CN115010724A - Preparation method and application of oligomer based on A-D-A type small molecular receptor - Google Patents
Preparation method and application of oligomer based on A-D-A type small molecular receptor Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000004414 alkyl thio group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
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- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 229910003472 fullerene Inorganic materials 0.000 abstract description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical compound C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 abstract 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 abstract 1
- 238000007171 acid catalysis Methods 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl sulfur Chemical compound 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000013087 polymer photovoltaic Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
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- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- HQOWCDPFDSRYRO-CDKVKFQUSA-N CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 Chemical compound CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 HQOWCDPFDSRYRO-CDKVKFQUSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- 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
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- 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
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Spectroscopy & Molecular Physics (AREA)
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method and application of an oligomer based on an A-D-A type micromolecular receptor, and relates to the field of organic semiconductors. In particular to a Knoevenagel condensation reaction based on Lewis acid catalysis. The invention discloses a novel synthesis method of an oligomer organic semiconductor material, wherein a unit D is a conjugated aromatic ring or a condensed ring constructed by the conjugated aromatic ring; the A unit is an electron-deficient group containing an active methylene group, such as 1, 3-indandione and derivatives thereof. Compared with the traditional method, the method disclosed by the invention has the characteristics of high yield, pure product and the like, has better substrate adaptability, and can be widely applied to synthesis of organic solar cell receptor materials. The synthesized product can be applied to non-fullerene organic solar cell devices.
Description
Technical Field
The invention belongs to the field of organic semiconductors, and particularly relates to a preparation method and application of an oligomer constructed by using an acceptor-donor-acceptor (A-D-A) type micromolecule acceptor as a basic construction unit.
Background
The organic solar cell has the potential advantages of light weight, good flexibility, simple processing mode, capability of large-area preparation, low cost and the like, and is widely concerned by academia and industry. Based on an A-D-A type organic Small molecule acceptor material (SMA for short, such as ITIC and Y6), the charge transfer between an electron donating group (D) and an electron withdrawing group (A) is utilized to realize the regulation and control of absorption and energy level and other photophysical properties, and further the great improvement of photovoltaic performance can be realized (Nat Rev Mater,2018,3, 18003). High photoelectric conversion efficiency is obtained based on the small molecule receptors, but the small molecule receptors are easy to crystallize and have poor device stability. The non-fullerene small molecule receptor is copolymerized with other units and is embedded into a conjugated polymer main chain, and the prepared polymer receptor is also called a polymerized small molecule receptor (PSMA), so that the defects of easy crystallization and poor photo-thermal stability of the small molecule receptor can be well overcome (Angew Chem Int Ed,2017,56,13503, Angew Chem. Int. Ed.2021,60(9) and 4422). Meanwhile, the obtained polymer receptor has the advantages of good film forming property and strong tensile resistance, and is particularly suitable for flexible and wearable equipment.
However, the polymerization degree of the polymer receptor is difficult to control in the preparation process, so that the polymer receptor has large batch difference and poor device performance stability. The oligomer acceptor (oligomer SMA) has the advantages of stable small molecular acceptor batch, determined structure and the like on the basis of the advantages of the polymer acceptor. The synthesis method of the oligomer acceptor and the photovoltaic performance research have important significance for researching the corresponding relation between the structure and the function and developing the high-performance organic solar cell acceptor material.
There is currently no relevant study on oligomer receptors. In the reactions known to date, the coupling using noble metal catalysts can theoretically lead to dimers. However, such reactions are much more limited in use, and therefore the development of new synthetic methods is very important for the theoretical research and commercial application of oligomer acceptor (oligomer SMA) acceptor materials.
Disclosure of Invention
The invention aims to provide a preparation method and application of an oligomer organic semiconductor material based on an A-D-A type micromolecular receptor.
The structural formula of the oligomer organic semiconductor material provided by the invention is shown as a formula I:
formula I
In formula I, the group D is selected from any one of the following units, the dotted line being the site of attachment to the double bond in formula I:
wherein, R1-R6 in the formula II are independently selected from H, halogen, straight chain or branched chain alkyl or alkoxy with 1-30 carbon atoms, alkylthio, silyl, and alkyl or alkoxy, alkylthio, and silane substituted aryl. The aryl group may be a benzene ring or a thiophene ring. The halogen may be F, Br or Cl;
in the formula II, X1-X3 are independently selected from one of O, S, Se and Te.
A is selected from any one of the following units:
wherein R in formula III is when A is linked to a linking group L 7 -R 10 One of the two is a connecting site, and the others are independently selected from one or more of F, Cl, Br, I, CN, H, trifluoromethyl, alkoxy and alkyl-sulfur bases, wherein the carbon atom number of alkyl in the alkoxy and alkylthio groups is 1-30 straight chains or branched chains;
when A is at the end of the oligomer of formula I, R 7 -R 10 Independently selected from one or more of F, Cl, Br, I, CN, H, trifluoromethyl, alkoxy and alkyl sulfur bases, wherein the number of alkyl carbon atoms in the alkoxy and the alkylthio group is 1-30 straight chains or branched chains;
x4 and X5 are selected from one or two of C-H, N.
