CN116606304A - High-charge-density organic semiconductor molecule and preparation method and application thereof - Google Patents
High-charge-density organic semiconductor molecule and preparation method and application thereof Download PDFInfo
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- CN116606304A CN116606304A CN202310824561.2A CN202310824561A CN116606304A CN 116606304 A CN116606304 A CN 116606304A CN 202310824561 A CN202310824561 A CN 202310824561A CN 116606304 A CN116606304 A CN 116606304A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229930192474 thiophene Natural products 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 20
- 238000006467 substitution reaction Methods 0.000 claims abstract description 14
- 230000005669 field effect Effects 0.000 claims abstract description 5
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- QCSLIRFWJPOENV-UHFFFAOYSA-N (2-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1F QCSLIRFWJPOENV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- HWKZNRABKQDKTC-UHFFFAOYSA-N 2,5-diphenylthiophene Chemical compound C=1C=C(C=2C=CC=CC=2)SC=1C1=CC=CC=C1 HWKZNRABKQDKTC-UHFFFAOYSA-N 0.000 claims description 5
- MSLOGOFSUAKXGW-UHFFFAOYSA-N 2-phenyl-5-[4-(5-phenylthiophen-2-yl)phenyl]thiophene Chemical compound C=1C=C(C=2C=CC(=CC=2)C=2SC(=CC=2)C=2C=CC=CC=2)SC=1C1=CC=CC=C1 MSLOGOFSUAKXGW-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- WNNUVWFCGFUJFU-UHFFFAOYSA-N 2,6-diphenylthieno[2,3-f][1]benzothiole Chemical compound S1C=2C=C3C=C(C=4C=CC=CC=4)SC3=CC=2C=C1C1=CC=CC=C1 WNNUVWFCGFUJFU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [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 claims 1
- 239000004305 biphenyl Substances 0.000 abstract description 6
- 238000013500 data storage Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 46
- 239000013078 crystal Substances 0.000 description 20
- 238000001819 mass spectrum Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 5
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical group C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- KNXQDJCZSVHEIW-UHFFFAOYSA-N (3-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC(F)=C1 KNXQDJCZSVHEIW-UHFFFAOYSA-N 0.000 description 1
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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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
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The application provides a high-charge-density organic semiconductor molecule, a preparation method and application thereof, and belongs to the technical field of organic semiconductors. The palladium-catalyzed cross-coupling reaction is utilized to realize different substitution positions of F atoms of the parent molecule of the 2, 6-diphenyl dithiophene [3,2-B:2',3' -D ] thiophene, and the fact that the different substitution positions of F atoms can regulate the charge density of a semiconductor is verified. It was further demonstrated through experimentation that F-S interactions are one of the reasons for this phenomenon. The preparation method is simple, and the organic semiconductor molecules with high charge density prepared by the method can adjust the threshold voltage of the device when the organic field effect transistor is prepared, and have potential application in various fields such as temperature sensing, light detection, data storage and the like.
Description
Technical Field
The application belongs to the technical field of organic semiconductors, and particularly relates to a high-charge-density organic semiconductor molecule, and a preparation method and application thereof.
Background
The semiconductor materials industry is a strategic base industry supporting economic developments. With the development of flexible electronic devices, organic semiconductors have gained widespread attention by virtue of their high solubility, low cost, flexible molecular design, and mechanical flexibility. The flexible photoelectric device using the organic semiconductor as the active material has been developed rapidly, and the device performance is improved remarkably. The organic light-emitting diode has been successfully applied to various fields such as organic field effect transistors, organic electroluminescent diodes, organic solar cells and the like.
Organic semiconductors have been widely focused on their physicochemical properties as a core component of semiconductor devices. The design strategies of the prior art on organic semiconductor materials mainly comprise (1) the adjustment of the PN junction or donor-acceptor structure on the material energy level; (2) The rigidity of the molecule is changed by covalent bond linkage to form a condensed ring; (3) The adjustment of the material space structure is realized through intermolecular/intramolecular interaction; and (4) carrying out functional application on the material by adopting hetero atoms. Charge density has been a significant physical parameter in regulating carrier concentration and has been receiving extensive attention from researchers. However, the traditional adjusting method is mainly realized by doping, and the preparation method is complex. Based on the above, the application provides a high-charge-density organic semiconductor molecule and a preparation method thereof, which make up for the blank of the research fields of regulating the charge density of a material by a molecular design rule.
Disclosure of Invention
In order to solve the technical problems, the application provides a high-charge-density organic semiconductor molecule, and a preparation method and application thereof.
