CN110003245B - Alkyl/thioalkyl nitrogen heterocyclic aromatic ring end D (A-Ar)2Conjugated compound, preparation method and application thereof - Google Patents
Alkyl/thioalkyl nitrogen heterocyclic aromatic ring end D (A-Ar)2Conjugated compound, preparation method and application thereof Download PDFInfo
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- CN110003245B CN110003245B CN201910279190.8A CN201910279190A CN110003245B CN 110003245 B CN110003245 B CN 110003245B CN 201910279190 A CN201910279190 A CN 201910279190A CN 110003245 B CN110003245 B CN 110003245B
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- alkyl
- conjugated compound
- thioalkyl
- tdpp
- dft
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
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- 238000006619 Stille reaction Methods 0.000 claims abstract 3
- -1 2, 5-dibromothienyl pyrrolopyrrole dione Chemical compound 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
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- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
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- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000005669 field effect Effects 0.000 claims description 2
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- 230000002194 synthesizing effect Effects 0.000 claims 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 claims 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- CIUZUJCGBNOCPY-UHFFFAOYSA-N 3-fluoro-2-(3-fluorothiophen-2-yl)thiophene Chemical compound FC1=C(SC=C1)C=1SC=CC=1F CIUZUJCGBNOCPY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002356 single layer Substances 0.000 abstract description 2
- 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 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
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- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 5
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
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- OSDMWTCDUDJNGI-UHFFFAOYSA-N 2-octyl-1,3-thiazole Chemical compound CCCCCCCCC1=NC=CS1 OSDMWTCDUDJNGI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
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- 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 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- CBSSXAWGKPSJNX-UHFFFAOYSA-N 2-(2-ethylhexyl)pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C(C)C(CC=1N=C2C(C=1)=NC(C2=O)=O)CCCC CBSSXAWGKPSJNX-UHFFFAOYSA-N 0.000 description 2
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 2
- ALDDXGSQUCGTDT-UHFFFAOYSA-N 4-fluoro-2h-benzotriazole Chemical compound FC1=CC=CC2=NNN=C12 ALDDXGSQUCGTDT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- MLCPSWPIYHDOKG-BUHFOSPRSA-N trans-isoindigo Natural products O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 description 2
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- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- SLLFVLKNXABYGI-UHFFFAOYSA-N 1,2,3-benzoxadiazole Chemical compound C1=CC=C2ON=NC2=C1 SLLFVLKNXABYGI-UHFFFAOYSA-N 0.000 description 1
- QKLYJKXBCXIGNZ-UHFFFAOYSA-N 1H-thieno[3,4-b]pyrrole-2,3-dione Chemical compound N1C(C(C=2C1=CSC=2)=O)=O QKLYJKXBCXIGNZ-UHFFFAOYSA-N 0.000 description 1
- WIFCKLPZYYALGY-UHFFFAOYSA-N 1h-pyrrole-2,3-dione Chemical compound O=C1NC=CC1=O WIFCKLPZYYALGY-UHFFFAOYSA-N 0.000 description 1
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- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ZTIJNCGRERWWOZ-UHFFFAOYSA-N CCCCCCCCC1=NC=C(C2=CC=C(C(C3=NC4=O)=C(CC(CC)CCCC)N=C3C4=O)S2)S1 Chemical compound CCCCCCCCC1=NC=C(C2=CC=C(C(C3=NC4=O)=C(CC(CC)CCCC)N=C3C4=O)S2)S1 ZTIJNCGRERWWOZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VOBWLFNYOWWARN-UHFFFAOYSA-N thiophen-3-one Chemical compound O=C1CSC=C1 VOBWLFNYOWWARN-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a D (A-Ar) at the tail end of an alkyl/sulfanyl nitrogen heteroaromatic ring2Conjugated compound, its preparation method and application are disclosed. Taking a 3,3 '-difluoro-2, 2' -bithiophene donor unit as a central nucleus, and obtaining D (A-Ar) through alkylation reaction, electrophilic substitution bromine-adding reaction and stille coupling reaction2Conjugated organic small molecule photovoltaic donor materials with a structure of type. D (A-Ar) according to the present invention2The conjugated compound has good solubility and stability, wide spectral absorption range, strong light absorption capacity and proper electrochemical energy level, and is expected to be used as a donor material of an organic solar cell. With fullerene PC71The maximum energy conversion efficiency and short-circuit current of the single-layer device body heterojunction solar cell with BM as an acceptor are respectively as high as 8.91% and 16.75mA cm‑2。
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a D (A-Ar) at the tail end of an alkyl/sulfanyl nitrogen heteroaromatic ring2Conjugated compound, its preparation method and application are disclosed.
