CN110746372A - Small molecule acceptor material with low lowest unoccupied molecular orbital energy level, preparation method and application - Google Patents
Small molecule acceptor material with low lowest unoccupied molecular orbital energy level, preparation method and application Download PDFInfo
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- CN110746372A CN110746372A CN201911187318.4A CN201911187318A CN110746372A CN 110746372 A CN110746372 A CN 110746372A CN 201911187318 A CN201911187318 A CN 201911187318A CN 110746372 A CN110746372 A CN 110746372A
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- dioctylfluorene
- difluorobenzaldehyde
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 title claims abstract description 26
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- -1 (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene Chemical compound 0.000 claims abstract description 26
- 229940123464 Thiazolidinedione Drugs 0.000 claims abstract description 15
- CZGVAISJIQNQEJ-UHFFFAOYSA-N 4-bromo-2,6-difluorobenzaldehyde Chemical compound FC1=CC(Br)=CC(F)=C1C=O CZGVAISJIQNQEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- UPCYEFFISUGBRW-UHFFFAOYSA-N 3-ethyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CCN1C(=O)CSC1=S UPCYEFFISUGBRW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 8
- 229940043376 ammonium acetate Drugs 0.000 claims description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004776 molecular orbital Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/36—Sulfur atoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a small molecule receptor material with low lowest unoccupied molecular orbital energy level, a preparation method and application thereof. The small molecule acceptor material comprises 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctyl fluorene and has a structure shown in a formula (I):
Description
Technical Field
The invention relates to a receptor material, in particular to a small molecule receptor material with low lowest unoccupied molecular orbital energy level, a preparation method and application thereof, and belongs to the technical field of photovoltaics.
Background
With the development of society, the problem of energy shortage has become more serious. Solar energy is inexhaustible clean energy, and if the solar energy can be fully utilized, the problem of energy shortage can be effectively solved. The organic solar cell can convert solar energy into electric energy, is low in price, can be produced by large-scale printing, and is a new-generation green energy technology. The most important light-absorbing layer material of organic solar cell is formed by blending donor material and acceptor material, wherein the main acceptor material is fullerene derivative, such as PC61BM and PC71BM, and the like. However, the fullerene derivative acceptor material has the disadvantages of high price, high lowest unoccupied molecular orbital level (3.7eV), influence on photoelectric conversion efficiency and the like.
Disclosure of Invention
The invention mainly aims to provide a small molecule acceptor material with low lowest unoccupied molecular orbital level and a preparation method thereof, so as to overcome the defects in the prior art.
Another object of the present invention is to provide the use of the small molecule acceptor material with low lowest unoccupied molecular orbital level.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
one embodiment of the present invention provides a small molecule acceptor material with a low lowest unoccupied molecular orbital level, which comprises 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene and has a structure represented by formula (I):
also provided in some embodiments of the present invention is a method of making a low lowest unoccupied molecular orbital level small molecule acceptor material, comprising:
subjecting 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene and 4-bromo-2, 6-difluorobenzaldehyde to a Suzuki coupling reaction in the presence of a catalyst to produce intermediate 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene;
subjecting 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene and 3-ethyl rhodanine to Knoevenagel coupling reaction to produce 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene having a structure represented by formula (I):
also provided in some embodiments of the invention are small molecule acceptor materials of low lowest unoccupied molecular orbital levels made by the foregoing methods.
The invention also provides the application of the small molecule acceptor material with the low lowest unoccupied molecular orbital level in the field of preparing the organic solar cell.
Accordingly, some embodiments of the present invention also provide an organic solar cell comprising the aforementioned low lowest unoccupied molecular orbital level small molecule acceptor material.
Compared with the prior art, the invention has at least the following remarkable effects:
1) the micromolecular electron acceptor material provided by the invention has a low lowest unoccupied molecular orbital level of 3.1eV, and can effectively improve the photoelectric conversion efficiency of the cell.
2) The micromolecule acceptor material with low lowest unoccupied molecular orbital energy level provided by the invention is simple to prepare and low in price, and can realize photovoltaic conversion efficiency equivalent to that of fullerene and derivatives thereof.
Detailed Description
As described above, in view of the problems of the fullerene derivative acceptor material in the prior art, the inventors of the present invention have made extensive studies and practice to provide a technical solution of the present invention, provide a small molecule electron acceptor material with simple synthesis, low cost, and low lowest unoccupied molecular orbital level, and obtain unexpectedly good technical effects. The technical solution of the present invention, its implementation process and principle, etc. will be further explained as follows.