Wherein the dotted line indicates the position of attachment to the double bond in formula I.
Wherein the linking group L of formula I is selected from any one of the units of formula IV
Wherein R in the formula IV 10 -R 13 Independently selected from one or more of F, Cl, Br, I, CN, H, trifluoromethyl, alkoxy and alkyl sulfur bases, wherein the carbon atom number of alkyl in the alkoxy and the alkyl sulfur is 1-30 straight chain or branched chain.
Wherein the curve indicates the position of attachment to the linking group L in formula I.
N in the formula I represents the number of the SMA repeating units, is a natural number between 1 and 50, and is preferably a natural number between 1 and 12.
When n is 1, the oligomer is specifically shown as formula V, but is not limited to the following formula:
the invention further provides a preparation method of the D-A polymer shown in the formula I, which comprises the following steps: carrying out condensation reaction on a compound shown as a formula VI and a compound shown as a formula VII under the action of a catalyst to obtain a D-A polymer shown as a formula I
Wherein m in formula VI is defined as n +1, 2m +2, wherein m is a natural number of 0-20, preferably 0-10.
D and A in formula VI are as defined in formula I.
When m is a natural number of 0, then n is a natural number of 1, and formula VI is represented by formula V:
d and A in formula VIII are as defined in formula VI.
The aldehyde-based compound in formula VIII is specifically shown below, but not limited thereto:
the linking group L of formula ii is the same as linking group L in formula I, and a is selected from any one of the following units:
wherein R in the formula X 7 -R 10 And X4 and X5 are as defined in formula III.
The compounds of formula VIII are specifically shown below, but are not limited thereto:
the preparation method can be specifically carried out according to the following method:
the catalyst being a Lewis acid, e.g. BF 3 ·Et 2 O、AlCl 3 、GaCl 3 、InCl 3 、Ga(OTf) 3 、GaBr 3 、GaI 3 Preferably GaCl 3 、BF 3 ·Et 2 O、Ga(OTf) 3 。
The adding amount of the catalyst is 0.01-20% of the total molar amount of the compound shown in the formula IV and the compound shown in the formula V, and the preferable amount is 5-10%.
The anhydride is a reactant and is shown as formula XII.
R in the formula XII 14 、R 15 Is independently ester group, alkoxy or one of F, Cl, Br, I, CN, H and OH. And a linear or branched alkyl group having 1 to 30 carbon atoms when the alkyl group is an ester group or an alkoxy group.
The anhydrides in formula XII are specifically shown below, but are not limited thereto:
the addition amount of the acid anhydride is 10-200%, preferably 200% of the total molar amount of the compound shown in the formula XI and the compound shown in the formula VIII.
The solvent is benzene, toluene, o-xylene, p-xylene, mesitylene, chlorobenzene or chlorobenzene. Toluene, p-xylene or chlorobenzene are preferred.
The molar ratio of the compound of formula VIII to the compound of formula XI is 1: 2-2.5, such as 1: 2;
the reaction temperature is 0-120 deg.C, preferably 20-100 deg.C.
The reaction time is 15 minutes to 24 hours, preferably 30 to 600 minutes.
The invention has the following beneficial effects:
the invention provides a synthesis method of an A-D-A type SMA based oligomerization receptor material, which has the characteristics of high yield, simple synthesis, pure product and the like. And has better substrate adaptability, and can be widely applied to the synthesis of A-D-A type SMA oligomerized polymer. The synthesized product is applied to a non-fullerene polymer solar cell device.
It is another object of the present invention to provide a photoactive layer. The photoactive layer is composed of an acceptor material shown in a formula I and a p-type electron donor material (polymer or micromolecule), wherein the mass ratio of the non-fullerene acceptor to the p-type donor material is 1: 0.1 to 10, such as 1: 1;
the p-type electron donor polymers of the present invention are suitable for use in any of a variety of p-type electron donor polymers, such as PBDB-T, that can be selected by one skilled in the art.
The photoactive layer can be prepared by mixing at least one solvent selected from toluene, xylene, trimethylbenzene, chloroform, chlorobenzene, dichlorobenzene and trichlorobenzene, and the concentration of the non-fullerene acceptor in the obtained mixture can be 0.5-50 mg/mL, preferably 4-20 mg/mL. The concentration of the p-type electron donor polymer may be from 0.5mg/mL to 50mg/mL, preferably from 3mg/mL to 20 mg/mL.