Background
With the rapid growth of the global population and the rapid development of the economy, the storage of fossil fuels, once an important natural energy source, is drastically reduced and will be exhausted in the near future, and the excessive use of fossil fuels also raises an untwistable environmental problem, and the occurrence frequency of haze weather is increasing. Besides water energy, wind energy, geothermal energy and the like, solar energy is the most important renewable energy source, and researches show that the energy from sunlight to the earth per year exceeds thousands of times of the total energy consumed by human at present, so that the solar energy is inexhaustible. Organisms in nature can convert solar energy into chemical energy through photosynthesis. The electric energy plays an indispensable role in human life as the main power for scientific and technical development and national economic leap. Therefore, there is an urgent need for converting solar energy into electric energy instead of conventional energy. It was discovered by the physicist Becquerel in france 19 th century that semiconductors produce an electromotive force when exposed to light, a phenomenon which is physically known as the photovoltaic effect. In 1954, the bell research institute in the united states successfully developed the first silicon solar cell, the photoelectric conversion efficiency reached 6%, and it was marked that an artificial device converts solar energy into electric energy. Through the development of decades, solar cell technologies of different materials are mature and characterized. Solar cells can be classified into: silicon solar cells (silicon solar cells), inorganic salt solar cells (inorganic solar cells), dye-sensitized solar cells (DSSC), Organic Solar Cells (OSCs), perovskite solar cells (perovskite solar cells), and the like. At present, the solar cell for realizing industrialization is mainly a silicon solar cell, the highest conversion efficiency in a laboratory reaches 26%, and the maximum conversion efficiency is close to the upper limit of the theoretical efficiency of 29%. However, the silicon single crystal processing technology is complex, the cost for manufacturing the solar cell is high, and the energy consumption is high, so that the further popularization of the solar cell is hindered.
Inorganic salt solar cell materials such as gallium arsenide, cadmium sulfide, copper indium selenide and the like have high photoelectric conversion efficiency, and the material price is expensive but the cost is lower than that of monocrystalline silicon. However, such solar cells have disadvantages in that they are highly toxic and cause serious environmental pollution, and in and se are relatively rare elements and have limited sources, which hinder practical use thereof. The dye-sensitized solar cell and the perovskite solar cell are low in preparation cost and ideal in photoelectric conversion efficiency, and particularly the efficiency of the perovskite solar cell exceeds 20%. But the defects of easy pollution to the environment, short service life of devices, low stability, difficult preparation of flexible devices and the like exist at present. The organic solar cell has the advantages of wide material source, low cost, easy molecular regulation, light weight, good flexibility and large-area flexible preparation. Therefore, the organic solar cell has the potential of long-term development, and provides a new choice for solving the global energy problem in the future.
So far, organic solar cells mainly include bulk heterojunction organic solar cells (BHJ-OSC) and dye-sensitized solar cells (DSSC) in two research directions. The bulk heterojunction organic solar cell (BHJ-OSC) is divided into a polymer organic solar cell material (BHJ-PSC) and a small molecule organic solar cell material (BHJ-SMOSC), the highest Photoelectric Conversion Efficiency (PCE) of a series device based on the polymer organic solar cell material (BHJ-PSC) reaches 17.3%, the PCE of the BHJ-SMOSC based on the highest photoelectric conversion efficiency of an organic small molecule ternary device reaches 13.6%, and the PCE of the single-layer device reaches 11.5%. BHJ-OSC is favored by more and more researchers because of simpler production process and more stable devices compared with DSSC. Compared with polymer photovoltaic materials, the organic small-molecule photovoltaic materials have more definite and reliable relationship between molecular structures and device performances, so that BHJ-SMOSC has great development potential and attracts more scientific families to further research and develop.
At present, the photoelectric conversion efficiency of organic small molecule materials is still lower than that of polymer materials on the whole, the development of high-efficiency organic small molecule solar cells is seriously hindered by the design principle of limited small molecule donor materials, and a great challenge exists on how to obtain the organic small molecule photovoltaic materials with high-efficiency photoelectric conversion efficiency through the design of a molecular structure. The work not only provides a novel high-performance small molecular donor material of the organic solar cell, but also provides a construction mode and a research idea of a high-efficiency organic small molecular material.
The invention content is as follows:
the invention provides a class of alkyl/thioalkyl nitrogen heteroaromatic ring end D (A-Ar)2The organic micromolecule photovoltaic material with the structure of the type is characterized in that a 3,3 '-difluoro-2, 2' -bithiophene donor unit (D) and a pyrrolopyrrole dione derivative (A) are taken as an acceptor unit (A), and 2-alkyl thiazole, 2-alkyl tin oxazole, 2-sulfanyl thiazole or 2-sulfanyl tin oxazole are respectively taken as a terminal unit (Ar). Construction D (A-Ar)2Linear small molecule photovoltaic donor material of structure, intended to enable molecular building of wide absorption, strong absorption and high mobility organic photovoltaic donor materials, for the fabrication of organic small molecule photovoltaic devices (OSCs) implementing D (A-Ar)2Higher conversion efficiency of the photovoltaic material with the structure.