An aspect of an embodiment of the present invention provides a small molecule acceptor material having a low lowest unoccupied molecular orbital level, which includes 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene, and has a structure represented by formula (I):
in another aspect of the embodiments of the present invention, there is provided a method for preparing a small molecule acceptor material with a low lowest unoccupied molecular orbital level, including:
subjecting 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene and 4-bromo-2, 6-difluorobenzaldehyde to a Suzuki coupling reaction in the presence of a catalyst to produce intermediate 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene;
subjecting 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene and 3-ethyl rhodanine to Knoevenagel coupling reaction to produce 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene having a structure represented by formula (I):
in some embodiments, the molar ratio of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene to 4-bromo-2, 6-difluorobenzaldehyde is 0.5: 1.1 to 1.5.
In some embodiments, the molar ratio of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene to catalyst is 0.5: 0.04 to 0.05.
In some embodiments, the catalyst comprises palladium tetratriphenylphosphine, but is not limited thereto.
In some embodiments, the method of making specifically comprises:
mixing 4-bromo-2, 6-difluorobenzaldehyde with a potassium carbonate aqueous solution, uniformly stirring, adding a catalyst and a first solvent, uniformly stirring, adding 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene, and uniformly stirring to form a first uniform mixed reaction system;
heating the first uniformly mixed reaction system to 80-90 ℃ at the speed of 10-15 ℃/min, stirring and reacting for 4-6 h at the temperature of 80-90 ℃, and then carrying out post-treatment to obtain the 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene.
In the invention, the pH value of the system can be regulated and controlled by adding the potassium carbonate aqueous solution, thereby promoting the successful synthesis.
Further, the organic solvent includes toluene, but is not limited thereto.
In some embodiments, the molar ratio of 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene to 3-ethyirhodanine is 1: 2.2 to 2.5.
In some embodiments, the molar ratio of 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene to ammonium acetate is 1: 0.4 to 0.6.
In some embodiments, the method of making specifically comprises:
mixing and stirring 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene, 3-ethyl rhodanine and a second solvent uniformly to form a second uniformly mixed reaction system;
heating the second uniformly mixed reaction system to 90-100 ℃ at the speed of 10-15 ℃/min, stirring and reacting at 90-100 ℃ for 12-16 h, and then carrying out post-treatment to obtain the 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctyl fluorene.
Further, the second solvent includes any one or a combination of two or more of chlorobenzene, glacial acetic acid, ammonium acetate, and the like, but is not limited thereto.
As a more specific preferred embodiment, the preparation method specifically comprises the following steps:
adding 1.1-1.5 mol parts of 4-bromo-2, 6-difluorobenzaldehyde and 20.0 ml of 2.0 mol per liter of potassium carbonate aqueous solution into a reaction kettle, magnetically stirring for 5 minutes at room temperature, then adding 0.04-0.05 mol part of tetratriphenylphosphine palladium and 20.0 ml of toluene, magnetically stirring for 30 minutes at room temperature, then adding 0.5 mol part of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene, magnetically stirring for 30 minutes at room temperature, heating to 80-90 ℃ at the speed of 10-15 ℃/minute, stirring for 4-6 hours at constant temperature of 80-90 ℃, stopping reaction, cooling to room temperature, adding 300.0 ml of distilled water, magnetically stirring for 10 minutes at room temperature, stopping stirring, separating out a toluene phase by using a separating funnel, transferring the toluene phase into a rotary evaporator, evaporating toluene at 60 ℃ under reduced pressure to obtain an intermediate product 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene;
adding 1.0 mol part of 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene and 2.2-2.5 mol parts of 3-ethyl rhodanine into a reaction kettle, adding 15.0 ml of chlorobenzene and 15.0 ml of glacial acetic acid, magnetically stirring for 30 minutes at room temperature, continuously adding 0.4-0.6 mol part of ammonium acetate, magnetically stirring for 30 minutes at room temperature, heating to 90-100 ℃ at the speed of 10-15 ℃/minute, stirring for 12-16 hours at constant temperature of 90-100 ℃, stopping the reaction, cooling to room temperature, adding 100.0 ml of distilled water, magnetically stirring for 30 minutes at room temperature, stopping stirring, separating out a chlorobenzene phase by using a separating funnel, transferring the chlorobenzene phase into a rotary evaporator, evaporating the chlorobenzene at 150 ℃ under reduced pressure to obtain 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene.
