CN108440574B - Thiazole-containing organic small molecule and preparation method and application thereof - Google Patents
Thiazole-containing organic small molecule and preparation method and application thereof Download PDFInfo
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- CN108440574B CN108440574B CN201810288440.XA CN201810288440A CN108440574B CN 108440574 B CN108440574 B CN 108440574B CN 201810288440 A CN201810288440 A CN 201810288440A CN 108440574 B CN108440574 B CN 108440574B
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- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000003384 small molecules Chemical class 0.000 title description 18
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical group C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 claims abstract description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- -1 4-hexylphenyl Chemical group 0.000 claims description 19
- 125000000732 arylene group Chemical group 0.000 claims description 17
- 125000005549 heteroarylene group Chemical group 0.000 claims description 17
- 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 claims description 16
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000002619 bicyclic group Chemical group 0.000 claims description 12
- 229940125898 compound 5 Drugs 0.000 claims description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 9
- 229940126214 compound 3 Drugs 0.000 claims description 9
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 3
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000013461 design Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 17
- 239000000370 acceptor Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910003472 fullerene Inorganic materials 0.000 description 9
- 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 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010200 validation analysis Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- JOZQXSUYCMNTCH-ODDCUFEPSA-N 2-[(2Z)-2-[[20-[(Z)-[1-(dicyanomethylidene)-5,6-difluoro-3-oxoinden-2-ylidene]methyl]-12,12,24,24-tetrakis(4-hexylphenyl)-5,9,17,21-tetrathiaheptacyclo[13.9.0.03,13.04,11.06,10.016,23.018,22]tetracosa-1(15),2,4(11),6(10),7,13,16(23),18(22),19-nonaen-8-yl]methylidene]-5,6-difluoro-3-oxoinden-1-ylidene]propanedinitrile Chemical compound CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7cc(F)c(F)cc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(\C=C4/C(=O)c5cc(F)c(F)cc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 JOZQXSUYCMNTCH-ODDCUFEPSA-N 0.000 description 2
- CZJKWNMXYPFWHP-UHFFFAOYSA-N 3-(2-ethylhexyl)thiophene-2-carbaldehyde Chemical compound CCCCC(CC)CC=1C=CSC=1C=O CZJKWNMXYPFWHP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KKQLCAVNJHQUMB-UHFFFAOYSA-N 2,5-bis[4-(2-ethylhexyl)thiophen-2-yl]-[1,3]thiazolo[5,4-d][1,3]thiazole Chemical compound C(C)C(CC=1C=C(SC=1)C=1SC=2N=C(SC=2N=1)C=1SC=C(C=1)CC(CCCC)CC)CCCC KKQLCAVNJHQUMB-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- UPCYEFFISUGBRW-UHFFFAOYSA-N 3-ethyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CCN1C(=O)CSC1=S UPCYEFFISUGBRW-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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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
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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
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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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- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Plural Heterocyclic Compounds (AREA)
- Photovoltaic Devices (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The invention discloses a thiazole-containing organic micromolecule and a preparation method and application thereof, wherein a high-performance benzodithiophene unit (BDT) is used as an electron donor core, thiazole is used as a bridging unit, and a series of brand-new A-D-A conjugated molecules which take thiazole as the bridging unit and have good solubility and good thermal stability are synthesized by changing the design of an electron pulling unit at the tail end.
Description
Technical Field
The invention relates to the technical field of molecules, in particular to a thiazole-containing organic micromolecule, a preparation method thereof and application of the thiazole-containing organic micromolecule as an active layer electron donor or electron acceptor material in an organic solar cell (OPV).