The invention also provides a polymer solar cell device comprising a first electrode, a second electrode spaced apart from the first electrode, and at least one semiconductor layer disposed between the first and second electrodes, the semiconductor layer comprising the polymer acceptor or the photoactive layer.
The application of the non-fullerene acceptor and the photoactive layer in the preparation of the following functional devices also belongs to the protection scope of the invention: thin film semiconductor devices, optical detection devices, polymer solar cell devices, and optoelectronic devices.
Aiming at the defects of the prior art, the invention develops a rapid polymerization method which avoids toxic tin reagents and has simpler and more convenient post-treatment. The present invention provides a large-scale and low-cost method for preparing a polymer acceptor material, which is required for commercialization of organic solar cells. Besides the application in organic solar cells, the method can also be applied to light-emitting diodes, field effect transistors, memory devices and the like.
Drawings
FIG. 1: nuclear magnetic spectrum of compound XI-11
FIG. 2 is a schematic diagram: nuclear magnetic spectrum of compound XI-12
FIG. 3: nuclear magnetic spectrum of compound IX-4
FIG. 4: nuclear magnetic spectrum of compound V-1
FIG. 5: nuclear magnetic spectrum of compound V-2
FIG. 6: synthetic route to oligomers
FIG. 7: J-V plot for devices fabricated with Compounds V-1 and V-2
FIG. 8: EQE curve chart of device prepared by using compounds V-1 and V-2
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. The pressures used in the following examples are at or near atmospheric pressure. All reagents and starting materials were obtained commercially unless otherwise indicated.
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the present invention is not limited to the following examples, and any changes or modifications may be made to the present invention without departing from the scope of the present invention. In the present invention, all percentages are units of matter, if not specified, and the equipment and materials employed are commercially available or commonly used in the art.
Nuclear magnetic resonance spectrometers and ESI mass spectrometers are used herein to characterize the synthesized structures.
Example 1
Synthesis of XI-11
The synthesis process is shown as the following formula:
a100 ml single neck flask was charged with 0.113g of formula XI-11a, 0.054g of formula XI-11a, 5ml of toluene, 5mg of tetrakis (triphenylphosphine) palladium. After heating at reflux for 5 hours, the solvent was dried by spinning off and separated by flash column chromatography (eluent dichloromethane) to give 0.11g of product XI-11 (92% yield). MS (ESI negative spectral mode) M/z [ M-1 ]] - :1185.3， [M-2] 2- :592.2。
Example 2
Synthesis of XI-12
The synthesis process is shown as the following formula:
in a 100ml single-mouth bottle0.113g of formula XI-11a, 0.054g of formula XI-11a, 5ml of toluene, 5mg of tetrakis (triphenylphosphine) palladium were added. After heating at reflux for 5 hours, the solvent was dried by evaporation and separated by flash column chromatography (eluent dichloromethane) to give 0.11g of product XI-11 (92% yield). MS (ESI negative spectral mode) M/z [ M-1 ]] - :1185.3， [M-2] 2- :592.2。
Example 3
Synthesis of IX-4
A100 ml single neck flask was charged with 1.08g of formula IX-4a, 50ml of 1, 2-dichloroethane, 0.30g of phosphorus oxychloride and 0.25g of DMF under ice bath. After stirring at room temperature for 3 hours, the mother liquor was poured into ice water, extracted with dichloromethane, and the organic phase was concentrated and then separated by column chromatography to give 0.98g of IX-4b (yield 90%).