In order to achieve the above purpose, the present application provides the following technical solutions:
the application provides a high-charge-density organic semiconductor molecule which is an F atom ortho-substituted parent molecule, wherein the parent molecule comprises 2, 6-diphenyl dithiophene [3,2-B:2',3' -D ] thiophene, 2, 5-diphenyl thiophene [3,2-B ] thiophene, 2, 6-diphenyl benzo [1,2-B:4,5-B ' ] dithiophene, 1, 4-bis (5-phenyl thiophene-2-yl) benzene or 5, 5' -diphenyl-2, 2':5', 2' -trithiophene.
The application also provides a preparation method of the high-charge-density organic semiconductor molecule, which realizes F atom ortho-substitution of a parent molecule by using palladium-catalyzed cross-coupling reaction, and comprises the following steps:
and (3) refluxing and stirring the compound, 2-fluorobenzeneboronic acid, a catalyst and potassium carbonate in a mixed solvent, carrying out suction filtration and drying after the reaction is finished to obtain yellow solid powder, separating the yellow solid powder by column chromatography, and standing to obtain the high-charge-density organic semiconductor molecule.
Further, the compound comprises 2, 5-dibromodithioeno [3,2-B:2',3' -D ] thiophene.
Further, the catalyst is tetraphenylphosphine palladium.
Further, the molar ratio of the compound to the 2-fluorobenzeneboronic acid, the catalyst and the potassium carbonate is 2:4.2:0.12:8.
Further, the mixed solvent consists of toluene, ethanol and water in a volume ratio of 4:1:1, and the volume molar ratio of the mixed solvent to the compound is 12 mL:2 mmol.
Further, the reflux stirring time is 12h.
Further, the column chromatography separation adopts petroleum ether and ethyl acetate with the volume ratio of 10:1.
The application also provides application of the high-charge-density organic semiconductor molecule in preparation of an organic field effect transistor.
Compared with the prior art, the application has the following advantages and technical effects:
(1) The application designs and synthesizes the semiconductor molecules by utilizing palladium catalytic cross-coupling reaction, has simple preparation method, can adjust the threshold voltage of a device when the organic semiconductor molecules with high charge density are prepared into the organic field effect transistor, has potential application in various fields such as temperature sensing, light detection, data storage and the like, and simultaneously discovers that the regulation and control of the charge density of the organic semiconductor material can be realized by utilizing the difference of F atom substitution positions.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a nuclear magnetic resonance spectrum of the product prepared in example 1;
FIG. 2 is a high resolution mass spectrum of the product prepared in example 1, where a is the liquid chromatograph and b is the mass spectrometer;
FIG. 3 is a nuclear magnetic resonance spectrum of the product prepared in comparative example 1;
FIG. 4 is a high resolution mass spectrum of the product prepared in comparative example 1, where a is a liquid chromatograph and b is a mass spectrometer;
FIG. 5 is a nuclear magnetic resonance spectrum of the product prepared in comparative example 2;
FIG. 6 is a high resolution mass spectrum of the product prepared in comparative example 2, where a is a liquid chromatograph and b is a mass spectrometer;
FIG. 7 is a nuclear magnetic resonance spectrum of the product prepared in comparative example 3;
FIG. 8 is a high resolution mass spectrum of the product prepared in comparative example 3, where a is a liquid chromatograph and b is a mass spectrometer;
FIG. 9 is a synthetic process of organic semiconductor molecules in example 1 and comparative examples 1-3;
FIG. 10 is a crystal structure diagram of the organic semiconductor molecules of example 1 and comparative examples 1-3, wherein (a) is example 1, (b) is comparative example 1, (c) is comparative example 3, and (d) is comparative example 4;
FIG. 11 is a graph showing the results of electrical property tests of single crystal devices prepared using the organic semiconductor molecules of example 1;
FIG. 12 is a graph showing the results of electrical property tests of single crystal devices prepared using the organic semiconductor molecules of comparative example 1;
FIG. 13 is a graph showing the results of electrical property tests of single crystal devices prepared using the organic semiconductor molecules of comparative example 2;
FIG. 14 is a graph showing the results of electrical property tests of single crystal devices prepared using the organic semiconductor molecules of comparative example 3;
FIG. 15 is an X-ray photoelectron spectrum of an organic semiconductor molecule prepared in example 1 and comparative examples 1 to 3, wherein (a) is example 1, (b) is comparative example 1, (c) is comparative example 3, and (d) is comparative example 4.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The application provides a high-charge-density organic semiconductor molecule, which is an F atom ortho-substituted parent molecule, wherein the parent molecule comprises 2, 6-diphenyl dithiophene [3,2-B:2',3' -D]Thiophene (structural formula:) 2, 5-diphenylthiophene [3,2-b ]]Thiophene (structural formula:) 2, 6-diphenylbenzo [1,2-b:4,5-b ]']Dithiophene (structural formula:) 1, 4-bis (5-phenylthiophen-2-yl) benzene (structural formula: />) Or 5,5 "-diphenyl-2, 2':5',2" -trithiophene (structural formula: />)。
The application also provides a preparation method of the high-charge-density organic semiconductor molecule, which realizes F atom ortho-substitution of a parent molecule by using palladium-catalyzed cross-coupling reaction, and comprises the following steps:
and (3) refluxing and stirring the compound, 2-fluorobenzeneboronic acid, a catalyst and potassium carbonate in a mixed solvent, carrying out suction filtration and drying after the reaction is finished to obtain yellow solid powder, separating the yellow solid powder by column chromatography, and standing to obtain the high-charge-density organic semiconductor molecule.