Background
Solution processed organic solar cells as a promising green energy technology have some unique advantages such as: the preparation method has the advantages of low cost, light weight, capability of preparing large-area devices and the like. Energy conversion efficiencies based on organic solar cells with conjugated polymers or small organic molecules as donors and fullerene derivatives as acceptors have exceeded 10% (J.Wan, X.Xu, G.Zhang, Y.Li, K.Feng and Q.Peng, Energy environ.Sci.,2017,10, 1739; B.Kan, M.Li, Q.Zhang, F.Liu, X.Wan, Y.Wang, W.Ni, G.Long, X.Yang and H.Feng, J.Am.Chem.Soc.,2015,137,3886; D.Deng, Y.Zhang, J.Zhang, Z.Wang, L.Zhu, J.Fang, B.Xia, Z.Wang, K.Lu and W.Ma, Nat.com., 7, U.S. 40, Y.Yang.40, Y.Yang.C, J.Yang, J.F.F.Wang, J.F.Wang, J.J.F.Wang, W.Ni, G.Long, X.Yang and H.F.J.F.Wang, J.Wang, J.J.J.J.Zong, B.Wang, Z.Wang, K.Lu.Lu.Lu.Wang, K.J.F.F.F.F.F.J.F.F.F.J.F.F.F.F.Wang, J.Wang, J.C.C.C.C.Wang, J.S.J.F.F.C.Wang, J.F.F.F.F.F.F.Wang, J.F.F.F.Wang, J.Wang, J.F.F.F.F.F.F.F.F.F.F.F.Wang. However, some inherent drawbacks, including high cost, poor absorption in the visible region of the solar spectrum, and difficult energy level control, still exist in fullerene acceptors. Thus, in recent years, high performance non-fullerene acceptor materials have been developed (Y.Lin, J.Wang, Z.G.Zhang, H.Bai, Y.F.Li, D.Zhu and X.W.Zhang, adv.Mater.,2015,27, 1170; Y.Lin, Q.He, F.ZHao, L.Huo, J.Mai, X.Lu, C.J.Su, T.Li, J.Wang, J.Zhu, Y.Sun, C.Wang and X.W.Zhang, J.Am.Chem. Soc, 2016,138,2973; Y.Lin, Z.Zhang, H.Bai, J.Wang, Y.Yao, Y.F.Li, D.Zhu X.W.Zhang, Energy.Yang, H.Zhu, J.Zhang, H.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.H.J.J.J.J.J.J.J.J.J.H.H.J.J.J.J.H.J.J.H.H.J.J.J.H.J.J.H.H.H.H.J.H.H.H.H.H.H.J.H.J.J.J.J.J..
Small organic molecules have specific advantages over polymers, such as: easy purification, defined molecular weight, easily controllable molecular energy levels and small batch-to-batch variation (W.Ni, M.Li, B.Kan, F.Liu, X.Wan, Q.Zhang, H.Zhang, T.P.Russelcdd and Y.Chen, chem. Commun.,2016,52, 465; C.H.Cui, X.Guo, J.Min, B.Guo, X.Cheng, M.J.Zhang, C.J.Brabec and Y.F.Li, adv.Mater.,2015,27, 7469; B.Kan, Q.Zhang, M.Li, X.Wan, W.Ni, G.Long, Y.Wang, X.Yang, H.Feng and Y.n, J.Am.Chen, 2014,136,15529). Thus, in PCBM-based small molecule organic solar cells, photovoltaic devices achieve very high Energy conversion efficiencies (J.Wan, X.xu, G.Zhang, Y.Li, K.Feng and Q.Peng, Energy environ.Sci.,2017,10, 1739; B.Kan, M.Li, Q.Zhang, F.Liu, X.Wan, Y.Wang, W.Ni, G.Long, X.Yang and H.Feng, J.Am. chem.Soc.,2015,137,3886; D.Deng, Y.Zhang, J.Zhang, Z.Wang, L.Zhu, J.Fang, B.Xia, Z.Wang, K.Lu and W.Ma, nat.commun.,2016,7, 13740.). However, organic solar cells achieve a relatively poor photovoltaic performance when non-fullerene acceptors are combined with small organic molecule donors (W.Ni, M.Li, B.Kan, F.Liu, X.Wan, Q.Zhang, H.Zhang, T.P.Russelcdd and Y.Chen, chem.Commun, 2016,52, 465; L.Yang, S.Zhang, C.He, J.Zhang, H.Yao, Y.Yang, Y.Zhang, W.ZHao, and J.H.Hou, J.Am.Chem.Soc, 2017,139,1958; G.Feng, Y.xu, J.Zhang, Z.Wang, Y.ZHou, Y.Li, Z.and Z.Li, C.Li, J.chem.A, Mater.A, 2016, 56, 2016). To date, the development of non-fullerene all small molecule organic solar cells lags behind polymer or fullerene based organic solar cells. Considering that a non-fullerene all-small molecule organic solar cell combines the advantages of both a non-fullerene receptor and a small molecule donor, the non-fullerene all-small molecule organic solar cell has great development potential, but low photovoltaic performance is an important problem to be solved. In the foregoing we have mentioned that high performance non-fullerene acceptor materials have evolved very rapidly in recent years. Therefore, the design of a novel efficient organic small molecule donor material matched with the organic small molecule donor material has important significance for improving the photovoltaic performance of the all-small molecule organic solar cell.