D(A-Ar)2The structural formula of the conjugated compound is shown as formula I:
wherein A is an electron-withdrawing bridging group; d is a central electron donating group; x ═ O, S, Se or Te; y ═ O or S, R1Independently is C6～C8An alkyl group;
the material is characterized in that alkyl/sulfanyl aromatic fused rings are used as terminal units.
Wherein the electron-withdrawing bridging group A can be selected from one of the following structures, R is independently C6～C12An alkyl group;
the bridging receptor A unit with electron withdrawing property is benzothiadiazole, monofluorobenzothiazole, difluoride benzothiadiazole, bithiophene monofluorobenzothiazole, benzooxadiazole, monofluorobenzothiazole, difluoride benzooxadiazole, bithiophene monofluorobenzothiazole, benzotriazole, monofluorobenzotriazole, difluoride benzotriazole, bithiophene benzotriazol, bithiophene monofluorobenzotriazole, thienopyrrolopyrrole dione, thiazolopyrrolopyrrole dione, pyridopyrrolopyrrole dione, phenylisoindigo, thienyl isoindigo, thiazolyl isoindigo, thiophene [3,4-b ] o-3-fluoro-thiophene ester, thiophene [3,4-b ] o-3-fluoro-thiophene ketone, Thieno [3,4-b ] 3-fluoro-thiophenone, thieno [3,4-b ] 3-thiophenone, thieno [3,4-b ] pyrroledione, bithio-thieno [3,4-b ] pyrroledione, bithio [4,5-b ] pyridophenoneobenzene, bithio [3,4-b ] cyclohexyl dione.
The central electron-donating group D can be selected from one of the following structures, R is independently C6～C12An alkyl group;
d is a functionalized condensed ring donor unit, and the conjugated unit of D is benzene, naphthalene, anthracene, phenanthrene, thiophene, alkyl bithiophene, alkyl trithiophene, alkyl thienothiophene, triarylamine, alkyl benzodithiophene, alkyl indacene, indenothiophene, fluorene, carbazole, bithiophene fluorene, bithiophene carbazole, benzo [ b ] thiazolosilene, alkyl stannophene, bisthiophene fluorene and alkyl benzo [ b ] bisstannazole.
The terminal heteroaromatic fused ring (Ar) is an alkyl/thioalkyl functionalized fused ring donor unit, and one of the following structures can be selected, R1Independently is C6～C12An alkyl group;
ar is an aromatic heterocyclic fused ring unit, and the Ar conjugated unit is 2-alkyl oxazole, 2-thioalkyl oxazole, 2-alkyl thiazole, 2-thioalkyl thiazole, 2-alkyl tin oxazole, 2-thioalkyl tin oxazole, 2-alkyl tellurium oxazole and 2-thioalkyl tellurium oxazole.
D (A-Ar) mentioned above2Conjugated compounds of type (organic small molecule photovoltaic materials), preferably:
d (A-Ar) with 3,3 '-difluoro-2, 2' -bithiophene (DFT) as electron donating group, pyrrolopyrrole dione derivative (TDPP) as electron withdrawing group and 2-octyl Thiazole (TZ) as terminal unit2Type small molecule photovoltaic material DFT (TDPP-TZ)2。
Or D (A-Ar) taking 3,3 '-difluoro-2, 2' -bithiophene (DFT) as an electron-pushing group, pyrrolopyrroledione derivative (TDPP) as an electron-withdrawing group and 2-Thioctylthiazole (TZS) as a terminal unit2Type small molecule photovoltaic material DFT (TDPP-TZS)2。
D (A-Ar) based on alkyl/thioalkyl nitrogen heteroaromatic ring ends2The preparation method of the conjugated compound comprises the following steps:
will carry R1Or SR1The molar ratio of the nitrogen heterocyclic aromatic ring (Ar) tin reagent to the electron-withdrawing bridging group A unit is 2-3: 1 in Pd (PPh)3)4(10% mol) in toluene solvent under the catalysis condition to prepare a corresponding compound with one side containing bromine and one side containing alkyl/sulfanyl nitrogen heteroaromatic ring (Ar).
