CN115991714A - Side chain modified non-fullerene receptor, and synthesis method and application thereof - Google Patents
Side chain modified non-fullerene receptor, and synthesis method and application thereof Download PDFInfo
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- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 47
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 107
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 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 claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000013508 migration Methods 0.000 claims abstract description 6
- 230000005012 migration Effects 0.000 claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 210000004556 brain Anatomy 0.000 claims abstract description 3
- 238000005893 bromination reaction Methods 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 14
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- -1 boric acid ester Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000002950 deficient Effects 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000077 silane Chemical group 0.000 claims description 3
- WIFCKLPZYYALGY-UHFFFAOYSA-N 1h-pyrrole-2,3-dione Chemical group O=C1NC=CC1=O WIFCKLPZYYALGY-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- BUOKUWQCVSZNCF-UHFFFAOYSA-N selenadiazole Chemical compound C1=C[se]N=N1 BUOKUWQCVSZNCF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 8
- 239000011261 inert gas Substances 0.000 claims 5
- 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 2
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 239000000370 acceptor Substances 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 16
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 91
- 239000012043 crude product Substances 0.000 description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000002904 solvent Substances 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 19
- 239000012074 organic phase Substances 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000004896 high resolution mass spectrometry Methods 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000005605 benzo group Chemical group 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
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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 Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a side chain modified non-fullerene acceptor and a synthesis method and application thereof, belongs to the technical field of organic photoelectric materials, and aims to solve the problems of complex synthesis process and high cost of Y-series non-fullerene acceptors. The synthesis of non-fullerene acceptor compounds of formula I includes the steps of: the compound formula V-1 is subjected to bromination reaction to obtain a compound formula V-2; the compound formula V-2 is subjected to bromine migration reaction to obtain a compound formula V-3; the compound formula V-3 is subjected to a coupling reaction to obtain a compound formula V-4; the compound of the formula V-4 is subjected to condensation reaction by brain Wen Ge to obtain a compound of the formula I; the application also discloses the application of the non-fullerene acceptor in a solar cell device. The invention constructs a simple and efficient side chain modification strategy by a halogen migration method, and can be used for side chain modification of Y-series receptor materials.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a side chain modified non-fullerene receptor, and a synthesis method and application thereof.
Background
Among various ways of utilizing solar energy, a solar cell that directly converts solar energy into electric energy by a photovoltaic effect is considered as one of the most promising technologies. The organic solar cell is used as one of the third-generation solar cell technologies, has the characteristics of solution processing, low cost, easy adjustment of material structure and the like, and is widely focused by global photovoltaic enterprises and scientific research institutions.
With the development of aromatic condensed ring non-fullerene acceptor materials, especially the development of Y series non-fullerene acceptors, the device efficiency of the organic solar cell is remarkably improved. The Y-series receptor is an aromatic condensed ring constructed by D-A-D units, and absorbs light in infrared and far infrared wave bands. Devices based on the Y-series non-fullerene receptors have been photovoltaic efficient by more than 18%. In addition, the non-fullerene acceptor has a modularized structure, so that the non-fullerene acceptor is convenient to functionally modify, the performance is further improved, and the preparation of a high-efficiency organic solar cell device is realized. The bithiophene 'beta' position of the condensed ring nucleus of the Y-series receptor is a modification site which can effectively regulate and control the photovoltaic performance. However, in the synthesis, 3-bromothiophene is usually adopted as a starting material, and if the beta position is to be regulated, the preparation can be started from the starting material, so that the process is complicated and various limitations exist when different beta-substituted Y-series non-fullerenes are prepared in the later stage (Energy Environ.Sci.2021,14,3469;Adv.Energ.Mater.2021,11 (47), 2102596;Energy Environ.Sci.2022,15 (5), 2011).
Disclosure of Invention
Aiming at the technical problems, the invention provides a side chain modified non-fullerene acceptor, a synthesis method and application thereof, and a simple and efficient side chain modification strategy is constructed by a halogen migration method and is used for side chain modification of Y-series acceptor materials.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a side chain modified non-fullerene acceptor, the structural formula is shown as formula I:
in the formula I, X, Y respectively represents any one of S, se, O, te;
in the formula I, R is independently selected from straight-chain or branched-chain alkyl or alkoxy, alkylthio and silane groups with the carbon number of 1-30, and alkyl or alkoxy, alkylthio and silane substituted aryl; the aryl group may be a benzene ring or a thiophene ring;
in the formula I, the A1 unit is an electron-deficient unit, is a thiadiazole, selenadiazole, oxadiazole, triazole, quinoline, pyrrole dione unit and derivatives thereof, and specifically is one of the structures in the formula II.
In formula II, the dotted line represents the position attached to the β position of the pyrrole ring in formula I; r is R 1 -R 4 Straight or branched alkyl or alkoxy groups having 1 to 30 carbon atoms, alkylthio groups, silyl groups, and alkyl or alkoxy groups, alkylthio groups, silane-substituted aryl groups which may be benzene rings or thiophene rings;
in the formula I, the A2 unit is an electron-deficient unit, and is any one of the following structures in the formula III.