For the design of the active layer electron donor or electron acceptor material, some elements include: good solubility, broad absorption spectrum and with high extinction coefficient, suitable energy levels and high mobility have to be taken into account and maintained in a good balance (b.kan, m.li, q.zhang, f.liu, x.wan, y.wang, w.ni, g.long, x.yang and h.feng, j.am.chem.soc.,2015,137, 3886; b.kan, q.zhang, m.li, x.wan, w.ni, g.long, y.wang, x.yang, h.feng and y.chen, j.am.chem.soc.,2014,136,15529.). The use of a framework of the acceptor-donor-acceptor (a-D-a) type, i.e. comprising one electron-rich unit D as electron donor core and two electron-strongly withdrawing units a as end groups, is an effective strategy for tuning the absorption spectrum and the molecular energy levels (y. Chen, x.wan and g.long, acc.chem.res.,2013,46, 2645; r.fitzner, e.mena-Osteritz, a.mishra, g.schulz, e.reinold, m.weil, c.korner, h. ziehlne, c.elscher, k.leo, m.riede, m.eipffer, c.uhrick and p.bauuerle, j.am.chem.sac. 2012,134,11064.). Past work has revealed that photovoltaic small molecule active layer materials based on Benzodithiophene (BDT) units as donor cores have exhibited excellent photovoltaic performance (j.wan, x.xu, g.zhang, y.li, k.feng and q.pen, Energy environ.sci.,2017,10, 1739; z.wang, x.xu, z.li, k.feng, k.li, y.li and q.pen, adv. electron.mater.,2016,2, 1600061; h.bin, y.yang, z.g.zhang, l.ye, m.ghasemii, s.n, y.zhang, c.zhang, c.sun, l.xue, c.yang, h.ad, y.j.am.m.m.m, par.zhang, c.zhang, c.su, l.xue, c.yang, h.ad, h.j.am.m.m.m.m.m.m.n, qi.s.n, y.zhang, y.z.z.g., qin, y.7, y.zhang, y.g, y.k.k.7, z.
The use of suitable bridging unit bridges is also one of the key factors in improving photovoltaic performance. It is noteworthy that thiazole units, which are strongly electron withdrawing, have attracted a great deal of attention, which is benefited from having properties such as: has good oxidation stability, planarity and structure of pi accumulation and high carrier mobility (B.Guo, X.Guo, W.Li, X.Meng, W.Ma, M.Zhang, and Y.Li, J.Mater.chem.A,2016,4, 13251; I.Osaka, M.Saito, T.Koganezawa, and K.Takimiya, adv.Mater.,2014,26, 331.). Thus, many high performance polymer systems based on thiazole units are widely used (B.Guo, X.Guo, W.Li, X.Meng, W.Ma, M.Zhang, and Y.Li, J.Mater.chem.A,2016,4, 13251; B.Guo, W.B.Li, X.Guo, X.Y.Meng, W.Ma, M.J.Zhang, and Y.F.Li, adv.Mater.,2017,29, 1702291), but they are rarely used in small molecule photovoltaic materials. Due to the huge application potential of the thiazole unit, the thiazole unit is introduced into organic small molecules, so that high-efficiency organic photovoltaic materials can be expected.
Disclosure of Invention
The invention aims to provide a thiazole-containing organic micromolecule, a preparation method and application thereof.
The invention has a technical scheme that:
the organic micromolecule containing thiazole is an A-D-A conjugated organic micromolecule which takes a benzodithiophene unit as a core and takes thiazole as a bridging unit and comprises the following general structure:
wherein,
x is selected from any one of O, S or Se;
R1~R3independently selected from hydrogen, C1~C30Alkyl of (C)1~C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represents any one of the following unsubstituted or substituted groups:
an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, an arylene group containing at least three rings, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a heteroarylene group containing at least three rings, wherein in the bicyclic arylene group, the arylene group containing at least three rings, the bicyclic heteroarylene group or the heteroarylene group containing at least three rings, the rings are fused with each other or connected through a single bond;
when Ar is1And Ar2When any one or two of them are substituted at the same time, Ar1Or Ar2Respectively has 1 to 2 substituents which are aryl and have C1~C30Or with C1~C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
r in the above A structure4Is C1~C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1~C8Any one of the alkyl groups of (1).
Further, X ═ S; the R is1~R3Independently of one another is hydrogen, C1~C8Any one of alkyl or 4-hexylphenyl; r in the structure of A4Is C1~C8Any one of the alkyl groups of (1).