The obtained corresponding nitrogen heterocyclic aromatic ring (Ar) containing bromine on one side and alkyl/sulfanyl on one side and electron-donating group D (the molar ratio is 2-2.5: 1) are in Pd (PPh)3)4(10% mol) in toluene solvent under catalytic conditionsPerforming combined reaction, performing deoxidation treatment, heating and refluxing for 12 hours under the protection of nitrogen to obtain D (A-Ar) with alkyl/sulfanyl nitrogen heteroaromatic ring (Ar) as a terminal2Linear small molecule conjugated compounds. The unit A refers to one of the electron-withdrawing bridging groups, and the unit D refers to one of the functionalized condensed ring donor units.
D (A-Ar) of the present invention2The main advantages of the small-molecule photovoltaic material are as follows:
(1) synthetic alkyl/thioalkyl nitrogen heteroaryl ring terminal-based D (A-Ar)2The conjugated molecule has good solubility, and can be dissolved in most organic solvents, such as dichloromethane, chloroform, tetrahydrofuran, chlorobenzene and the like.
(2) Synthetic alkyl/thioalkyl nitrogen heteroaryl ring-based terminal D (A-Ar) due to planar molecular structure2The small molecular material has higher carrier mobility.
(3) Synthetic alkyl/thioalkyl nitrogen heteroaromatic ring end based conjugated molecule D (A-Ar)2Has stronger intermolecular interaction and tighter pi-pi accumulation.
(4) Synthetic alkyl/thioalkyl nitrogen heteroaryl ring terminal-based D (A-Ar)2The existence of donor-receptor interaction in the conjugated molecules forms a stronger ICT function, and the charge transmission performance is enhanced.
(5) Synthetic alkyl/thioalkyl nitrogen heteroaryl ring terminal-based D (A-Ar)2The solubility of the conjugated molecule is easy to adjust due to the introduction of terminal alkyl and sulfanyl chains, so that the conjugated molecule has better film-forming property.
(6) Synthetic alkyl/thioalkyl nitrogen heteroaryl ring terminal-based D (A-Ar)2The conjugated molecule has proper electrochemical energy level and is suitable for electron donor material.
(7) Synthetic alkyl/thioalkyl nitrogen heteroaryl ring terminal-based D (A-Ar)2The conjugated molecule is used as an electron acceptor material to obtain higher energy conversion efficiency in the organic solar cell.
D (A-Ar) prepared by the invention2The conjugated compound has high hole mobility, and can be used with PC71BM blending to manufacture a small molecular photovoltaic device; wherein, D (A-Ar)2Conjugated compound of type (III) and PC71The blending mass ratio of BM is 1: 1.
The method specifically comprises the following steps: d (A-Ar)2The conjugated compound is used as an active layer to be applied to devices such as organic solar cells, organic field effect transistors or organic electroluminescent diodes.
The anode modification layer of the small-molecule photovoltaic device is a Poly Ethylenedioxythiophene (PEDOT) coating.
The organic small molecule photovoltaic device comprises an indium tin oxide conductive glass substrate layer (ITO) and an anode layer, wherein an anode modification layer is a poly ethylenedioxythiophene (PEDOT, 30nm) coating; the cathode is a deposited layer of Ca (10nm)/Al (100 nm); the material of the active layer is D (A-Ar)2Molecule and PC71BM。
The thickness of the active layer is between 20 nanometers and 1000 nanometers.
The active layer is realized by a solution processing method, and comprises spin coating, brush coating, spray coating, dip coating, roll coating, screen printing, printing or ink-jet printing methods, wherein the used solvent is an organic solvent.
Drawings
FIG. 1 shows DFT (TDPP-TZ) of the present invention2Graph of thermal weight loss.
FIG. 2 shows DFT (TDPP-TZ) of the present invention2UV-VIS absorption spectrum in dichloromethane solution.
FIG. 3 shows DFT (TDPP-TZ) of the present invention2UV-VIS absorption spectrum in solid film.
FIG. 4 shows DFT (TDPP-TZ) of the present invention2Cyclic voltammogram on solid films.
FIG. 5 shows DFT (TDPP-TZ) of the present invention2And PC71J-V plot at 1:1(w/w,12mg/mL) BM mixing ratio.
FIG. 6 shows DFT (TDPP-TZ) of the present invention2And PC71EQE curve at 1:1(w/w,12mg/mL) BM mix ratio.
FIG. 7 shows DFT (TDPP-TZ)2And PC71The mixing ratio of BM is 1:1 (w-w,12mg/mL) of single-electron device1 /2-a V curve.
FIG. 8 shows DFT (TDPP-TZS) of the present invention2Graph of thermal weight loss.
FIG. 9 shows DFT (TDPP-TZS) of the present invention2UV-VIS absorption spectrum in dichloromethane solution.
FIG. 10 shows DFT (TDPP-TZS) of the present invention2UV-VIS absorption spectrum in solid film.
FIG. 11 shows DFT (TDPP-TZS) of the present invention2Cyclic voltammogram on solid films.