In formula III, the dotted line indicates the position of attachment to the group; r is R 5 -R 8 Are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a straight or branched alkyl or alkoxy group having 1 to 30 carbon atoms, an alkylthio group, a silane group, and an alkyl or alkoxy group, an alkylthio group, a silane-substituted aryl group. The aryl group may be a benzene ring or a thiophene ring; the halogen may be F, br or Cl.
Preferably, the non-fullerene acceptor in formula I is any one of the following formulas IV-1 to IV-5, but is not limited to the following compounds:
the invention also provides a preparation method of the non-fullerene acceptor, which comprises the following steps:
in the formulae V-1 to V-4, A1, A2 and R, R 1 、R 2 Is as defined for formula I.
The synthesis of non-fullerene acceptor compounds of formula I includes the steps of:
the compound formula V-1 is subjected to bromination reaction to obtain a compound formula V-2;
the compound formula V-2 is subjected to bromine migration reaction to obtain a compound formula V-3;
the compound formula V-3 is subjected to a coupling (Suzuki or Stille) reaction to obtain a compound formula V-4;
compound formula V-4 is obtained by a brain Wen Ge (Knoevenagel) condensation reaction.
The specific synthetic steps of the non-fullerene acceptor compound of formula I are:
1) Synthesis of Compound V-1
Under argon atmosphere, adding dibromodinitro substituted benzo condensed ring nucleus (thieno [3, 2-b) with 2-10 times of the molar weight of the condensed ring nucleus into a two-mouth bottle]Thiophene-2-yl) tributyltin, a proper amount of toluene solvent and 0.01-10% of tetraphenylpalladium phosphate catalyst. Heating to 110 ℃ for light-shielding reaction for 5-24 hours, and then decompressing to remove the solvent to obtain the coupled crude product, and directly carrying out the next step without other treatment. Under argon atmosphere, adding the obtained coupling crude product into a two-mouth bottle, wherein the molar quantity of the crude product is 5-10 times of that of triphenylphosphine, and a proper quantity of dichlorobenzene solvent is used. Heating to 180 ℃ for reaction for 12-24 hours, filtering and washing with methylene dichloride to obtain a ring-closed crude product. Under argon environment, adding closed-loop crude product, potassium carbonate 2-10 times of the molar weight of the crude product, potassium iodide 5-10 times of the molar weight of the crude product and R10-20 times of the molar weight of the crude product into a two-mouth bottle 1 、R 2 BrominationAlkane and proper amount of N, N-dimethylformamide solvent. After heating to 110 ℃ for 10-24 hours, adding water for quenching, washing the mixture with saturated saline, extracting with dichloromethane, collecting an organic phase, drying the organic phase with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a V-1 crude product. The crude product is separated by column chromatography, and the eluent is petroleum ether/dichloromethane, thus obtaining the compound shown as the intermediate formula V-1.
2) Synthesis of Compound V-2
Under the argon environment, the condensed nucleus of the compound shown in the formula V-1 and a proper amount of tetrahydrofuran solvent are added into a two-mouth bottle, and in an ice-water bath, N-bromosuccinimide with the molar quantity of 8-10 times is poured into the system for reaction for 4-10 hours. After the reaction, water was added to quench, washed with saturated aqueous sodium thiosulfate solution and extracted three times with methylene chloride, and the organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a crude product. The crude product is separated by column chromatography, and the eluent is petroleum ether/dichloromethane, thus obtaining the compound shown as the intermediate formula V-2.
Preferably, the mass to volume ratio of the compound of formula V-1 to the tetrahydrofuran solvent is (1-2) g:15mL. More preferably, the mass to volume ratio of compound formula V-1 to tetrahydrofuran solvent is 1g:15mL.
3) Synthesis of Compound formula V-3
Under argon environment, adding a compound shown in a formula V-2 and a proper amount of tetrahydrofuran solvent into a two-mouth bottle, slowly dripping lithium diisopropylamide with a molar quantity of 4-8 times into the system at a temperature of-78 to-50 ℃, reacting for 1-2h, taking out and reacting for 3-4h at room temperature. In an ice-water bath, N-dimethylformamide with the molar quantity of 5-10 times is added into the system, and the reaction is carried out at room temperature overnight, preferably for 8-12h; more preferably, the reaction time is 12 hours. After the reaction, the mixture was quenched with water, washed with saturated brine and extracted with dichloromethane, and the organic phase was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give a crude product. The crude product is separated by column chromatography, and the eluent is petroleum ether/dichloromethane, thus obtaining the compound shown as the intermediate formula V-3.
Preferably, the mass to volume ratio of the compound of formula V-2 to the tetrahydrofuran solvent is (1-2) g:15mL. More preferably, the mass to volume ratio of compound formula V-2 to tetrahydrofuran solvent is 1g:15mL.
4) Synthesis of Compound formula V-4
The preparation method can be classified into the following two types according to the boric acid, borate and alkyltin reagent based on R unit used.
