CN105017264B - A kind of organic molecule photoelectric functional material and preparation method thereof - Google Patents
A kind of organic molecule photoelectric functional material and preparation method thereof Download PDFInfo
- Publication number
- CN105017264B CN105017264B CN201510371994.2A CN201510371994A CN105017264B CN 105017264 B CN105017264 B CN 105017264B CN 201510371994 A CN201510371994 A CN 201510371994A CN 105017264 B CN105017264 B CN 105017264B
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- China
- Prior art keywords
- double
- bromide
- porphyrins
- functional material
- organic molecule
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 150000004032 porphyrins Chemical group 0.000 claims abstract description 15
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims abstract description 3
- 238000006069 Suzuki reaction 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 31
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 11
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- CXDVQWISYFKBFZ-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(C#C)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical class [N]1C2=CC=C1C=C(N1)C=C(C#C)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 CXDVQWISYFKBFZ-UHFFFAOYSA-N 0.000 claims description 9
- AUTYMVKGXZNMRC-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.B(O)(O)O Chemical class C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.B(O)(O)O AUTYMVKGXZNMRC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- -1 recrystallize again Substances 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005227 gel permeation chromatography Methods 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000975 dye Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000003205 fragrance Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 238000013086 organic photovoltaic Methods 0.000 description 6
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- CRBREIOFEDVXGE-UHFFFAOYSA-N dodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1 CRBREIOFEDVXGE-UHFFFAOYSA-N 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 0 CCCCCC(CC)CN(C(c1ccc[o]1)=C1*2=C(C(O)=CC=C(C)*)N(CC(CCCCC)C3CC3)C1=[O+])C2=O Chemical compound CCCCCC(CC)CN(C(c1ccc[o]1)=C1*2=C(C(O)=CC=C(C)*)N(CC(CCCCC)C3CC3)C1=[O+])C2=O 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229930002875 chlorophyll Natural products 0.000 description 2
- 235000019804 chlorophyll Nutrition 0.000 description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910001453 nickel ion Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical class BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 description 1
- GFBVUFQNHLUCPX-UHFFFAOYSA-N 5-bromothiophene-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)S1 GFBVUFQNHLUCPX-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GYSSMGHLXVTUPO-UHFFFAOYSA-N N=1C(C(C=2C1C=CN2)=O)=O.C2(=CC=CC=C2)O.[Se] Chemical class N=1C(C(C=2C1C=CN2)=O)=O.C2(=CC=CC=C2)O.[Se] GYSSMGHLXVTUPO-UHFFFAOYSA-N 0.000 description 1
- SMCMWBCARVAUEA-UHFFFAOYSA-N N=1C(C(C=2C1C=CN2)=O)=O.S2C=NC=C2 Chemical compound N=1C(C(C=2C1C=CN2)=O)=O.S2C=NC=C2 SMCMWBCARVAUEA-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- RBFRSIRIVOFKDR-UHFFFAOYSA-N [C].[N].[O] Chemical compound [C].[N].[O] RBFRSIRIVOFKDR-UHFFFAOYSA-N 0.000 description 1
- NHCSMTQRYWPDDW-UHFFFAOYSA-N [C].[N].[S] Chemical compound [C].[N].[S] NHCSMTQRYWPDDW-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- PBTPREHATAFBEN-UHFFFAOYSA-N dipyrromethane Chemical compound C=1C=CNC=1CC1=CC=CN1 PBTPREHATAFBEN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- MYFOYOXMFDOSPN-UHFFFAOYSA-N ethyl 2-bromo-4-phenyl-1,3-thiazole-5-carboxylate Chemical compound S1C(Br)=NC(C=2C=CC=CC=2)=C1C(=O)OCC MYFOYOXMFDOSPN-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- VWTSXINFCUODBJ-UHFFFAOYSA-L zinc methanol diacetate Chemical compound [Zn++].CO.CC([O-])=O.CC([O-])=O VWTSXINFCUODBJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- 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
-
- H—ELECTRICITY
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Abstract
The invention discloses a kind of organic molecule photoelectric functional material, by selecting a variety of dyestuffs to obtain the organic molecule photoelectric functional material containing porphyrin unit and different dyes unit using acetylene bond or fragrance (miscellaneous) ring as bridge.The invention also discloses the method for being prepared using Suzuki coupling reactions or preparing above-mentioned organic molecule photoelectric functional material using Sonogashira coupling reactions.The organic molecule photoelectric functional material of the present invention has good processing characteristics, appropriate band structure, energy conversion efficiency height.
Description
Technical field
The present invention relates to organic photoelectrical material field, more particularly to a kind of organic molecule photoelectric functional material and its preparation
Method.