The other technical scheme of the invention is as follows:
a preparation method of thiazole-containing organic micromolecules comprises the following steps:
(1) dissolving the compound 1 in a mixed solvent of chloroform and glacial acetic acid, slowly adding N-bromosuccinimide in an ice-water bath under the condition of keeping out of the sun, removing the ice-water bath after half an hour, carrying out normal-temperature stirring reaction for 10 hours, and separating and purifying to obtain a compound 2;
(2) stirring phosphorus oxychloride and N, N-dimethylformamide to react for 1-2 hours under the condition of ice-water bath, removing the ice-water bath, dissolving the compound 2 in chloroform, adding the chloroform into the product obtained by the reaction of the phosphorus oxychloride and the N, N-dimethylformamide by using an injector, stirring at 70 ℃, refluxing for 12 hours, separating and purifying to obtain a compound 3;
(3) stirring and reacting the compound 3, the compound 4 and a catalyst tetrakis (triphenylphosphine) palladium in toluene at 110 ℃ for 20-30 hours, and separating and purifying to obtain a compound 5;
(4) and (2) carrying out stirring reaction on the compound 5, an electron withdrawing group A and piperidine or pyridine in chloroform at 70 ℃ for 12 hours, and finally separating and purifying to obtain an A-D-A conjugated molecular product 6 which has the following general structure and takes a benzodithiophene unit as a core and thiazole as a bridging unit:
wherein,
x is selected from any one of O, S or Se;
R1~R3independently selected from hydrogen, C1~C30Alkyl of (C)1~C30Any one of alkoxy or 4-alkylphenyl;
the electron withdrawing group A is selected from one of the following structures:
r in the above A structure4Is C1~C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1~C8Any one of the alkyl groups of (1).
Furthermore, the molar ratio of the added piperidine or pyridine to the compound 5 is 1: 0.001-0.5.
Further, the steps (2), (3) and (4) are stirred and reacted under the inert gas atmosphere.
Further, the molar ratio of the added tetrakis (triphenylphosphine) palladium to the compound 4 is 1: 10-100.
The thiazole-containing organic micromolecules prepared in the mode are used as an electron donor or electron acceptor material of an active layer for light capture and applied to preparation of organic solar cells.
The invention provides a thiazole-containing organic micromolecule, which has the main advantages that:
1. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit can be processed by a solution method and can be dissolved in organic solvents such as chloroform, tetrahydrofuran, chlorobenzene and the like;
2. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit has good thermal stability, and the initial thermal decomposition temperature exceeds 400 ℃;
3. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit has good light absorption and is suitable for being used as an organic solar cell material;
4. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit has a proper electron energy level and is suitable for an electron donor material or an electron acceptor material in an organic solar cell;
5. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit is used as an electron donor material or an electron acceptor material to show high photoelectric conversion efficiency in an organic solar cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein,
FIG. 1 is a diagram of an ultraviolet-visible absorption spectrum of a thiazole-containing small organic molecule according to the present invention;
FIG. 2 is a cyclic voltammogram of a thiazole-containing small organic molecule of the present invention;
FIG. 3 is a thermogravimetric analysis graph of a thiazole-containing small organic molecule according to the present invention;
FIG. 4 is a differential scanning calorimetry trace of a thiazole-containing small organic molecule according to the present invention;
FIG. 5 is a J-V curve of a thiazole-containing organic small molecule in an organic solar cell according to the present invention;
FIG. 6 is a synthetic route of a thiazole-containing small organic molecule according to the present invention;
FIG. 7 shows the synthetic route of BTTzR of a thiazole-containing small organic molecule according to the invention.
Detailed Description
The organic micromolecule is an A-D-A conjugated organic micromolecule which takes a benzodithiophene unit as a core and takes thiazole as a bridging unit, and comprises the following general structure:
wherein,
x is selected from any one of O, S or Se;
R1~R3independently selected from hydrogen, C1~C30Alkyl of (C)1~C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represents any one of the following unsubstituted or substituted groups:
vinylene, ethynylene, monocyclic arylene, bicyclic arylene, arylene containing at least three rings, monocyclic heteroarylene, bicyclic heteroarylene or heteroarylene containing at least three rings, Ar1And Ar2The bicyclic arylene, arylene containing at least three rings, bicyclic heteroarylene, heteroarylene containing at least three rings may be the same or different, and the rings are fused with each other or connected by a single bond;
when Ar is1And Ar2Any ofWhen one or two are substituted at the same time, Ar1Or Ar2Respectively has 1 to 2 substituents which are aryl and have C1~C30Or with C1~C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
r in the above A structure4Is C1~C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1~C8Any one of the alkyl groups of (1).