FIG. 12 shows DFT (TDPP-TZS) of the present invention2And PC71J-V plot at 1:1(w/w,12mg/mL) BM mixing ratio.
FIG. 13 shows DFT (TDPP-TZS) of the present invention2And PC71EQE curve at 1:1(w/w,12mg/mL) BM mix ratio.
FIG. 14 shows DFT (TDPP-TZS)2And PC71J of single electron device with BM mixing ratio of 1:1(w/w,12mg/mL)1/2-a V curve.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention in any way.
D (A-Ar) based on alkyl/thioalkyl nitrogen heteroaromatic ring ends2The preparation route of the conjugated molecule of type (II) is shown below,
example 1, Compound 2-octyl Thiazole (TZR)1) The synthetic route of (2) is as follows:
under the protection of nitrogen, 2-bromothiazole (6.0g,36.58 mmol) was dissolved in dry ether in a 100mL three-necked flask, and 2.5M n-butyl was added dropwise at-78 deg.CLithium (16.0ml,40.24mmol), reacting at-78 deg.C for two hours, adding bromo-n-octane (7.0g,36.58mmol) at one time, reacting for half an hour under constant temperature, and reacting at room temperature overnight. Directly spin-drying the solvent under reduced pressure to obtain pale yellow liquid, and separating by column chromatography with petroleum ether as eluent to obtain product (TZR)1)6.0g, 84% yield.1H NMR(500MHz,CDCl3)δ7.66(d, J＝3.3Hz,1H),7.18(d,J＝3.3Hz,1H),3.05–2.97(m,2H),1.79(dt,J＝15.4,7.6 Hz,2H),1.33–1.26(m,11H),0.87(s,3H).
Example 2, 2-octyl thiazole-5-tributyltin (SnTZR)1) The synthetic route of (2) is as follows:
under the protection of nitrogen, 2-octyl thiazole (2.46 g,10.8mmol) was dissolved in dry tetrahydrofuran in a 100mL three-necked flask, 2.5M n-butyllithium (4.75mL,11.88mmol) was added dropwise at-78 ℃ for reaction at-78 ℃ for two hours, tributyltin chloride (3.22mL,11.88mmol) was added all at once, and after the reaction was maintained for half an hour, the reaction was switched to room temperature for overnight. Directly spin-drying the solvent under reduced pressure to obtain light yellow thick liquid (SnTZR)1) And directly used for the next reaction.1H NMR(400MHz,CDCl3)δ7.58(s,1H),3.06–3.03(m,2H), 1.80(dt,J＝15.0,7.4Hz,2H),1.58–1.51(m,6H),1.46(dt,J＝16.1,8.7Hz,6H), 1.39-1.17(m,22H),0.89(t,J＝7.2Hz,12H).
Example 3,3- (5-bromo-2-thienyl) -2, 5-bis (2-ethylhexyl) -6- (5- (2-octyl-5-thiazolyl) -2-thienyl) pyrrolopyrroledione (BrTDPP-TZR)1) The synthetic route of (2) is as follows:
20mL of toluene, 2-octylthiazole-5-tributyltin (286mg, 0.59mmol), 3, 6-bis (5-bromo-2-thienyl) -2, 5-bis (2-ethylhexyl) -pyrrolopyrroledione (400mg, 0.59mmol), and palladium tetratriphenylphosphine (34mg, 0) were added to a 100mL three-necked flask under nitrogen.03 mmol). Stirring and heating to 80 ℃ under the nitrogen atmosphere, stopping the reaction after 4h, and cooling to room temperature. Removing solvent by rotary evaporation, and performing column chromatography with mixed solution of petroleum ether/dichloro-alkane at volume ratio of 5:1 as eluent to obtain product (BrTDPP-TZR)1)172mg, yield 30.0%.1H NMR(400MHz,CDCl3)δ8.90(d,J＝4.1Hz,1H), 8.64(d,J＝4.2Hz,1H),7.84(s,1H),7.27(s,1H),7.23(d,J＝4.2Hz,1H),3.98(dt, J＝13.7,7.2Hz,4H),3.02(t,J＝7.7Hz,2H),1.82(dt,J＝15.3,7.6Hz,4H),1.32 (ddd,J＝25.4,15.9,8.4Hz,34H),0.94–0.86(m,15H).