Method 1: under argon environment, adding a compound shown in a formula V-3, boric acid or boric acid ester based on an R unit in an amount which is 32-10 times the molar amount of the compound in the formula V-3, potassium carbonate in an amount which is 1-10 times the molar amount, aliquat 336 in an amount which is 0.1-4 times the molar amount, a proper amount of toluene solvent and deionized water into a two-port bottle, wherein the amount of the tetra-triphenylphosphine palladium catalyst in the formula V-3 is 0.01-10%. Heating to 90-110 ℃ to react for 5-24 hours in the dark, adding water to quench, washing the mixture with saturated saline, extracting with dichloromethane, collecting an organic phase, drying with anhydrous magnesium sulfate, decompressing and removing the solvent to obtain a crude product, and directly carrying out the next step without other treatment.
Preferably, the mass to volume ratio of compound formula V-3 to toluene and deionized water is (1-2) g: (80-120) mL: (40-60) mL. More preferably, the mass to volume ratio of compound formula V-3 to toluene and deionized water is 1g:120mL:60mL.
Method 2: under the argon environment, adding a compound shown in a formula V-3, an alkyl tin reagent based on an R unit, 2-10 times of the molar quantity of the compound shown in the formula V-3, and a proper amount of toluene solvent into a two-mouth bottle, wherein the molar quantity of the compound shown in the formula V-3 is 0.01% -10% of a tetraphenylpalladium phosphorus catalyst. Heating to 90-110 ℃ for reaction in dark place for 5-24h, adding water for quenching, washing the mixture with saturated saline, extracting with dichloromethane, collecting an organic phase, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product, and directly carrying out the next step without other treatment.
Preferably, the mass to volume ratio of compound formula V-3 to toluene is (1-2) g:120mL. More preferably, the mass to volume ratio of compound of formula V-3 to toluene is 1g:120mL.
5) Synthesis of Compound of formula I
Adding the compound shown in the formula V-4 into a two-mouth bottle, adding 2-10 times of the compound shown in the formula III at the tail end and a proper amount of chloroform solution, introducing argon for 10 minutes to remove oxygen, stirring at room temperature for 10 minutes, then adding 10-40 times of pyridine, and reacting at the reaction temperature of 20-65 ℃ for 3-12 hours. The reaction system is poured into methanol and filtered to obtain a crude product. Separating the crude product by column chromatography, eluting with petroleum ether/dichloromethane to obtain the compound shown in formula I.
Preferably, the molar volume ratio of compound of formula V-4 to chloroform is (0.1-0.2) mmol:30mL. More preferably, the molar volume ratio of compound of formula V-4 to chloroform is 0.1mmol:30mL.
It is still another object of the present invention to provide a photoactive layer consisting of a non-fullerene acceptor and a p-type electron donor polymer represented by formula I, the mass ratio of the non-fullerene acceptor to the p-type electron donor polymer being 1:0.1 to 10, preferably the mass ratio of non-fullerene acceptor to p-type electron donor polymer is 1:1.5.
the p-type electron donor polymers of the present invention are suitable for use in any of a variety of p-type electron donor polymers, such as PM6, which may be selected by one of skill in the art.
The photoactive layer may be mixed with at least one of toluene, xylene, trimethylbenzene, chloroform, chlorobenzene, dichlorobenzene, and trichlorobenzene as solvents, and the concentration of the non-fullerene acceptor may be 0.5 to 50mg/mL, preferably 4 to 20mg/mL, and the concentration of the p-type electron donor polymer may be 0.5 to 50mg/mL, preferably 3 to 20mg/mL, in the resulting mixture.
The invention also provides a polymer solar cell device comprising a first electrode, a second electrode spaced apart from the first electrode, and at least one semiconductor layer disposed between the first electrode and the second electrode, the semiconductor layer comprising the non-fullerene acceptor or the photoactive layer.
The use of the non-fullerene acceptor and the photoactive layer in the preparation of the following functional energy devices also falls within the scope of the present invention: thin film semiconductor devices, light detecting devices, polymer solar cell devices, and photovoltaic devices.
The invention has the beneficial effects that:
the invention constructs a simple and efficient side chain modification strategy by a halogen migration method, and can be used for side chain modification of Y-series receptor materials. In the synthesis, the expensive 3-bromothiophene is avoided being used as a starting material, so that on one hand, the synthesis cost of the non-fullerene acceptor material is reduced, and on the other hand, the side chain modification step is optimized, the performance of the non-fullerene material is simpler and more efficient through side chain engineering optimization, and the structure-activity relationship between the side chain structure of the non-fullerene acceptor material and the performance of a device is further explored later.