Referring to fig. 6, fig. 6 is a synthetic route of a thiazole-containing small organic molecule according to the present invention. As shown in fig. 6, the method comprises the following steps:
(1) dissolving the compound 1 in a mixed solvent of chloroform and glacial acetic acid, slowly adding N-bromosuccinimide in an ice-water bath under the condition of keeping out of the sun, removing the ice-water bath after half an hour, carrying out normal-temperature stirring reaction for 10 hours, and separating and purifying to obtain a compound 2;
(2) stirring phosphorus oxychloride and N, N-dimethylformamide under the conditions of an ice water bath and an inert gas atmosphere for reacting for 1-2 hours, then removing the ice water bath, dissolving the compound 2 in chloroform, adding the chloroform into the product obtained by the reaction of the phosphorus oxychloride and the N, N-dimethylformamide by using an injector, stirring at 70 ℃, refluxing for 12 hours, and separating and purifying to obtain a compound 3;
(3) stirring and reacting the compound 3, the compound 4 and a catalyst tetrakis (triphenylphosphine) palladium in toluene at the temperature of 110 ℃ under an inert gas atmosphere for 20-30 hours, and separating and purifying to obtain a compound 5, wherein the molar ratio of the added amount of the tetrakis (triphenylphosphine) palladium to the molar ratio of the tetrakis (triphenylphosphine) palladium catalyst to a benzodithiophene unit trimethyltin compound with Ar substituent, namely the compound 4, is 1: 10-100;
(4) stirring the compound 5, an electron withdrawing group A and piperidine or pyridine in chloroform at 70 ℃ for 12 hours, and finally separating and purifying to obtain an A-D-A conjugated molecular product 6 which has the following general structure and takes a benzodithiophene unit as a core and thiazole as a bridging unit, wherein the molar ratio of the added piperidine or pyridine to the aldehyde compound which has R1, R2 and R3 substituents and takes the benzodithiophene unit as the core and the thiazole as the bridging unit, namely the compound 5, is 1: 0.001-0.5:
wherein,
x is selected from any one of O, S or Se;
R1~R3independently selected from hydrogen, C1~C30Alkyl of (C)1~C30Any one of alkoxy or 4-alkylphenyl;
the electron withdrawing group A is selected from one of the following structures:
r in the above A structure4Is C1~C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1~C8Any one of the alkyl groups of (1).
The characteristics of the prepared thiazole-containing organic micromolecules refer to the figures 1 to 4:
as shown in FIG. 1, the absorption is stronger in the range of 300-700nm, and the film absorption has a distinct absorption shoulder at 610 nm, indicating that stronger interaction and aggregation exist among molecules;
as shown in FIG. 2, the initial oxidation potential of the small moleculeIs 0.73V vs Ag/Ag+Initial reduction potentialis-1.14V vs Ag/Ag+. By the formula HOMO ═ Eox+4.73) (eV) and LUMO ═ Ere+4.73) (eV) the HOMO and LUMO levels of BTTzR can be calculated to be-5.46 eV and-3.59 eV, respectively;
as shown in FIG. 3, the thermal decomposition temperature (T) when the weight loss of the small molecule is 5%d) The temperature is 402 ℃, which shows that the small molecule BTTzR has good thermal stability;
as shown in FIG. 4, the small molecule has a sharp melting endothermic peak (T) at 315 ℃ during heatingm) Correspondingly, a distinct exothermic crystallization peak (T) occurs at 291 ℃ during the exothermc) It can be concluded that the small molecule BTTzR has good crystallization properties.
The invention also claims application of the thiazole-containing organic micromolecules as an electron donor or electron acceptor material of an active layer for light capture in preparation of organic solar cells.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The present invention will be described in detail by using structural schematic and the like, and in the detailed description of the embodiments of the present invention, the schematic is not partially enlarged in general proportion for convenience of description, and the schematic is only an example, which should not limit the scope of the present invention. In addition, the actual fabrication process should include three-dimensional space of length, width and depth.
Example 1
Referring to fig. 7, fig. 7 is a synthesis route of BTTzR of a thiazole-containing small organic molecule according to the present invention. As shown in FIG. 7, the present embodiment shows the synthetic route of thiazole-containing small organic molecules as follows:
note: r1Represents 2-ethylhexyl, R2Represents n-hexyl.