Example 4, 2-Thiooctyl Thiazole (TZSR)1) The synthetic route of (2) is as follows:
80mL of absolute ethanol, potassium tert-butoxide (14.36g, 0.128mol) and 2-thiazolethiol (5g, 42.7mmol) were added to a 100mL single-neck flask under nitrogen protection and ice bath, and after stirring for 30min, bromo-n-octane (8.66g,44.8mmol) was slowly added. After the addition, the reaction is performed for 12 hours under reflux, and after the reaction is completed, water is added for quenching. Washing with water, extracting with diethyl ether (3 × 20mL), mixing organic layers, drying with anhydrous magnesium sulfate, filtering to obtain filtrate, removing solvent, and separating by column chromatography with petroleum ether as eluent to obtain product (TZSR)1)9.06g, yield 92.4%.1H NMR(400MHz,CDCl3)δ7.66(d,J＝3.4Hz,1H),7.20(d,J＝3.4 Hz,1H),3.30–3.15(m,2H),1.75(dt,J＝15.0,7.4Hz,2H),1.51–1.36(m,2H), 1.33–1.15(m,9H),0.88(t,J＝6.9Hz,3H).
Example 5, 2-Thiooctyl thiazole-5-tributyltin (SnTZSR)1) The synthetic route of (2) is as follows:
under the protection of nitrogen, 2-thiactyl thiazole (2.0 g,8.90mmol) was dissolved in dry tetrahydrofuran in a 100mL three-necked flask, 2.5M n-butyllithium (3.92mL,9.8mmol) was added dropwise at-78 deg.C, and the reaction was carried out at-78 deg.C for two hoursTributyltin chloride (2.66ml,9.8mmol) was added in one portion, and after half an hour of incubation, the reaction was turned to room temperature for overnight reaction. Directly decompressing and spin-drying the solvent to obtain light yellow thick liquid (SnTZSR)1) And directly used for the next reaction.1H NMR(400MHz,CDCl3)δ7.57(s,1H),7.26(s,1H),3.30–3.05(m, 3H),1.76(dt,J＝15.0,7.4Hz,3H),1.58–1.48(m,6H),1.45(dt,J＝16.1,8.7Hz, 5H),1.39-1.18(m,22H),0.89(t,J＝7.2Hz,18H).
Example 6,3- (5-bromo-2-thienyl) -2, 5-bis (2-ethylhexyl) -6- (5- (2-thiooctyl-5-thiazolyl) -2-thienyl) pyrrolopyrroledione (BrTDPP-TZSR)1) The synthetic route of (2) is as follows:
20mL of toluene, 2-thienylthiazole-5-tributyltin (213mg, 0.41mmol), 3, 6-bis (5-bromo-2-thienyl) -2, 5-bis (2-ethylhexyl) -pyrrolopyrroledione (280mg, 0.41mmol), and tetrakistriphenylphosphine palladium (7.12mg, 0.0062mmol) were added to a 100mL three-necked flask under nitrogen. Stirring and heating to 80 ℃ under the nitrogen atmosphere, stopping the reaction after 4h, and cooling to room temperature. Removing solvent by rotary evaporation, and performing column chromatography with mixed solution of petroleum ether/dichloro-hexane at volume ratio of 5:1 as eluent to obtain product (BrTDPP-TZSR)1)172mg, yield 30.0%.1H NMR(300MHz,CDCl3)δ8.89(d,J＝ 4.2Hz,1H),8.64(d,J＝4.1Hz,1H),7.80(s,1H),7.22(dd,J＝4.2,1.7Hz,2H), 3.97(dd,J＝12.7,7.6Hz,4H),3.29–3.18(m,2H),1.84(dd,J＝11.8,7.2Hz,2H), 1.81–1.68(m,2H),1.30(d,J＝14.3Hz,30H),0.89–0.79(m,15H).
Example 7 FBT Compound of interest (TDPP-TZR)1)2The synthetic route of (2) is as follows:
under the protection of nitrogen, 10mL of toluene and 3- (5-bromo-2-thienyl) -2, 5-di (2-ethylhexyl) -6 are added into a 100mL single-neck bottle- (5- (2-octyl-5-thiazolyl) -2-thienyl) pyrrolopyrroledione (126mg, 0.157mmol), (3,3 '-difluoro- [2,2' -bithiophene)]5,5' -di-tributyltin (42mg, 0.078mmol), tetrakistriphenylphosphine palladium (5.46mg, 0.0048 mmol). The mixture is stirred and heated to 110 ℃ under the nitrogen atmosphere, the reaction is stopped after 12h, and the mixture is cooled to room temperature. Removing solvent by rotary evaporation, and performing column chromatography with mixed solution of petroleum ether/dichloro-alkane at volume ratio of 2:1 as eluent to obtain product FBT (TDPP-TZR)1)2160mg, yield 72.0%.1H NMR(400MHz,CDCl3)δ8.93(d,J＝4.3Hz,2H),7.75(s,1H),7.22(s, 1H),7.15(s,1H),6.99(s,1H),3.98(s,4H),2.91(t,J＝7.1Hz,2H),1.88(s,2H), 1.75(s,2H),1.31(d,J＝47.2Hz,60H),0.93–0.86(m,30H).