The prepared non-fullerene acceptor material has good film forming performance, higher molar absorptivity and thermal stability, better charge transmission performance and proper electron energy level, can be used as an electron acceptor material to be matched with a p-type electron donor polymer, and is applied to a polymer solar cell device. Thanks to the above advantages, the non-fullerene acceptor materials IV-1 and IV-3 synthesized in the embodiments of the present invention achieve high photoelectric conversion efficiencies of 17.83% and 15.81% respectively after matching with the polymer donor PM6, and simultaneously have higher open-circuit voltage and short-circuit current due to their good light absorption performance, excellent charge transport capability and suitable electron energy level.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a hydrogen spectrum of the compound IV-1 of example 1 of the present invention;
FIG. 2 is a hydrogen spectrum of the compound IV-3 of example 2 of the present invention;
FIG. 3 is a hydrogen spectrum of the compound IV-4 of example 3 of the present invention;
FIG. 4 is a graph of current-voltage (I-V) curve for preparing a polymer solar cell according to the present invention;
fig. 5 is an External Quantum Efficiency (EQE) graph of a polymer solar cell prepared according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
A synthesis of a side chain modified non-fullerene acceptor compound IV-1 comprising the steps of:
(1) Into a 250mL two-necked flask under argon atmosphere was added 4, 7-dibromo-5, 6-dinitrobenzo [ c ]][1,2,5]Thiadiazoles (5 g,13.03 mmol), (thieno [3, 2-b)]Thiophene-2-yl) tributyltin (34 g,78.15 mmol), toluene (50 mL), 5% Pd (PPh 3 ) 4 (0.75 g,0.65 mmol). After heating reaction to 110 ℃ and light-shielding reaction for 14 hours, decompressing and removing the solvent to obtain a coupled crude product, and directly carrying out the next step without other treatment. To a 250mL two-necked flask under argon was added the resulting crude coupled product, triphenylphosphine (17.08 g,65.11 mmol), in the presence of dichlorobenzene (50 mL). After heating to 180 ℃ for 24 hours, the ring-closed crude product is obtained after filtration and washing by methylene dichloride. To a 250mL two-necked flask under argon was added the ring-closed crude product, potassium carbonate (5.41 g,39.09 mmol), potassium iodide (17.31 g,104.24 mmol), 2-ethylhexyl bromide (37.73 g,195.45 mmol), N, N-dimethylformamide (80 mL). After heating to 110℃for 15 hours, the reaction mixture was quenched with water, washed with saturated brine, extracted with dichloromethane, and the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give V-1 as a crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 1 as an orange liquid (3.55 g, 41%).
(2) To a 100mL two-necked flask under argon was added intermediate 1 (2 g,3.02 mmol) and tetrahydrofuran (30 mL). N-bromosuccinimide (4.29 g,24.14 mmol) was poured into the system at 0deg.C and reacted for 8h. After the reaction, it was quenched with water, washed with saturated aqueous sodium thiosulfate (100 mL) and extracted with methylene chloride (3X 100 mL), and the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 2 as an orange solid (2.11 g, 85%).
Nuclear magnetic characterization data for intermediate 2:
1 H NMR(400MHz,CDCl 3 ，ppm)δ7.45(s,2H),4.53(m,4H),1.97(t,J＝4Hz,2H),1.95,1.03(m,5H),0.89(m,11H),0.62(m,12H).
(3) To a 100mL two-necked flask was added intermediate 2 (2 g,2.44 mmol) and anhydrous tetrahydrofuran solution (40 mL) under argon. LDA in THF/n-Hexane solution (2M, 6.09mL,12.19 mmol) was slowly added dropwise to the system at-50℃and reacted for 1 hour, and the reaction was carried out at room temperature for 4 hours. N, N-dimethylformamide (1.88 mL) was added to the system at 0deg.C, and the reaction was carried out overnight at room temperature. After the reaction was quenched with water, washed with saturated brine (100 mL) and extracted with dichloromethane (3X 100 mL), the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 2 as an orange solid (1.38 g, 65%).
Nuclear magnetism and mass spectrometry characterization data for intermediate 3:
1 H NMR(400MHz，CDCl 3 ，ppm)δ10.09(s,2H),4.62(m,4H),1.97(m,2H),1.05(m,5H),0.89(m,11H),0.64(m,12H).HR-MS(MALDI-TOF)m/z calcd.for(C36H36Br2N4O2S5):875.9788.Found:875.9783.
(4) 50mL of the mixture was purged under argonIn a bottle was added intermediate 3 (0.1 g,0.12 mmol), 3- (2-butyloctyloxy) phenylboronic acid pinacol ester (0.45 g,1.14 mmol), K 2 CO 3 (0.79 g,0.57 mmol), aliquat 336 (0.2 mmol, about 2 drops), toluene (12 mL), deionized water (6 mL), and Pd (PPh) 3 ) 4 (6.59 mg,0.0057 mmol) was heated to 110℃and allowed to react for 24h in the absence of light, quenched with water, the mixture was washed with saturated brine (100 mL), extracted with dichloromethane (3X 100 mL), the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to give crude intermediate 4, which was directly used in the next step without additional work-up.