Another aspect of embodiments of the invention also provides a small molecule acceptor material with a low lowest unoccupied molecular orbital level prepared by the foregoing method.
In another aspect of the embodiments of the present invention, there is also provided a use of the small molecule acceptor material with the aforementioned low lowest unoccupied molecular orbital level in the field of preparing an organic solar cell.
Accordingly, another aspect of the embodiments of the present invention also provides an organic solar cell including the aforementioned small molecule acceptor material with a low lowest unoccupied molecular orbital level.
In summary, by the above technical scheme, the lowest unoccupied molecular orbital level of the small-molecule electron acceptor material provided by the invention is lower, namely 3.1eV, so that the photoelectric conversion efficiency of the cell can be effectively improved; and the preparation is simple, the price is low, and the photovoltaic conversion efficiency equivalent to that of the fullerene and the fullerene derivative can be realized.
In order to make the present invention more comprehensible, the technical solutions of the present invention will be further described below with reference to several embodiments, and it should be noted that these embodiments are only exemplary illustrations of the present invention, and are only a part of the embodiments of the present invention, rather than all of the embodiments. Although various product structure parameters, various reaction participants and process conditions are typical examples, the inventors of the present invention have proved through a lot of experiments that other types of reaction participants and other process conditions listed above are also applicable and can achieve the claimed technical effects. The technical aspects of the present invention will be described below with reference to some preferred embodiments, but the present invention is not limited to the following embodiments, and variations and implementations are included in the technical scope of the present invention without departing from the spirit of the present invention.
Example 1
Adding 1.1 mol parts of 4-bromo-2, 6-difluorobenzaldehyde and 20.0 ml of 2.0 mol/l aqueous potassium carbonate solution into a reaction kettle, magnetically stirring at room temperature for 5 minutes, then adding 0.04 mol parts of tetratriphenylphosphine palladium and 20.0 ml of toluene, magnetically stirring at room temperature for 30 minutes, then adding 0.5 mol parts of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene, magnetically stirring at room temperature for 30 minutes, heating to 90 ℃ at the speed of 10 ℃/minute, stirring at constant temperature of 90 ℃ for 4 hours, stopping the reaction, cooling to room temperature, adding 300.0 ml of distilled water, magnetically stirring at room temperature for 10 minutes, stopping the stirring, separating out a toluene phase by using a separating funnel, transferring the toluene phase into a rotary evaporator, evaporating the toluene at 60 ℃ under reduced pressure, obtaining an intermediate product 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene;
adding 1.0 mol part of 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene and 2.2 mol parts of 3-ethyl rhodanine into a reaction kettle, adding 15.0 ml of chlorobenzene and 15.0 ml of glacial acetic acid, magnetically stirring at room temperature for 30 minutes, continuously adding 0.5 mol part of ammonium acetate, magnetically stirring at room temperature for 30 minutes, heating to 90 ℃ at the speed of 10 ℃/minute, stirring at the constant temperature of 90 ℃ for 16 hours, stopping the reaction, cooling to room temperature, adding 100.0 ml of distilled water, magnetically stirring at room temperature for 30 minutes, stopping the stirring, separating out a chlorobenzene phase by using a separating funnel, transferring the chlorobenzene phase into a rotary evaporator, evaporating at 150 ℃ under reduced pressure to remove the chlorobenzene, and obtaining 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene.
Example 2
Adding 1.2 mol parts of 4-bromo-2, 6-difluorobenzaldehyde and 20.0 ml of 2.0 mol/l aqueous potassium carbonate solution into a reaction kettle, magnetically stirring at room temperature for 5 minutes, then adding 0.05 mol parts of tetratriphenylphosphine palladium and 20.0 ml of toluene, magnetically stirring at room temperature for 30 minutes, then adding 0.5 mol parts of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene, magnetically stirring at room temperature for 30 minutes, heating to 80 ℃ at the speed of 12 ℃/minute, stirring at constant temperature 80 ℃ for 6 hours, stopping the reaction, cooling to room temperature, adding 300.0 ml of distilled water, magnetically stirring at room temperature for 10 minutes, stopping the stirring, separating out a toluene phase by using a separating funnel, transferring the toluene phase into a rotary evaporator, evaporating the toluene at 60 ℃ under reduced pressure, obtaining an intermediate product 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene;
adding 1.0 mol part of 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene and 2.3 mol parts of 3-ethyl rhodanine into a reaction kettle, adding 15.0 ml of chlorobenzene and 15.0 ml of glacial acetic acid, magnetically stirring at room temperature for 30 minutes, continuously adding 0.4 mol part of ammonium acetate, magnetically stirring at room temperature for 30 minutes, heating to 100 ℃ at the speed of 15 ℃/minute, stirring at constant temperature of 100 ℃ for 12 hours, stopping the reaction, cooling to room temperature, adding 100.0 ml of distilled water, magnetically stirring at room temperature for 30 minutes, stopping stirring, separating out a chlorobenzene phase by using a separating funnel, transferring the chlorobenzene phase into a rotary evaporator, evaporating at 150 ℃ under reduced pressure to remove chlorobenzene, and obtaining 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene.