The detailed synthesis steps of the product in each step are as follows:
step 1) synthesizing a compound 2,2- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) -5- (4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazole;
starting with compound 1, i.e., 2, 5-bis (4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazole, in a 100ml single neck round bottom flask, chloroform (25ml) and glacial acetic acid (25ml) were added. N-bromosuccinimide (0.71g,4.01mmol) was slowly added to the single-necked flask in an ice-water bath protected from light. After the addition of N-bromosuccinimide was completed, a spherical drying tube with anhydrous magnesium sulfate was attached to the single-necked flask, and reacted for 10 hours with stirring. The reaction mixture was then poured into water (60ml) and chloroform and extracted three times and dried over anhydrous magnesium sulfate. After removal of the organic solvent by rotary evaporation, the crude product was isolated by column chromatography using petroleum ether as eluent to give compound 2 (1.16g, 50% yield) as an orange solid, i.e. 2- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) -5- (4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazole.
The structure validation data is as follows:1H NMR(400MHz,CDCl3),δ(ppm):7.38(s,1H),7.21(s, 1H),7.04(d,1H),2.56-2.55(d,2H),2.52-2.50(d,2H),1.35-1.29(m,18H), 0.93-0.88(m,12H),(MALDI-TOF)MS:calcd.for C28H37BrN2S4m/z=609.77; found 611.23.
step 2) synthesizing a compound 3, 5- (5- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazolo-2-yl) -3- (2-ethylhexyl) thiophene-2-carbaldehyde;
phosphorus oxychloride (1.32ml,14.16mmol) was injected into a 100ml two-necked round bottom flask with a syringe under an inert atmosphere of argon. N, N-dimethylformamide (1.36ml,17.7mmol) was then slowly added dropwise to the two-necked flask with a syringe under ice-water bath conditions and reacted for one and a half hours with stirring. Compound 2(1.08g,1.77mmol) was dissolved in chloroform (30 ml). The chloroform solution containing compound 2 dissolved therein was injected into a two-necked flask by a syringe. Thereafter, the reaction mixture was transferred to a 70 ℃ oil bath, and after refluxing the reaction for 12 hours with stirring, the mixture was extracted with methylene chloride (120 ml). The crude product was separated by column chromatography using petroleum ether/dichloromethane (1:1) as eluent to give compound 3(0.99g, 88% yield) as an orange solid, 5- (5- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazolo-2-yl) -3- (2-ethylhexyl) thiophene-2-carbaldehyde.
The structure validation data is as follows:1H NMR(400MHz,CDCl3),δ(ppm):10.04(s,1H),7.40 (s,1H),7.24(s,1H),2.90-2.88(d,2H),2.52-2.51(d,2H),1.38-1.25(m,18H), 0.93-0.89(m,12H),(MALDI-TOF)MS:calcd.for C29H37BrN2OS4m/z=637.78; found 638.23.
step 3) synthesis of the compound 5,5, 5'- (5,5' - (5,5'- (4,8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) benzo [1,2-b:4,5-b' ] dithiophene-2, 6-diyl) bis (4- (2-ethylhexyl) thiophen-5, 2-diyl)) bis (thiazolo [5,4-d ] thiazolo-5, 2-diyl)) bis (3- (2-ethylhexyl) thiophen-2-carbaldehyde);
in a dried 100ml two-necked round-bottom flask, compound 3(0.87g,1.36mmol), compound 4(4, 8-bis (5- (2-ethylhexyl) -4-hexane)Thien-2-yl) benzo [1,2-b:4,5-b']Dithiophene-2, 6-diyl) bis (trimethylstannyl) (0.59g,0.55mmol) (Compound 4 was purchased from Nakay Co.) and tetrakis (triphenylphosphine) palladium [ Pd (PPh) as a catalyst3)4](0.047g,0.04mmol) were dissolved together in dry purified toluene. The reaction mixture was placed in an oil bath under argon protection (the temperature in the oil bath was slowly raised to 110 ℃) and reacted for 24 hours with stirring. After completion of the reaction, the reaction mixture was poured into a mixture of water and methylene chloride (100ml) and extracted three times. Drying the organic layer with anhydrous magnesium sulfate, removing the solvent by rotary evaporation to obtain a crude product, and separating by column chromatography silica gel method, wherein the specific polarity of the column chromatography separation eluent is petroleum ether: chloroform-1: 1, compound 5 was finally obtained as a red solid (0.75g, 73% yield), i.e., 5'- (5,5' - (5,5'- (4,8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) benzo [1,2-b:4,5-b']Dithiophene-2, 6-diyl) bis (4- (2-ethylhexyl) thiophene-5, 2-diyl)) bis (thiazole [5,4-d]Benzothiazole-5, 2-diyl)) bis (3- (2-ethylhexyl) thiophene-2-carbaldehyde).