(5) To a 50mL two-necked flask were added intermediate 4 (0.1 mmol), IC-2F (106 mg,0.5 mmol) and chloroform solution (30 mL), followed by argon for 10 minutes to remove oxygen, stirring at room temperature for 10 minutes, and then pyridine (0.1 mL) was added, and the system was heated to 55℃to react for 12 hours. The reaction mixture was poured into methanol (100 mL) and filtered to give a crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give compound IV-1 as a dark blue solid (130 mg, 78%).
Nuclear magnetism (FIG. 1) and mass spectrometry characterization data for compound IV-1:
1 H NMR(400MHz,CDCl 3 ，ppm)δ8.91(s,2H),8.52(m,2H),7.73(t,J＝8Hz,2H),7.54(t,J＝8Hz,2H),7.19(m,6H),4.80(m,4H),3.96(d,J＝4Hz,4H),2.13(m,2H),1.85(m,2H),1.56(s,2H),1.50(m,4H),1.43(m,2H),1.35(m,13H),1.29(m,10H),1.21(m,4H),1.04(m,12H),0.91(t,J＝4Hz,6H),0.87(m,7H),0.72(m,12H)； 13 C NMR(151MHz,CDCl 3 )δ185.82,171.64,159.05,155.21,153.55,153.46,153.37,147.50,144.91,143.10,138.90,137.63,136.78,136.69,135.08,134.34,134.27,133.81,132.45,132.40,131.46,120.90,119.15,114.89,114.80,114.67,114.25,113.57,112.60,112.46,107.45,68.80,55.72,40.56,38.15,31.94,31.27,30.95,29.88,29.83,29.75,29.11,27.92,27.85,26.89,23.35,23.28,23.13,22.96,22.94,22.79,14.22,14.20,13.89,13.87,10.26,10.17.HR-MS(MALDI-TOF)m/z calcd.for(C96H98F4N8O4S5):1662.6251.Found:1662.6291.
example 2
A synthesis of a side chain modified non-fullerene acceptor compound IV-3 comprising the steps of:
(1) To a 100mL two-necked flask were added intermediate 1 (2 g,3.02 mmol) (prepared from example 1) and tetrahydrofuran (30 mL) under argon. N-bromosuccinimide (4.29 g,24.14 mmol) was poured into the system at 0deg.C and reacted for 8h. After the reaction, it was quenched with water, washed with saturated aqueous sodium thiosulfate (100 mL) and extracted with methylene chloride (3X 100 mL), and the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 2 as an orange solid (2.11 g, 85%).
Nuclear magnetic characterization data for intermediate 2:
1 H NMR(400MHz,CDCl 3 ，ppm)δ7.45(s,2H),4.53(m,4H),1.97(t,J＝4Hz,2H),1.95,1.03(m,5H),0.89(m,11H),0.62(m,12H).
(2) To a 100mL two-necked flask was added intermediate 2 (2 g,2.44 mmol) and anhydrous tetrahydrofuran solution (40 mL) under argon. LDA in THF/n-Hexane solution (2M, 6.09mL,12.19 mmol) was slowly added dropwise to the system at-50℃and reacted for 1 hour, and the reaction was carried out at room temperature for 4 hours. N, N-dimethylformamide (1.88 mL) was added to the system at 0deg.C, and the reaction was carried out overnight at room temperature. After the reaction was quenched with water, washed with saturated brine (100 mL) and extracted with dichloromethane (3X 100 mL), the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 2 as an orange solid (1.38 g, 65%).
Nuclear magnetism and mass spectrometry characterization data for intermediate 3:
1 H NMR(400MHz,CDCl 3 ，ppm)δ10.09(s,2H),4.62(m,4H),1.97(m,2H),1.05(m,5H),0.89(m,11H),0.64(m,12H).HR-MS(MALDI-TOF)m/z calcd.for(C36H36Br2N4O2S5):875.9788.Found:875.9783.
(3) In a 50mL two-necked flask under argon was added intermediate 3 (0.1 g,0.12 mmol), pinacol 3- (2-butyloctyloxy) phenylboronate (0.45 g,1.14 mmol), K 2 CO 3 (0.79 g,0.57 mmol), aliquat 336 (0.2 mmol, about 2 drops), toluene (12 mL), deionized water (6 mL), pd (PPh 3 ) 4 (6.59 mg,0.0057 mmol) was heated to 110℃and reacted in the absence of light for 24h, quenched with water, the mixture was washed with saturated brine (100 mL), extracted with dichloromethane (3X 100 mL), the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to give crude intermediate 4, which was carried forward without further work.
(4) To a 50mL two-necked flask, intermediate 4 (0.1 mmol), IC-2Cl (132 mg,0.5 mmol) and chloroform solution (30 mL) were added, argon was introduced for 10 minutes to remove oxygen, and the mixture was stirred at room temperature for 10 minutes, followed by pyridine (0.1 mL) and the system was heated to 55℃to react for 12 hours. The reaction mixture was poured into methanol (100 mL) and filtered to give a crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give compound IV-3 as a dark blue solid (123 mg, 71%).