Background technology
Solar energy has the characteristics that cleaning, resource are extensive, it is considered to be the preferred resources of fossil resources is substituted, to solar energy
Utilization increasingly paid close attention to by the mankind.But the energy density of solar energy is low, is not easy directly to utilize, it is necessary to change into it
Its energy can just better profit from.In effective utilization of solar energy, it is near to be converted solar energy into electrical energy using photocell
One of with fastest developing speed, most active research field over year.
The organic solar batteries of solution processable have (such as can spin coating, inkjet printing) inexpensive, easy to process, suitable
In preparing the potential advantage such as large area flexible device, it can not only simplify the preparation process of device, can also greatly reduce
Cost is prepared, so as to of great interest.Donor material in battery active material can be divided into according to the size of molecular weight
Conjugated polymer and organic molecule, the easy film forming of polymer, but product is not allowed to be easily purified, and molecular weight distribution is wide, and per batch
The product being synthesized is had differences due to molecular weight and its distribution and is caused the efficiency of solar cell to be usually present larger difference
It is different, and these problems are not present in organic molecule, therefore its uniqueness in organic solar batteries be present in organic molecule
Advantage.Photosynthesis be green plants by Chlorophyll absorption light after, carry out photochemical reaction and store energy, so as to be the mankind
Food and the energy etc. are provided.The structure of porphyrin is similar with chlorophyll, has big pi-conjugated system and high molar absorption coefficient,
Electronics rapidly can be transferred to acceptor from donor, and it is physico to change its easily by the modification of peripheral groups and cavity metal
Property is learned, Porphyrin and its derivative is to be applied to one of material of organic solar batteries as light active material earliest.So
And the photoelectric transformation efficiency based on Porphyrin and its derivative organic solar batteries is but very low.
The content of the invention
In order to overcome the disadvantages mentioned above of prior art and deficiency, it is an object of the invention to provide a kind of organic molecule light
Sulfate ferroelectric functional material, there is good processing characteristics, appropriate band structure, energy conversion efficiency height.
The purpose of the present invention is achieved through the following technical solutions：
A kind of organic molecule photoelectric functional material, its chemical constitution are as follows:
Wherein：A is the aromatic rings conjugated bridge being substituted or unsubstituted；B is end group dye groups, and M is metal ion or hydrogen
Element；Ar is the aromatic group being substituted or unsubstituted；M is 0 or 1.
The Ar is the aromatic rings being made up of ethene support group, acetylene support group, hydrocarbon atom；The virtue being made up of carbon nitrogen hydrogen atom
Fragrant heterocycle, the aromatic heterocycle being made up of carbon nitrogen oxygen hydrogen atom；The aromatic heterocycle being made up of carbon sulphur hydrogen atom；By carbon silicon hydrogen atom structure
Into aromatic heterocycle；The aromatic heterocycle being made up of carbon nitrogen sulphur hydrogen atom；One in the aromatic heterocycle be made up of carbon silicon sulphur hydrogen atom
More than kind.
The A is aromatic heterocycle, the carbon nitrogen oxygen hydrogen atom structure that aromatic rings, the carbon nitrogen hydrogen atom being made up of hydrocarbon atom are formed
Into aromatic heterocycle, carbon sulphur hydrogen atom form aromatic heterocycle, carbon silicon hydrogen atom form aromatic heterocycle, carbon nitrogen sulphur hydrogen atom structure
Into the conjugation emigrant that forms of one or more of the aromatic heterocycle aromatic heterocycle that forms of aromatic heterocycle and carbon silicon sulphur hydrogen atom, construction
The elementary cell number of conjugation emigrant is 0,1,2,3 or 4.
In substituted aromatic group substituted radical be alkyl, fluoro-alkyl, alkoxy, ester group, in carbonyl it is a kind of with
On.
Substituted radical is one in alkyl, fluoro-alkyl, alkoxy, ester group, carbonyl in substituted aromatic rings conjugated bridge
More than kind.
The M is zinc ion, copper ion, magnesium ion or nickel ion.
The B is one kind in following structure：
The preparation method of described organic molecule photoelectric functional material, comprises the following steps：
Prepared using Suzuki coupling reactions：By the double borate porphyrins of 5,10- and bromide under argon gas atmosphere protection
It is dissolved in the reaction bulb for filling 1,2- dimethoxy-ethanes, adds four (triphenyl phosphorus) and close palladium, in 95~105 DEG C of heating conditions
At two days two nights of lower stirring reaction, room temperature is cooled to, is extracted with chloroform, is spin-dried for solvent, it is pure by silica gel column chromatography and GPC HPLC
Change, be finally spin-dried for solvent, recrystallize again, product is dried under vacuum, and obtains organic molecule photoelectric functional material；
The mol ratio of the double borate porphyrins of the 5,10- and bromide is 1：(2.5~3.5)；The 1,2- dimethoxys
The mole of ethane is 90~110 times of the double borate porphyrins of 5,10- and bromide integral molar quantity；Four (triphenyl phosphorus) close
The mole of palladium is the double borate porphyrins of 5,10- and the 9%~11% of bromide integral molar quantity.