Example 3
Adding 1.5 mol parts of 4-bromo-2, 6-difluorobenzaldehyde and 20.0 ml of 2.0 mol/l aqueous potassium carbonate solution into a reaction kettle, magnetically stirring at room temperature for 5 minutes, then adding 0.045 mol parts of tetratriphenylphosphine palladium and 20.0 ml of toluene, magnetically stirring at room temperature for 30 minutes, then adding 0.5 mol parts of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene, magnetically stirring at room temperature for 30 minutes, heating to 85 ℃ at the speed of 15 ℃/minute, stirring at constant temperature of 85 ℃ for 5 hours, stopping the reaction, cooling to room temperature, adding 300.0 ml of distilled water, magnetically stirring at room temperature for 10 minutes, stopping the stirring, separating out a toluene phase by using a separating funnel, transferring the toluene phase into a rotary evaporator, evaporating the toluene at 60 ℃ under reduced pressure, obtaining an intermediate product 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene;
adding 1.0 mol part of 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene and 2.5 mol parts of 3-ethyl rhodanine into a reaction kettle, adding 15.0 ml of chlorobenzene and 15.0 ml of glacial acetic acid, magnetically stirring at room temperature for 30 minutes, continuously adding 0.6 mol part of ammonium acetate, magnetically stirring at room temperature for 30 minutes, heating to 95 ℃ at the speed of 13 ℃/minute, stirring at constant temperature of 95 ℃ for 14 hours, stopping the reaction, cooling to room temperature, adding 100.0 ml of distilled water, magnetically stirring at room temperature for 30 minutes, stopping stirring, separating a chlorobenzene phase by using a separating funnel, transferring the chlorobenzene phase into a rotary evaporator, evaporating at 150 ℃ under reduced pressure to remove chlorobenzene, and obtaining 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene.
Test example 1
The photoelectric conversion efficiency of 2, 7-bis (2, 6-difluorophenyl-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene was tested by a forward organic solar cell device. The device structure is as follows: ITO/PEDOT PSS/poly [ [4, 8-bis [ (2-ethylhexyl) oxo ]]Benzo [1,2-b:4,5-b']Dithiophene-2, 6-diyl]-alt- [ 3-fluoro-2- [ (2-ethylhexyl) carbonyl]Thieno [3,4-b]Thiophenediyl]](PTB7), 2, 7-bis (2, 6-difluorophenyl-1- (3-ethyl-2-thioxo-4-thiazolidinedione)) -9, 9-dioctylfluorene/PFN/aluminum (Al) prepared in example 1 and example 2. The mass ratio of PTB7 to example 1 or example 2 was 1: 1. The thickness of PEDOT and PSS is 30-40 nm. The thickness of the PFN is 5-10 nanometers. The evaporation thickness of Al is 80-100 nm. For comparison, PC was also used61BM Acceptor made the same organic SunCan be used as a battery. The prepared organic solar cell was further tested for photoelectric conversion efficiency by a Keithley2400 system. The photoelectric conversion efficiency was an average of 10 cells. The data such as the photoelectric conversion efficiency of the battery are shown in the table 1:
TABLE 1
| Receptor material | PCE/％ |
| Example 1 | 6.8 |
| Example 2 | 7.0 |
| PC61BM | 6.9 |
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A small molecule acceptor material having a low lowest unoccupied molecular orbital level, comprising 2, 7-bis (2, 6-difluorophenyl-1- (3-ethyl-2-thioxo-4-thiazolidinedione)) -9, 9-dioctylfluorene and having the structure shown in formula (I):
2. a preparation method of a small molecule acceptor material with low lowest unoccupied molecular orbital level is characterized by comprising the following steps:
subjecting 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene and 4-bromo-2, 6-difluorobenzaldehyde to a Suzuki coupling reaction in the presence of a catalyst to produce intermediate 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene;
subjecting 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene and 3-ethyl rhodanine to Knoevenagel coupling reaction to produce 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctylfluorene having a structure represented by formula (I):
3. the method of claim 2, wherein: the molar ratio of the 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene to 4-bromo-2, 6-difluorobenzaldehyde is 0.5: 1.1 to 1.5.