Example 8 FBT (TDPP-TZSR) Compound of interest1)2The synthetic route of (2) is as follows:
10mL of toluene, 3- (5-bromo-2-thienyl) -2, 5-bis (2-ethylhexyl) -6- (5- (2-thiooctyl-5-thiazolyl) -2-thienyl) pyrrolopyrroledione (150mg, 0.18mmol), (3,3 '-difluoro- [2,2' -bithiophene) were added to a 100mL single-neck flask under nitrogen protection]5,5' -di-tributyltin (48mg, 0.09mmol), tetrakistriphenylphosphine palladium (6.3mg, 0.0054 mmol). The mixture is stirred and heated to 110 ℃ under the nitrogen atmosphere, the reaction is stopped after 12h, and the mixture is cooled to room temperature. Removing solvent by rotary evaporation, and performing column chromatography with mixed solution of petroleum ether/dichloro-hexane at volume ratio of 2:1 as eluent to obtain product FBT (TDPP-TZSR)1)2160mg, yield 72.0%.1H NMR(400MHz,CDCl3)δ8.96–8.90(m,2H),7.67(s,1H),7.12(s,1H), 7.03(d,J＝4.0Hz,1H),6.89(s,1H),3.93(d,J＝13.3Hz,4H),3.11(t,J＝7.3Hz, 2H),1.87(s,2H),1.73–1.65(m,2H),1.32(dd,J＝38.3,7.0Hz,60H),0.93(ddd,J ＝19.8,18.9,6.3Hz,30H).
Example 9
D(A-Ar)2The performance characterization of the small-molecule photovoltaic material, the manufacture of a photovoltaic optical device and the test of the light-emitting performance.
D(A-Ar)2Of small molecule photovoltaic materials1H NMR spectra were measured by a Bruker Dex-400NMR instrument, UV-visible absorption spectra by an HP-8453 UV-visible spectrometer, and fluorescence spectra by a HITACHI-850 fluorescence spectrometer.
Based on D (A-Ar)2The photovoltaic device of the small molecule material comprises: indium Tin Oxide (ITO) conductive glass anode layer, and polyethylene dioxythiophene (PEDOT) anode modifying layer. The activated layer is formed by the micromolecular material and PC71BM blending, and the blending ratio is 1: 1. The cathode was composed of a Ca (10nm)/Al (100nm) layer.
Example 10
DFT(TDPP-TZ)2Photophysical properties and small molecule photovoltaic device properties thereof
DFT(TDPP-TZ)2The graph of the thermal weight loss of (a) is shown in fig. 1. The decomposition temperature was 378 ℃.
DFT(TDPP-TZ)2In CHCl3The ultraviolet absorption spectrum in the solution is shown in FIG. 2; wherein the absorption peak at 363nm is a pi-pi transition absorption peak of the small molecular material, and the absorption peak at 650nm is a charge transfer (ICT) transition absorption peak from a donor unit (DFT) to an acceptor unit (DPP).
DFT(TDPP-TZ)2The ultraviolet absorption spectrum in the solid film is shown in FIG. 3. Where the absorption spectra are approximately the same pattern but the absorption peaks are all red-shifted to different degrees due to pi-pi stacking in the solid film. The band gap of the material was calculated to be 1.56eV from the peak position.
DFT(TDPP-TZ)2The cyclic voltammogram in the solid film is shown in FIG. 4. It exhibits two sets of reversible oxidation peaks, which can be assigned to the oxidation peaks of the donor unit DFT and the acceptor unit DPP, respectively. This indicated that the HOMO level of the material was-5.41 eV.
DFT(TDPP-TZ)2And PC71The J-V curve at a BM mixing ratio of 1:1(w/w,12mg/mL) is shown in FIG. 5; under this condition, the short-circuit current of the device was 16.12mA/cm2The open circuit voltage was 0.75V, the fill factor was 63.09%, and the photovoltaic efficiency was 7.63%.
DFT(TDPP-TZ)2And PC71The EQE curve chart under the mixing ratio of BM 1:1(w/w,12mg/mL) is shown in FIG. 6; the graph shows the EQE test range of 300-800nm with a maximum EQE value of 78.64% at 610 nm.
DFT(TDPP-TZ)2And PC71J of single electron device with BM mixing ratio of 1:1(w/w,12mg/mL)1/2the-V curve is shown in FIG. 7, and the hole mobility is at most 4.95X 10-4cm2V-1s-1。
Example 11
DFT(TDPP-TZS)2Photophysical properties and small molecule photovoltaic device properties thereof
DFT(TDPP-TZS)2The thermogravimetry of (c) is shown in fig. 8, and the decomposition temperature is 367 ℃.