Nuclear magnetism (fig. 2) and mass spectrometry characterization data for compound IV-3:
1 H NMR(400MHz,CDCl 3 ，ppm)δ8.92(s,2H),8.73(s,2H),7.98(s,2H),7.56(t,J＝7.9Hz,2H),7.20(m,6H),4.79(m,4H),3.97(d,J＝5.6Hz,4H),2.19–2.09(m,2H),1.85(m,2H),1.50(m,4H),1.33(m,31H),1.07(m,12H),0.89(m,13H),0.74(m,12H).HR-MS(MALDI-TOF)m/z calcd.for(C96H98F4N8O4S5):1729.992.Found:1729.173.
example 3
The synthesis of the side chain modified non-fullerene acceptor compound IV-4 comprises the following steps:
(1) To a 100mL two-necked flask were added intermediate 1 (2 g,3.02 mmol) (prepared from example 1) and tetrahydrofuran (30 mL) under argon. N-bromosuccinimide (4.29 g,24.14 mmol) was poured into the system at 0deg.C and reacted for 8h. After the reaction, it was quenched with water, washed with saturated aqueous sodium thiosulfate (100 mL) and extracted with methylene chloride (3X 100 mL), and the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 2 as an orange solid (2.11 g, 85%).
Nuclear magnetic characterization data for intermediate 2:
1 H NMR(400MHz，CDCl 3 ，ppm)δ7.45(s,2H),4.53(m,4H),1.97(t,J＝4Hz,2H),1.95,1.03(m,5H),0.89(m,11H),0.62(m，12H).
(2) To a 100mL two-necked flask was added intermediate 2 (2 g,2.44 mmol) and anhydrous tetrahydrofuran solution (40 mL) under argon. LDA in THF/n-Hexane solution (2M, 6.09mL,12.19 mmol) was slowly added dropwise to the system at-50℃and reacted for 1 hour, and the reaction was carried out at room temperature for 4 hours. N, N-dimethylformamide (1.88 mL) was added to the system at 0deg.C, and the reaction was carried out overnight at room temperature. After the reaction was quenched with water, washed with saturated brine (100 mL) and extracted with dichloromethane (3X 100 mL), the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give intermediate 2 as an orange solid (1.38 g, 65%).
Nuclear magnetism and mass spectrometry characterization data for intermediate 3:
1 H NMR(400MHz,CDCl 3 ，ppm)δ10.09(s,2H),4.62(m,4H),1.97(m,2H),1.05(m,5H),0.89(m,11H),0.64(m,12H).HR-MS(MALDI-TOF)m/z calcd.for(C36H36Br2N4O2S5):875.9788.Found:875.9783.
(3) In a 50mL two-necked flask under argon was added intermediate 3 (0.1 g,0.12 mmol), 5- (2-butyloctyloxy) -2- (trimethylstannyl) thiophene (0.52 g,1.2 mmol), toluene (12 mL), pd (PPh) 3 ) 4 (6.59 mg,0.0057 mmol) was heated to 110℃and reacted in the absence of light for 24h, quenched with water, the mixture was washed with saturated brine (100 mL), extracted with dichloromethane (3X 100 mL), the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to give crude intermediate 5, which was carried forward without further work.
(4) To a 50mL two-necked flask, intermediate 5 (0.1 mmol), IC-2F (106 mg,0.5 mmol) and chloroform solution (30 mL) were added, argon was introduced for 10 minutes to remove oxygen, and the mixture was stirred at room temperature for 10 minutes, followed by pyridine (0.1 mL) and the system was heated to 55℃to react for 12 hours. The reaction mixture was poured into methanol (100 mL) and filtered to give a crude product. The crude product was isolated by column chromatography eluting with petroleum ether/dichloromethane to give compound IV-4 as a dark blue solid (134 mg, 80%).
Nuclear magnetism (fig. 3) and mass spectrometry characterization data for compound IV-4:
1 H NMR(400MHz,CDCl 3 ，ppm)δ9.07,8.54,8.52,8.52,8.50,7.74,7.72,7.70,7.41,7.40,7.28,7.27,4.82,4.79,4.77,4.75,4.71,3.04,3.03,2.12,2.10,2.09,1.79,1.78,1.76,1.74,1.73,1.56,1.51,1.47,1.46,1.44,1.43,1.33,1.32,1.31,1.20,1.10,1.08,1.05,1.03,1.02,1.00,0.98,0.96,0.94,0.92,0.89,0.88,0.86,0.78,0.76,0.73,0.72,0.70,0.68,0.66.HR-MS(MALDI-TOF)m/z calcd.for(C92H94F4N8O4S7):1674.5379.Found:1674.5371.