In an embodiment of the application, the compound comprises 2, 5-dibromodithioeno [3,2-B:2',3' -D]Thiophene (structural formula:) But not limited to 2, 5-dibromodithioeno [3,2-B:2',3' -D]Thiophene, e.g. 2, 5-diphenylthiophene [3,2-b ] ortho-substituted with F atom]Thiophene, 2, 6-diphenylbenzo [1,2-b:4,5-b ]']The compounds need to be modified with dithiophene, 1, 4-bis (5-phenylthiophen-2-yl) benzene or 5,5 "-diphenyl-2, 2':5',2" -trithiophene.
In the embodiment of the application, the catalyst is tetraphenylphosphine palladium.
In the embodiment of the application, the molar ratio of the compound to the 2-fluorobenzeneboronic acid, the catalyst and the potassium carbonate is 2:4.2:0.12:8.
In the embodiment of the application, the mixed solvent consists of toluene, ethanol and water in the volume ratio of 4:1:1, and the volume molar ratio of the mixed solvent to the compound is 12 mL:2 mmol.
In the embodiment of the application, the reflux stirring time is 12 hours.
In the embodiment of the application, the column chromatography separation adopts petroleum ether and ethyl acetate with the volume ratio of 10:1.
The raw materials used in the examples of the present application are all commercially available.
In the embodiment of the application, the room temperature is 25+/-2 ℃.
The technical scheme of the application is further described by the following examples.
Example 1
Preparation of 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene:
0.71g of 2, 5-dibromodithioeno [3,2-B:2',3' -D]Thiophene (2 mmol), 0.59g 2-fluorobenzeneboronic acid (4.2 mmol), 0.14g triphenylphosphine palladium (0.12 mmol) and 1.10g potassium carbonate (8 mmol) are put into a two-mouth flask, the mixture is replaced by vacuum nitrogen for three times, 12mL of a mixed solvent consisting of toluene, ethanol and water in a volume ratio of 4:1:1 is added into the two-mouth flask by adopting a syringe injection method, after the mixture is refluxed and stirred for 12h, the reaction of the raw materials is tracked by a thin layer chromatography method to be complete, then the mixture is cooled to room temperature, filtered by suction, and dried, thus obtaining yellow solid powder. Then the yellow solid powder is subjected to column chromatography separation by petroleum ether and ethyl acetate with the volume ratio of 10:1, and a large amount of yellow flocculent solid is separated out after standing for 30 minutes, and finally yellow flocculent crystal is obtainedThe body is 2, 6-di (2-fluorophenyl) dithiophene [3,2-B:2',3' -D]Thiophene. The yield was tested: 76%. 1 H NMR(600MHz,DMSO-d 6 ) δ8.04 (s, 2H), 7.83 (t, J=7.8 Hz, 2H), 7.39 (dt, J=16.4, 9.3Hz, 4H), 7.30 (t, J=7.3 Hz, 2H). HRMS (ESI) theory M/z:383.99, found M/z: [ M+H: + ]:384.9989.
the nuclear magnetic resonance spectrum of the product prepared in example 1 is shown in figure 1; the high resolution mass spectrum is shown in figure 2, wherein a is a liquid chromatogram and b is a mass spectrum;
the nuclear magnetic resonance spectrograms and the high-resolution mass spectrum of fig. 1 and 2 clearly analyze the molecular structure, and an X-single crystal ray diffractometer verifies the F atom substitution position, so that the product prepared in the example 1 is determined to be F atom ortho-substituted 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene.