The structure validation data is as follows:1H NMR(400MHz,CD2Cl2),δ(ppm):9.98(s,2H),7.74 (s,2H),7.37-7.36(d,4H),7.32(s,2H),2.83-2.80(t,12H),2.69-2.66(t,4H), 1.50-1.28(m,70H),1.00-0.84(m,42H),(MALDI-TOF)MS:calcd.For C104H138N4O2S12m/z=1861.01;found 1860.03.
step 4) synthesis of BTTzR, (5Z,5'Z) -5,5' - ((5,5'- (5,5' - (5,5'- (4,8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) benzo [1,2-b:4,5-b' ] dithiophene-2, 6-diyl) bis (4- (2-ethylhexyl) thiophen-5, 2-diyl)) bis (thiazolo [5,4-d ] benzothiazole-5, 2-diyl)) bis (3- (2-ethylhexyl) thiophen-5, 2-diyl)) bis (methylidene)) bis (3-ethyl-rhodanine);
compound 5(0.39g,0.21mmol) was dissolved in a clean and purified chloroform solvent (40 ml). Then Lawstronic end-group rhodanine (0.34g,2.1mmol) and 5 drops of piperidine were added. The reaction mixture was then stirred under an inert atmosphere of argon for 12 hours. After stirring the reaction for 12 hours, the reaction mixture was extracted three times with chloroform. The organic layer was washed with water three times and then dried over anhydrous magnesium sulfate. And (3) after removing the anhydrous magnesium sulfate by suction filtration, removing the organic solvent by rotary evaporation to obtain a crude product, and separating the crude product by using a column chromatography silica gel method, wherein the specific polarity of an eluent for column chromatography separation is petroleum ether: chloroform 2:3, the final product BTTzR was obtained as a black solid (0.32g, 71% yield).
The structure validation data is as follows:1H NMR(400MHz,CDCl3),δ(ppm):7.87(s,2H),7.77(s, 2H),7.38(d,2H),7.36(s,2H),7.28(s,2H),4.19-4.14(m,4H),2.84-2.76(m,8H), 2.72-2.70(d,4H),2.67-2.63(t,4H),1.38-1.25(m,70H),1.00-0.84(m,48H), (MALDI-TOF)MS:calcd.For C114H148N6O2S16m/z=2147.47;found 2145.56.
preparing a solar photovoltaic device and testing the performance of the solar photovoltaic device:
commercially available Indium Tin Oxide (ITO) glass is firstly cleaned by a detergent, then is sequentially cleaned by water, deionized water, acetone and isopropanol through ultrasonic cleaning, and is dried and then is spin-coated with a layer of polyethylene dioxythiophene with the thickness of 40 nm: and (3) drying the anode modification layer of the polystyrene sulfonate PEDOT: PSS (weight ratio of 1:1) (AL 4083) at 150 ℃ for 15 minutes for later use. The active layer of the device is formed by dripping the blending solution of the A-D-A conjugated molecule BTTzR based on thiazole as the bridging unit and the small molecule acceptor material IT-4F (weight ratio is 1.5:1,1:1 and 1:1.5) on the anode modification layer of PEDOT: PSS (AL 4083) respectively, and the concentration of the donor small molecule BTTzR is 10mg ml-1. Then, zinc oxide (ZnO-NPs) with nano particles is spin-coated on the active layer to be used as a cathode interface layer. The effective area of each cell in the active layer of the photovoltaic device is 0.2cm-2. Vacuum (1X 10) on the active layer-4Pa) evaporating metal aluminum with the thickness of about 100nm as a cathode of the photovoltaic device.
SS-F5-3A (Enli Technology CO., Ltd.) xenon lamp equipped with AM 1.5 filter was used as the simulated solar light source at 100mWcm-2Carrying out photovoltaic performance test on the device under light intensity, wherein the light intensity is calibrated through a standard monocrystalline silicon solar cell; the J-V curve was measured using Keithley 2450.
Referring to FIG. 5, FIG. 5 shows a thiazole-containing organic small molecule in organic solar cell according to the present inventionJ-V curve of the cell. As shown in FIG. 5, the short-circuit current J of the device was measuredscIs 17.84mA cm-1Open circuit voltage VocAt 0.89V, a fill factor FF of 66.45% and an energy conversion efficiency PCE of 10.59%.