application example 4
The preparation method of the polymer solar cell device with the forward structure comprises the following steps:
any one of the compounds prepared in the invention and a donor material (PM 6) are blended and dissolved in chloroform according to the weight ratio of 1:1 to prepare 16mg/mL of blended active layer solution. OSCs are fabricated using ITO/PEDOT PSS/Active Layer/PDINN/Ag forward device structures. The ITO glass is sequentially ultrasonically cleaned for 10 minutes by deionized water, acetone and isopropanol, then transferred to a 150 ℃ oven for 15 to 30 minutes to dry the surface isopropanol, and finally the ITO glass is subjected to ultraviolet ozone treatment for 35 minutes. And spin-coating PEDOT: PSS on the surface of the ITO glass after treatment, and then placing the ITO glass into a baking oven at 150 ℃ for baking and transferring the ITO glass into a glove box. Next, the desired active layer solution is prepared in proportion, the thickness of the active layer is controlled by adjusting the rotation speed, and then annealing is performed. After the annealing was completed and cooled to room temperature, a cathode-modified layer PDINN (1 mg/mL) was spin-coated on the surface at 4000rpm, and the active layers on both sides were scraped off with a knife to expose the ITO glass. And finally evaporating Ag electrodes on the top layer of the device. In a glove box filled with nitrogen, a solar simulator was used at AM 1.5G (100 mW/cm 2 ) And testing the open-circuit voltage, the short-circuit current, the filling factor and the energy conversion efficiency of the prepared organic solar cell under the illumination intensity.
Test example 5
Characterization of device performance
Based on the compound of formula IV-1 prepared in example 1 and the compound of formula IV-3 prepared in example, devices were prepared according to the procedure of application example 4, and the organic solar cell device parameters of the forward structure were tested. The device performance parameters obtained from the test are shown in table 1. Wherein the open circuit voltage is 0.863V and the short circuit current is 26.21mA/cm 2 The filling factor is 78.81%, and the energy conversion efficiency is 17.83%.
Fig. 4 is a graph of current-voltage curves (I-V curves) obtained by characterization after preparation of an organic solar cell device by blending non-fullerene acceptors IV-1 and IV-3 with PM6 polymer donors, respectively, as active layer materials, from which the open-circuit voltage, short-circuit current, and fill factor of the device can be obtained. The IV-1 based device finally achieves a photoelectric conversion efficiency of 17.83% due to its suitable electron energy level, good light absorption properties and charge transport capabilities.
FIG. 5 is a graph of external quantum efficiency of a device, in which the IV-1 and IV-3 synthesized in this example are complementary to the absorption of PM6, effective utilization of visible-near infrared light is achieved, and higher short-circuit currents of 26.21 and 24.06mA/cm, respectively 2 . The parameters of the organic solar cell device prepared under the same conditions by using the compound shown in the formula IV-3 as an active layer acceptor material are that the open circuit voltage is 0.854V and the short circuit current is 24.06mA/cm 2 And a fill factor 76.95%, resulting in an energy conversion efficiency of 15.81%.
TABLE 1
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A synthesis method of a side chain modified non-fullerene acceptor is characterized in that the process flow is as follows:
the method comprises the following steps:
the compound formula V-1 is subjected to bromination reaction to obtain a compound formula V-2;
the compound formula V-2 is subjected to bromine migration reaction to obtain a compound formula V-3;
the compound formula V-3 is subjected to a coupling reaction to obtain a compound formula V-4;
the compound of the formula V-4 is subjected to condensation reaction by brain Wen Ge to obtain a compound of the formula I;
in the formula I, X, Y respectively represents any one of S, se, O and Te;
in the formula I, R units are independently straight-chain or branched-chain alkyl, alkoxy, alkylthio or silane groups with the carbon number of 1-30 and aryl substituted by alkyl, alkoxy, alkylthio or silane, wherein the aryl is benzene ring or thiophene ring;
in the formula I, the A1 unit is an electron-deficient unit, is any one of thiadiazole, selenadiazole, oxadiazole, triazole, quinoline, pyrrole dione unit and derivatives thereof, and is any one of the following structures in the formula II;
in the formula II, a dotted line represents a position connected to the beta position of the pyrrole ring;
R 1 -R 4 each independently is a straight-chain or branched alkyl, alkoxy, alkylthio or silyl group having 1 to 30 carbon atoms, and an alkyl, alkoxy, alkylthio or silane substituted aryl group which is a benzene ring or a thiophene ring;
in the formula I, the A2 unit is an electron-deficient unit and is any one of the following structures in the formula III;
in formula III, the dotted line indicates the position of attachment to the group; r is R 5 -R 8 Are each independently selected from a hydrogen atom, a halogen atom, or a straight-chain or branched alkyl or alkoxy group having 1 to 30 carbon atoms, an alkylthio group, a silane group, and an alkyl or alkoxy group, an alkylthio group, a silane-substituted aryl group, which is a benzene ring or a thiophene ring; the halogen atom is any one of F, br or Cl;
in the formulae V-1 to V-4, A1, A2 and R, R 1 、R 2 Is as defined for formula I.