Comparative example 1 (no F atom substitution)
Preparation of 2, 6-diphenyldithiophene [3,2-B:2',3' -D ] thiophene:
0.71g of 2, 5-dibromodithioeno [3,2-B:2',3' -D]Thiophene (2 mmol), 0.24g phenylboronic acid (4.2 mmol), 0.14g tetraphenylphosphine palladium (0.12 mmol) and 1.10g potassium carbonate (8 mmol) are put into a two-neck flask, the mixture is replaced by vacuum nitrogen for three times, 12mL of a mixed solvent consisting of toluene, ethanol and water in a volume ratio of 4:1:1 is added into the two-neck flask by adopting a syringe injection method, after the mixture is refluxed and stirred for 12 hours, the raw materials are completely reacted by using a thin layer chromatography method, and then the mixture is cooled to room temperature, filtered by suction, and dried to obtain light gray solid powder. Separating the light gray solid powder by column chromatography with petroleum ether and ethyl acetate at volume ratio of 8:1, standing for 30 min to obtain a large amount of yellow flocculent solid, and finally obtaining yellow flocculent crystal, namely 2, 6-diphenyl dithiophene [3,2-B:2',3' -D]Thiophene. The yield was tested: 82%. 1 H NMR(600MHz,DMSO-d 6 ) Delta 7.83 (d, J=5.7 Hz, 2H), 7.68 (s, 4H), 7.44 (d, J=7.9 Hz, 4H), 7.33 (s, 2H) HRMS (ESI) theory M/z:348.01, found M/z: [ M+H ] + ]:349.0176.
The nuclear magnetic resonance spectrum of the product prepared in comparative example 1 is shown in fig. 3; the high resolution mass spectrum is shown in figure 4, wherein a is a liquid chromatogram and b is a mass spectrum;
the molecular structure is clearly analyzed by the nuclear magnetic resonance spectrograms and the high-resolution mass spectrum of fig. 3 and 4, so that the product prepared in the comparative example 1 is determined to be 2, 6-diphenyl dithiophene [3,2-B:2',3' -D ] thiophene without F atom substitution.
Comparative example 2 (meta-substitution of F atom)
Preparation of 2, 6-bis (3-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene:
0.71g of 2, 5-dibromodithioeno [3,2-B:2',3' -D]Thiophene (2 mmol), 0.59g 3-fluorobenzeneboronic acid (4.2 mmol), 0.14g triphenylphosphine palladium (0.12 mmol) and 1.10g potassium carbonate (8 mmol) are put into a two-mouth flask, the mixture is replaced by vacuum nitrogen for three times, 12mL of a mixed solvent consisting of toluene, ethanol and water in a volume ratio of 4:1:1 is added into the two-mouth flask by adopting a syringe injection method, after the mixture is refluxed and stirred for 12h, the raw materials are tracked to be completely reacted by a thin layer chromatography method, and then the mixture is cooled to room temperature, filtered by suction, dried, and light gray solid powder is obtained. Separating the light gray solid powder by column chromatography with petroleum ether and ethyl acetate at volume ratio of 15:1, standing for 30 min to obtain a large amount of yellow flocculent solid, and finally obtaining yellow flocculent crystal, namely 2, 6-bis (3-fluorophenyl) dithiophene [3,2-B:2',3' -D]Thiophene. The yield was tested: 89%. 1 H NMR(600MHz,DMSO-d 6 ) Delta 7.97 (d, J=4.2 Hz, 2H), 7.51 (d, J=10.9 Hz, 6H), 7.14 (t, J=8.5 Hz, 2H) HRMS (ESI) theory M/z:383.99, found M/z: [ M+H) + ]:384.9989.
The nuclear magnetic resonance spectrum of the product prepared in comparative example 2 is shown in fig. 5; the high resolution mass spectrum is shown in figure 6, wherein a is a liquid chromatogram and b is a mass spectrum;
the nuclear magnetic resonance spectrograms and the high-resolution mass spectrum of fig. 5 and 6 clearly analyze the molecular structure, and an X-single crystal ray diffractometer verifies the F atom substitution position, so that the product prepared in the comparative example 2 is determined to be F atom meta-substituted 2, 6-bis (3-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene.