The structure of the small molecule receptor IT-4F used in the invention is as follows:
compared with the prior art, the invention has the beneficial effects that: according to the organic micromolecules containing thiazole, a high-performance benzodithiophene unit (BDT) is used as an electron donor core, thiazole is used as a bridging unit, and a series of brand-new A-D-A conjugated molecules which are good in solubility and thermal stability and take the thiazole as the bridging unit are synthesized by changing the design of a terminal electron withdrawing unit.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (6)
1. The organic micromolecule containing thiazole is an A-D-A conjugated organic micromolecule which takes a benzodithiophene unit as a core and takes thiazole as a bridging unit and is characterized by having the following structure:
wherein,
x is selected from any one of O, S or Se;
R1~R3independently selected from hydrogen, C1~C30Alkyl of (C)1~C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represents any one of the following unsubstituted or substituted groups:
an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, an arylene group containing at least three rings, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a heteroarylene group containing at least three rings, wherein in the bicyclic arylene group, the arylene group containing at least three rings, the bicyclic heteroarylene group or the heteroarylene group containing at least three rings, the rings are fused with each other or connected through a single bond;
when Ar is1And Ar2When any one or two of them are substituted at the same time, Ar1Or Ar2Each having 1 to 2 substituents of aryl group and C1~C30Or with C1~C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
r in the above A structure4Is C1~C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1~C8Any one of the alkyl groups of (1).
2. A thiazole-containing small organic molecule according to claim 1, wherein: said X ═ S; the R is1~R3Independently of one another is hydrogen, C1~C8In alkyl or 4-hexylphenyl ofAny one of (a); r in the structure of A4Is C1~C8Any one of the alkyl groups of (1).
3. A preparation method of thiazole-containing organic micromolecules is characterized by comprising the following steps:
(1) dissolving the compound 1 in a mixed solvent of chloroform and glacial acetic acid, slowly adding N-bromosuccinimide in an ice-water bath under the condition of keeping out of the sun, removing the ice-water bath after half an hour, carrying out normal-temperature stirring reaction for 10 hours, and separating and purifying to obtain a compound 2;
(2) stirring phosphorus oxychloride and N, N-dimethylformamide to react for 1-2 hours under the condition of ice-water bath, removing the ice-water bath, dissolving the compound 2 in chloroform, adding the chloroform into the product obtained by the reaction of the phosphorus oxychloride and the N, N-dimethylformamide by using an injector, stirring at 70 ℃, refluxing for 12 hours, separating and purifying to obtain a compound 3;
(3) stirring and reacting the compound 3, the compound 4 and a catalyst tetrakis (triphenylphosphine) palladium in toluene at 110 ℃ for 20-30 hours, and separating and purifying to obtain a compound 5;
(4) stirring the compound 5, an electron withdrawing group A and piperidine or pyridine in chloroform at 70 ℃ for 12 hours, and finally separating and purifying to obtain an A-D-A conjugated molecular product 6 which has the following general structure and takes benzodithiophene as a core and thiazole as a bridging unit;
wherein,
x is selected from any one of O, S or Se;
R1~R3independently selected from hydrogen, C1~C30Alkyl of (C)1~C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represent any of the following groups which are unsubstituted or have a substituentOne of them is:
an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, an arylene group containing at least three rings, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a heteroarylene group containing at least three rings, wherein in the bicyclic arylene group, the arylene group containing at least three rings, the bicyclic heteroarylene group or the heteroarylene group containing at least three rings, the rings are fused with each other or connected through a single bond;
when Ar is1And Ar2When any one or two of them are substituted at the same time, Ar1Or Ar2Each having 1 to 2 substituents of aryl group and C1~C30Or with C1~C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
r in the above A structure4Is C1~C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1~C8Any one of the alkyl groups of (1).
4. A method for preparing thiazole-containing small organic molecules as claimed in claim 3, wherein: the molar ratio of the added piperidine or pyridine to the compound 5 is 1: 0.001-0.5.
5. A method for preparing thiazole-containing small organic molecules as claimed in claim 3, wherein: and (3) and (4) are stirred to react under the inert gas atmosphere.
6. A method for preparing thiazole-containing small organic molecules as claimed in claim 3, wherein: the molar ratio of the catalyst tetrakis (triphenylphosphine) palladium to the compound 4 is 1: 10-100.
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