4. The method of claim 2, wherein: the molar ratio of the 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene to the catalyst is 0.5: 0.04 to 0.05;
and/or, the catalyst comprises palladium tetratriphenylphosphine.
5. The method according to claim 2, comprising:
mixing 4-bromo-2, 6-difluorobenzaldehyde with a potassium carbonate aqueous solution, uniformly stirring, adding a catalyst and a first solvent, uniformly stirring, adding 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene, and uniformly stirring to form a first uniform mixed reaction system;
heating the first uniformly mixed reaction system to 80-90 ℃ at the speed of 10-15 ℃/min, stirring and reacting at 80-90 ℃ for 4-6 h, and performing post-treatment to obtain the 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctyl fluorene;
preferably, the organic solvent comprises toluene.
6. The method of claim 2, wherein: the molar ratio of the 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene to the 3-ethyoxyl rhodanine is 1: 2.2 to 2.5;
and/or the molar ratio of the 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene to the ammonium acetate is 1: 0.4 to 0.6.
7. The method according to claim 2 or 6, characterized in that it comprises in particular:
mixing and stirring 2, 7-bis (2, 6-difluorobenzaldehyde) -9, 9-dioctylfluorene, 3-ethyl rhodanine and a second solvent uniformly to form a second uniformly mixed reaction system;
heating the second uniformly mixed reaction system to 90-100 ℃ at the speed of 10-15 ℃/min, stirring and reacting at 90-100 ℃ for 12-16 h, and then carrying out post-treatment to obtain 2, 7-bis (2, 6-difluorobenzene-1- (3-ethyl-2-thio-4-thiazolidinedione)) -9, 9-dioctyl fluorene;
preferably, the second solvent comprises one or more of chlorobenzene, glacial acetic acid and ammonium acetate.
8. A small molecule acceptor material of low lowest unoccupied molecular orbital level prepared by the method of any one of claims 2-7.
9. Use of the low lowest unoccupied molecular orbital level small molecule acceptor material of claim 1 or 8 in the field of preparing organic solar cells.
10. An organic solar cell comprising the low lowest unoccupied molecular orbital level small molecule acceptor material of claim 1 or 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115197129A (en) * | 2022-08-08 | 2022-10-18 | 南昌航空大学 | Fluorene micromolecule cathode interface layer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191466A1 (en) * | 2016-05-06 | 2017-11-09 | Imperial Innovations Limited | Organic ternary blends |
| CN108129447A (en) * | 2017-12-30 | 2018-06-08 | 武汉理工大学 | A kind of Novel Fluorene class organic solar batteries acceptor material and its preparation method and application |
| CN108218887A (en) * | 2017-10-23 | 2018-06-29 | 华南理工大学 | A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application |
| CN110003245A (en) * | 2019-04-09 | 2019-07-12 | 常州大学 | A kind of alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound and the preparation method and application thereof |
-
2019
- 2019-11-28 CN CN201911187318.4A patent/CN110746372A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191466A1 (en) * | 2016-05-06 | 2017-11-09 | Imperial Innovations Limited | Organic ternary blends |
| CN108218887A (en) * | 2017-10-23 | 2018-06-29 | 华南理工大学 | A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application |
| CN108129447A (en) * | 2017-12-30 | 2018-06-08 | 武汉理工大学 | A kind of Novel Fluorene class organic solar batteries acceptor material and its preparation method and application |
| CN110003245A (en) * | 2019-04-09 | 2019-07-12 | 常州大学 | A kind of alkyl/sulfanyl nitrogen heteroaromatic rings end D (A-Ar)2Type conjugated compound and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 姜鸿基 等: "基于芴和2,4-二氟苯的寡聚物的合成与表征", 《南京邮电大学学报(自然科学版)》 * |
| 李盛彪 等: "新型含氟光电材料单体的合成", 《有机氟工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197129A (en) * | 2022-08-08 | 2022-10-18 | 南昌航空大学 | Fluorene micromolecule cathode interface layer and preparation method thereof |
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