymer and application
KR20190086210A (en) * 2018-01-12 2019-07-22 주식회사 엘지화학 Heterocyclic compound and organic photovoltaic device comprising the same
CN108250222A (en) * 2018-01-30 2018-07-06 常州大学 (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHONG-YU MEI ET AL.: "A Family of Donor-Acceptor Photovoltaic Polymers with Fused 4,7-Dithienyl-2,1,3-benzothiadiazole Units: Effect of Structural Fusion and Side Chains", 《MACROMOLECULES》 *
JIE ZHANG ET AL.: "Synthesis of Quinoxaline-Based Donor−Acceptor Narrow-Band-Gap Polymers and Their Cyclized Derivatives for Bulk-Heterojunction Polymer Solar Cell Applications", 《MACROMOLECULES》 *
YONG ZHANG ET AL.: "Synthesis, Characterization, Charge Transport, and Photovoltaic Properties of Dithienobenzoquinoxaline- and Dithienobenzopyridopyrazine-Based Conjugated Polymers", 《MACROMOLECULES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316216A (en) * 2021-11-17 2022-04-12 厦门华厦学院 Symmetric polymer based on dithienoquinoxaline-containing matrix as center and flexible electrochromic device
CN114349766A (en) * 2021-12-20 2022-04-15 淮阴工学院 D-A-D type organic semiconductor material and preparation method and application thereof
CN115386068A (en) * 2022-08-18 2022-11-25 东华大学 Conjugated polymer material containing benzodithiophene-4, 5-diketone and preparation method and application thereof

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