A100 ml single neck flask was charged with 0.88g of formula IX-4b, 30ml of chloroform, 0.36g of 2F-Ic. After heating and refluxing for 3 hours, the mother liquor is settled into methanol, and solid powder is collected after centrifugation. The solid powder obtained by dissolution was separated by column chromatography to obtain 0.85g of IX-4b (yield 82%)
A100 ml single neck flask was charged with 0.66g of formula IX-4b, 20ml of 1, 2-dichloroethane, 0.30g of phosphorus oxychloride and 0.25g of DMF under ice bath. After stirring at room temperature for 3 hours, the mother liquor was poured into ice water, extracted with dichloromethane, and the organic phase was concentrated and then separated by column chromatography to give 0.62g of IX-4b (92% yield). MALDI-TOF M/z [ M +1 ]] + :1351.698。
Example 4
Synthesis of V-1
59.3mg of formula XI-11, 135.0mg of V-1, 10ml of toluene, 0.1ml of acetic anhydride and 50. mu.l of boron trifluoride diethyl etherate were charged in a 100ml one-neck flask. After stirring at 60 ℃ for 30 minutes, the solvent was spin-dried, and the residue was separated by column chromatography to give 182.9mg of V-1 (yield 95%). MALDI-TOF M/z [ M +1 ]] + :3852.998。
Example 5
Synthesis of V-1
59.3mg of formula XI-11, 135.0mg of V-1, 10ml of toluene, 0.1ml of acetic anhydride and 50. mu.l of boron trifluoride diethyl etherate were charged in a 100ml single-neck flask. After stirring at 60 ℃ for 30 minutes, the solvent was spin-dried, and the residue was separated by column chromatography to give 182.9mg of V-2 (yield 95%). MS-tof M/z [ M +1 ]] + :3852.898。
Example 6
Preparation of Polymer photovoltaic devices of conventional construction
The acceptor materials of examples 4 and 5 according to the invention were mixed with a commercially available polymer donor PM6 in a weight ratio of 1: 1 blending and dissolving in trichloromethane to prepare a blending active layer solution. Polymer photovoltaic devices were fabricated on transparent Indium Tin Oxide (ITO) substrates. The commonly used anode modification layer poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS) was spin-coated on the ITO surface for modification, and the thickness of the PEDOT: PSS layer was measured using a film thickness meter to be 30 nm. The blended active layer solution described above was then spin coated to a thin layer. Then at about 10 -4 And evaporating the silver-plated thin layers under the pressure of Pa to obtain the polymer photovoltaic device with the conventional structure. In filling with N 2 In the glove box of (1), AAA level solar simulator AM1.5G (100 mW/cm) 2 ) The open circuit voltage, short circuit current, fill factor and energy conversion efficiency of the prepared polymer photovoltaic device are tested. Which comprises the following steps: the open-circuit voltage of the PM6 system is 0.93V, and the short-circuit current is 15.73mA/cm 2 The fill factor was 64.50% and the energy conversion efficiency was 9.44%.
The invention is described with reference to specific embodiments and examples. However, the present invention is not limited to only the above-described embodiments and examples. It will be recognized by those of ordinary skill in the art based on the teachings herein that many alternatives and modifications may be made without departing from the scope of the invention as defined in the claims.
Claims (9)
1. A preparation method and application of an oligomer based on an A-D-A type micromolecular receptor are characterized in that a polymer receptor structure with the following structural general formula is synthesized.
2. The polymer structure according to claim 1, characterized in that D is an aromatic ring group or is formed by linking said aromatic ring groups, group D being selected from any one of the following units:
wherein, R1-R6 are independently selected from H, halogen, straight chain or branched chain alkyl or alkoxy with 1-30 carbon atoms, alkylthio, silyl, and alkyl or alkoxy, alkylthio, silane substituted aryl; the aryl group can be a benzene ring or a thiophene ring; the halogen may be F, Br or Cl; x 1 -X 3 Are all independently selected from one of O, S, Se and Te.
3. Polymeric organic semiconducting material according to claim 1, characterized in that a 1 And A 2 Independently selected from any one of the following units:
wherein R is 7 -R 10 Independently selected from the group consisting of F, Cl, Br, I, CN, H, trifluoromethyl, alkoxy, alkylthioThe number of carbon atoms of alkyl in alkoxy and alkylthio groups is 1-30 straight chain or branched chain; x 4 And X 5 One or two selected from C, N; the dotted line indicates the position of attachment to the double bond in formula I; wherein the linker is selected from any one of the following units
4. The small molecule receptor according to claim 1, characterized in that it is carried out according to the following method:
5. the process according to claim 4, characterized by BF 3 ·C 2 H 5 OC 2 H 5 、AlCl 3 、GaCl 3 、InCl 3 、Ga(OTf) 3 、GaBr 3 、GaI 3 Preferably GaCl 3 、BF 3 ·C 2 H 5 OC 2 H 5 、Ga(OTf) 3 。
6. The production method according to claim 4, characterized in that the acid anhydride used is independently selected from any one of the following units:
wherein R is C 2 -C 10 One of linear alkyl, tertiary butyl, isopropyl and allyl; x 6 Is one of F, Cl, Br, I, CN, H and OH.
7. The method according to claim 4, wherein the solvent is benzene, toluene, o-xylene, p-xylene, mesitylene, chlorobenzene. Toluene or xylene is preferred.
8. The process according to claim 4, wherein the condensation reaction conditions comprise a temperature of 20 to 110 ℃, preferably 60 ℃; the reaction time is 10 minutes to 6 hours, preferably 3 hours.
9. The method of claim 4, wherein:
and
the molar ratio of the compounds is 1: 1,; the addition amount of the acid anhydride is
0.01-20%, preferably 10-30% of the total molar amount of the compound; the addition amount of the acid anhydride is
The total molar weight of the compound is 0.01-20%, preferably 10-30%.
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| CN117603228B (en) * | 2024-01-23 | 2024-04-02 | 内蒙古大学 | Near infrared two-region organic fluorescent probe and preparation method and application thereof |
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