DFT(TDPP-TZS)2In CHCl3The ultraviolet absorption spectrum in the solution is shown in FIG. 9. Wherein the absorption peak around 377nm is the pi-pi transition absorption peak of the small molecular material, and the absorption peak around 632nm is the charge transfer (ICT) transition absorption peak from a donor unit (DFT) to an acceptor unit (DPP).
DFT(TDPP-TZS)2The ultraviolet absorption spectrum in the solid film is shown in FIG. 10. In which the absorption spectra have approximately the same peak shape but the absorption peaks are all red-shifted to different degrees due to pi-pi stacking in the solid film. The band gap of the material was calculated to be 1.57eV from the peak position.
DFT(TDPP-TZS)2Cyclic voltammograms in solid films are shown in figure 11. It exhibits two sets of reversible oxidation peaks, which can be assigned to the oxidation peaks of the donor unit DFT and the acceptor unit DPP, respectively. This indicated that the HOMO level of the material was-5.25 eV.
DFT(TDPP-TZS)2And PC71The J-V curve at a 1:1(w/w,12mg/mL) BM mixing ratio is shown in FIG. 12. Under this condition, the short-circuit current of the device was 16.75mA/cm2The open circuit voltage was 0.795V, the fill factor was 66.93%, and the photovoltaic efficiency was 8.91%.
DFT(TDPP-TZS)2And PC71The EQE curve at 1:1(w/w,12mg/mL) BM mix ratio is shown in FIG. 13. The figure showsThe EQE test range is 300-800nm, and the maximum EQE value is 78.89% around 661 nm.
DFT(TDPP-TZS)2And PC71J of single electron device with BM mixing ratio of 1:1(w/w,12mg/mL)1/2the-V curve is shown in FIG. 14, and the hole mobility is 7.78X 10 at maximum-4cm2V-1s-1。
While the present invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In light of the present inventive concept, those skilled in the art will recognize that certain changes may be made in the embodiments of the invention to which the invention pertains without departing from the spirit and scope of the claims.
Claims (8)
1. Alkyl/thioalkyl nitrogen heterocyclic aromatic ring end D (A-Ar)2Conjugated compound of type (I), wherein D (A-Ar)2The conjugated compound of type (I) is:
2. the alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 12A process for producing a conjugated compound of the formula (I), which comprises the steps of:
synthesis of side chain DPP-TZ-Br: under the action of palladium tetratriphenylphosphine, carrying out stille coupling reaction on 2, 5-dibromothienyl pyrrolopyrrole diketone and 2-octyl-5-thiazole tributyltin to synthesize a DPP-TZ-Br crude product containing bromine at one side, and carrying out column chromatography separation to obtain a pure product;
or, synthesizing side chain DPP-TZS-Br: under the action of palladium tetratriphenylphosphine, carrying out still coupling reaction on 2, 5-dibromothienyl pyrrolopyrrole dione and 2-thienyltributyltin to synthesize a DPP-TZS-Br crude product containing bromine at one side, and carrying out column chromatography separation to obtain a pure product;
synthesis of target molecule DFT (TDPP-TZ)2Or DFT (TDPP-TZS)2: side chain DPP-TZ-Br or DPP-TZS-Br and difluoride bithiophene are subjected to stille coupling reaction under the catalysis of palladium tetratriphenylphosphine, and D (A-Ar) is synthesized2Type small molecule photovoltaic material DFT (TDPP-TZ)2Or DFT (TDPP-TZS)2And the crude product is separated by column chromatography to obtain a pure product.
3. The alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 12Use of a conjugated compound of the formula (I), wherein D (A-Ar)2Conjugated compound of type (III) and PC71And BM blending to manufacture the small molecular photovoltaic device.
4. The alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 32Use of a conjugated compound of the type D (A-Ar)2The conjugated compound is used as an active layer to be applied to an organic solar cell, an organic field effect transistor, an organic electroluminescent diode or an organic near infrared photoelectric detector.
5. The alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 32Use of a conjugated compound of the formula (I), wherein D (A-Ar)2Conjugated compound of type (III) and PC71The blending mass ratio of BM is 1: 1.
6. The alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 32The application of the conjugated compound is characterized in that an anode modification layer of the small-molecule photovoltaic device is a Poly Ethylenedioxythiophene (PEDOT) coating.
7. The alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 42The application of the conjugated compound is characterized in that the thickness of the active layer is between 20 nanometers and 1000 nanometers.
8. Root of herbaceous plantThe alkyl/thioalkyl nitrogen heteroaryl ring-terminated D (A-Ar) according to claim 42The application of the conjugated compound is characterized in that the active layer is realized by a solution processing method.
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