2. The method of synthesizing a side-chain modified non-fullerene receptor according to claim 1, wherein the synthesis of the non-fullerene receptor compound of formula I specifically comprises the steps of:
synthesis of Compound formula V-2: mixing a compound formula V-1 with a tetrahydrofuran solvent in an inert gas atmosphere, adding N-bromosuccinimide for reaction, and obtaining a compound formula V-2 after the reaction is finished;
synthesis of Compound formula V-3: mixing a compound formula V-2 with a tetrahydrofuran solvent in an inert gas atmosphere, dropwise adding lithium diisopropylamide for reaction, and finally adding N, N-dimethylformamide for reaction to obtain a compound formula V-3 after the reaction is finished;
synthesis of Compound formula V-4: mixing the compound formula V-3 with boric acid or boric acid ester based on an R unit, potassium carbonate, methyl trioctyl ammonium chloride, toluene, deionized water and catalyst tetra-triphenylphosphine palladium in an inert gas atmosphere, and reacting to obtain a compound formula V-4 after the reaction is finished;
synthesis of compound of formula I: mixing a compound shown in a formula V-4, a compound shown in a formula III at the tail end and chloroform, adding pyridine in an inert gas atmosphere for reaction, and obtaining a non-fullerene acceptor compound shown in a formula I after the reaction is finished.
3. The method of synthesizing a side-chain modified non-fullerene receptor according to claim 2, wherein the method of synthesizing the compound formula V-3 is changed to: and mixing the compound formula V-3 with alkyl tin based on R unit, toluene, deionized water and catalyst tetra-triphenyl palladium phosphate in inert gas atmosphere, and reacting to obtain the compound formula V-4 after the reaction is finished.
4. A method of synthesizing a side chain modified non-fullerene acceptor according to claim 2 or 3 wherein the mass to volume ratio of compound formula V-1 to tetrahydrofuran solvent in the synthesis of compound formula V-2 is (1-2) g:15mL; the molar ratio of compound formula V-1 to N-bromosuccinimide is 1: (8-10), the reaction time is 4-10h.
5. The method for synthesizing a side chain modified non-fullerene acceptor according to claim 3, wherein the mass to volume ratio of the compound formula V-2 to the tetrahydrofuran solvent in the synthesis of the compound formula V-3 is (1-2) g:15mL; the reaction temperature is-78-50 ℃ in the process of dropwise adding lithium diisopropylamide, the reaction is carried out for 1-2h at the temperature, then the reaction is carried out for 3-4h at room temperature, and the molar ratio of the compound formula V-2 to the lithium diisopropylamide is 1: (4-8); the molar ratio of compound formula V-2 to N, N-dimethylformamide is 1: (5-10), adding N, N-dimethylformamide, and reacting for 8-12h at room temperature.
6. The method of synthesizing a side chain modified non-fullerene acceptor according to claim 4 wherein the molar ratio of compound formula V-4, the compound represented by formula III at the end, and pyridine in the synthesis of compound formula I is 1: (2-10): (10-40) the molar volume ratio of the compound of formula V-4 to chloroform was (0.1-0.2) mmol:30mL; the reaction condition is that the temperature is 20-65 ℃ and the reaction time is 3-12h.
7. The method of synthesizing a side chain modified non-fullerene acceptor according to claim 2 wherein the molar ratio of the compound formula V-3, the R unit based boric acid or borate, potassium carbonate and methyltrioctylammonium chloride in the synthesis of the compound formula V-4 is 1: (2-10): (1-10): (0.1-4); the mass volume ratio of the compound formula V-3 to toluene and deionized water is (1-2) g: (80-120) mL: (40-60) mL; the molar quantity of the catalyst tetra-triphenyl palladium phosphate is 0.01% -10% of the molar quantity of the compound formula V-3; the reaction condition is that the reaction is carried out for 5 to 24 hours at the temperature of between 90 and 110 ℃ in a dark place.
8. A method of synthesizing a side chain modified non-fullerene acceptor according to claim 3 wherein the molar ratio of compound formula V-3 to the alkyl tin based on R units in the synthesis of compound formula V-4 is 1: (2-10); the mass volume ratio of the compound of the formula V-3 to toluene is (1-2) g:120mL, the molar quantity of the catalyst tetra-triphenylphosphine palladium is 0.01% -10% of the molar quantity of the compound formula V-3; the reaction condition is that the reaction is carried out for 5 to 24 hours at the temperature of between 90 and 110 ℃ in a dark place.
9. A side chain modified non-fullerene receptor synthesized by the method of any one of claims 1-3 or 5-8, wherein the structure of the non-fullerene receptor is as shown in formula
As shown.
10. Use of the side-chain modified non-fullerene receptor of claim 9 in a solar cell device.
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| CN109134513A (en) * | 2018-09-10 | 2019-01-04 | 中南大学 | A kind of non-fullerene acceptor material of condensed ring diazosulfide base and its preparation method and application |
| CN114478583A (en) * | 2022-02-22 | 2022-05-13 | 中国科学院化学研究所 | Application of n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chain in high-efficiency organic solar cell |
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| CN109134513A (en) * | 2018-09-10 | 2019-01-04 | 中南大学 | A kind of non-fullerene acceptor material of condensed ring diazosulfide base and its preparation method and application |
| CN114478583A (en) * | 2022-02-22 | 2022-05-13 | 中国科学院化学研究所 | Application of n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chain in high-efficiency organic solar cell |
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