Comparative example 3 (F atom para-substitution)
Preparation of 2, 6-bis (4-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene:
0.71g of 2, 5-dibromodithioeno [3,2-B:2',3' -D]Thiophene (2 mmol), 0.59g 4-fluorobenzeneboronic acid4.2 mmol), 0.14g of tetraphenylphosphine palladium (0.12 mmol) and 1.10g of potassium carbonate (8 mmol) are put into a two-neck flask, the mixture is replaced by vacuum nitrogen for three times, 12mL of a mixed solvent consisting of toluene, ethanol and water with the volume ratio of 4:1:1 is added into the two-neck flask by adopting a syringe injection method, after the mixture is refluxed and stirred for 12 hours, the reaction of the raw materials is tracked to be complete by a thin layer chromatography method, and then the mixture is cooled to room temperature, filtered by suction and dried to obtain light gray solid powder. Separating the light gray solid powder by column chromatography with petroleum ether and ethyl acetate with volume ratio of 10:1, standing for 30 min to obtain a large amount of yellow flocculent solid, and finally obtaining yellow flocculent crystal, namely 2, 6-bis (4-fluorophenyl) dithiophene [3,2-B:2',3' -D]Thiophene. The yield was tested: 81%. HRMS (ESI) theory M/z 383.99, found M/z: [ M+H ] + ]:384.9989. 1 H NMR(600MHz,Chloroform-d)δ7.59(s,4H),7.43(s,2H),7.11(s,4H).
The nuclear magnetic resonance spectrum of the product prepared in comparative example 3 is shown in fig. 7; the high resolution mass spectrum is shown in figure 8, wherein a is a liquid chromatogram and b is a mass spectrum;
the nuclear magnetic resonance spectrograms and the high-resolution mass spectrum of fig. 7 and 8 clearly analyze the molecular structure, and an X-single crystal ray diffractometer verifies the F atom substitution position, so that the product prepared in the comparative example 3 is determined to be F atom para-substituted 2, 6-bis (4-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene.
The synthetic procedure of the organic semiconductor molecules in example 1 and comparative examples 1-3 is shown in FIG. 9.
The crystal structure of the organic semiconductor molecules in example 1 and comparative examples 1-3 is shown in FIG. 10, wherein (a) is example 1, (b) is comparative example 1, (c) is comparative example 3, and (d) is comparative example 4.
Performance testing
The micro-nano crystals carrying the four semiconductor materials prepared in example 1 and comparative examples 1-3 were prepared on an Octadecyl Trichlorosilane (OTS) modified silicon wafer by a physical vapor transport method, and single crystal devices were prepared by a gold level transfer method, and the single crystal devices had a structure of gold, semiconductor materials, OTS, silicon dioxide and silicon in this order.
The above four single crystal devices were subjected to electrical property test using an Agilent B1500 type electrical property test system, the results being shown in fig. 11 to 14, fig. 11 being the electrical property test result of the single crystal device prepared using the organic semiconductor molecule of example 1, fig. 12 being the electrical property test result of the single crystal device prepared using the organic semiconductor molecule of comparative example 1, fig. 13 being the electrical property test result of the single crystal device prepared using the organic semiconductor molecule of comparative example 2, and fig. 14 being the electrical property test result of the single crystal device prepared using the organic semiconductor molecule of comparative example 3. As can be seen from FIGS. 11 to 14, the threshold voltages of the 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene prepared in example 1 of the present application were +60V, and the 2, 6-diphenyl dithiophene [3,2-B:2',3' -D ] thiophene prepared in comparative example 1 and the 2, 6-bis (3-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene prepared in comparative example 2 were-5V, and the 2, 6-bis (4-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene prepared in comparative example 3 were +10V, thereby indicating that the ortho F atom-substituted 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene had high conductivity.
Calculating the charge density of the organic semiconductor molecule using formula (1):
sigma=nqμ formula (1)
Where σ is conductivity, q is unit charge, n is charge density, and μ is mobility.
Calculation of 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D]Thiophene (example 1) has a high charge density, up to 7.5X10 17 cm -3 2, 6-diphenyldithiophene [3,2-B:2',3' -D]Thiophene (comparative example 1) having a charge density of 8.4X10 12 cm -3 2, 6-bis (3-fluorophenyl) dithiophene [3,2-B:2',3' -D]Thiophene (comparative example 2) having a charge density of 1.4X10 13 cm -3 2, 6-bis (4-fluorophenyl) dithiophene [3,2-B:2',3' -D]The charge density of the thiophene (comparative example 3) is extremely weak, thus indicating that ortho F atom-substituted 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D]Thiophene has a high charge density.
The X-ray photoelectron spectra of the organic semiconductor molecules prepared in example 1 and comparative examples 1 to 3 are shown in fig. 15, wherein (a) is example 1, (b) is comparative example 1, (c) is comparative example 3, and (d) is comparative example 4; it can be seen from a combination of FIGS. 10 and 15 that the reason for the high charge density of 2, 6-bis (2-fluorophenyl) dithiophene [3,2-B:2',3' -D ] thiophene is the interaction between F-S.
Thus, the present application is not limited to 2, 6-diphenyl-dithien [3,2-B:2',3' -D ] thiophene as a parent molecule, but also includes the following parent molecules and produces semiconductor molecules of high charge density: 2, 5-diphenylthiophene [3,2-b ] thiophene, 2, 6-diphenylbenzo [1,2-b:4,5-b ' ] dithiophene, 1, 4-bis (5-phenylthiophen-2-yl) benzene, 5 "-diphenyl-2, 2':5',2" -trithiophene, and the like.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. A high charge density organic semiconductor molecule characterized in that the F atom is ortho-substituted with a parent molecule comprising 2, 6-diphenyl-dithiophene [3,2-B:2',3' -D ] thiophene, 2, 5-diphenyl-thiophene [3,2-B ] thiophene, 2, 6-diphenyl-benzo [1,2-B:4,5-B ' ] dithiophene, 1, 4-bis (5-phenyl-thiophen-2-yl) benzene or 5,5 "-diphenyl-2, 2':5',2" -trithiophene.
2. A method for preparing a high charge density organic semiconductor molecule according to claim 1, wherein F atom ortho-substitution of 2, 6-diphenyl-dithiophene [3,2-B:2',3' -D ] thiophene is achieved by palladium-catalyzed cross-coupling reaction.
3. The method for preparing a high charge density organic semiconductor molecule according to claim 2, comprising the steps of:
and (3) refluxing and stirring the compound, 2-fluorobenzeneboronic acid, a catalyst and potassium carbonate in a mixed solvent, carrying out suction filtration and drying after the reaction is finished to obtain yellow solid powder, separating the yellow solid powder by column chromatography, and standing to obtain the high-charge-density organic semiconductor molecule.
4. A method of preparing a high charge density organic semiconductor molecule according to claim 3, wherein said compound comprises 2, 5-dibromodithio [3,2-B:2',3' -D ] thiophene.
5. A method of preparing a high charge density organic semiconductor molecule according to claim 3, wherein said catalyst is tetrakis triphenylphosphine palladium.
6. A method of preparing a high charge density organic semiconductor molecule according to claim 3 wherein the molar ratio of said compound to 2-fluorobenzeneboronic acid, catalyst, potassium carbonate is 2:4.2:0.12:8.
7. The method for producing a high charge density organic semiconductor molecule according to claim 3, wherein said mixed solvent is composed of toluene, ethanol and water in a volume ratio of 4:1:1, and a volume molar ratio of said mixed solvent to said compound is 12 ml:2 mmol.
8. A method of preparing a high charge density organic semiconductor molecule according to claim 3, wherein said reflux stirring is for a period of 12 hours.
9. The method for producing a high charge density organic semiconductor molecule according to claim 3, wherein the column chromatography is performed using petroleum ether and ethyl acetate in a volume ratio of 10:1.
10. Use of the high charge density organic semiconductor molecule of claim 1 in the preparation of an organic field effect transistor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003040886A (en) * | 2001-07-30 | 2003-02-13 | Sumitomo Seika Chem Co Ltd | Method for producing (thiophene/phenylene) cooligomer |
| JP2004059457A (en) * | 2002-07-26 | 2004-02-26 | Sumitomo Seika Chem Co Ltd | Method for producing (thiophene/phenylene)cooligomers |
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| JP2007261961A (en) * | 2006-03-27 | 2007-10-11 | Shinshu Univ | (thiophene/phenylene) cooligomer compound |
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| JP2003040886A (en) * | 2001-07-30 | 2003-02-13 | Sumitomo Seika Chem Co Ltd | Method for producing (thiophene/phenylene) cooligomer |
| JP2004059457A (en) * | 2002-07-26 | 2004-02-26 | Sumitomo Seika Chem Co Ltd | Method for producing (thiophene/phenylene)cooligomers |
| JP2006076928A (en) * | 2004-09-09 | 2006-03-23 | Hiroshima Univ | Method for producing heterocyclic aromatic compound having pentafluorophenyl group |
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