The preparation method of described organic molecule photoelectric functional material, comprises the following steps：
Prepared using Sonogashira coupling reactions：It is under an argon atmosphere that the double ethynyl porphyrins of 5,10-, bromide is molten
Solution adds four (triphenyl phosphorus) and closes palladium, cuprous iodide, heat and stir at 75~85 DEG C in the reaction bulb of toluene and triethylamine is filled
Three days three nights of reaction are mixed, room temperature is cooled to, is extracted with chloroform, be spin-dried for solvent, are purified by silica gel column chromatography and GPC, HPLC, most
After be spin-dried for solvent, recrystallize again, product is dried under vacuum；
The mol ratio of the double ethynyl porphyrins of the 5,10- and bromide is 1：(2.5~3.5)；The mole of the toluene
90~110 times for the double ethynyl porphyrins of 5,10- with bromide integral molar quantity；The mole of the triethylamine is the double second of 5,10-
40~60 times of alkynyl porphyrin and bromide integral molar quantity；The mole that four (triphenyl phosphorus) close palladium is the double acetenyls of 10-
Porphyrin and the 9%~11% of bromide integral molar quantity；The mole of the cuprous iodide is the double ethynyl porphyrins of 10- and bromination
The 9%~11% of thing integral molar quantity.
The organic molecule photoelectric functional material of the present invention has the characteristics that：
(1) by the connection of conjugated bridge, reach whole intramolecular and be effectively conjugated, so as to promote the effective of intramolecular
Electric charge transfer (ICT), molecule has very wide absorption；
(2) by introducing different dyestuff end groups, can make it that ICT effects are stronger, then absorb can more red shift, in addition certain
A little dyestuffs itself have absorption well, then absorbing can be stronger, so as to applied in organic photovoltaic, device be caused to capture more
More photon, so as to increase short circuit current；
(3) introduce after inhaling electrical dyestuff, can effective drawing molecule HOMO energy levels, widening the basis of absorption
On, moreover it is possible to so that construction Porphyrin Molecule as small molecule donor material, in the devices with larger open-circuit voltage.So certain
A little molecules can obtain less energy loss value (numerical difference of optical band gap and open-circuit voltage)；
(4) by introducing different fragrance (miscellaneous) rings to two meso positions of porphyrin, Porphyrin Molecule can effectively be adjusted
Frontier orbit, and the dissolubility of molecule can be changed by modification；
(5) by modifying the side chain of fragrant (miscellaneous) ring, end group dyestuff, conjugated bridge, can be effectively improved deliquescent same
When, it is possibility to have the frontier orbit of the regulation molecule of effect；
(6) different metal ions are inserted, because different metal ions has different outer layer distribution of charges, and are inserted
Slight change can also occur for the configuration of Porphyrin Molecule after different metal ions, and this can all cause final Porphyrin Molecule to have difference
Frontier orbit, never can influence the absorption of Porphyrin Molecule.Eventually influence short circuit current, the open-circuit voltage of resulting devices.Institute
So that suitable metal can be sought, to obtain with efficient Porphyrin Molecule；
(7) (by) body suitably can be given come selected by the frontier orbit of final molecule so that the molecule can conduct
Organic thin film solar cell by (giving) body material.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) organic photovoltaic devices prepared using the organic molecule photoelectric functional material of the present invention can have width simultaneously
Absorption and high open circuit voltage, you can with less energy loss numerical value (band gap and the numerical difference of open-circuit voltage)；
(2) organic molecule photoelectric functional material of the invention has a good processing characteristics, and film forming is superior；
(3) deep absorb of organic molecule photoelectric functional material of the invention causes it to have as the latent of infrared detector
Power.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1C16TPTRD synthesis
Step 1：The synthesis of double (5- (the 2- hexyls decyl) thiophene) porphyrins of 15,15-
In two mouthfuls of round-bottomed flasks of 1000mL, addition 5- (2- hexyls decyl) thiophene -2-formaldehyde (1.632g,
4.86mmol), dipyrromethane (700mg, 4.86mmol) and 500mL dichloromethane, ventilated 30 minutes with nitrogen, Ran Houjia
Enter 0.25mL trifluoroacetic acid, reaction 12 hours is stirred at room temperature, adds 1.8g 2, chloro- 5, the 6- dicyanos-Isosorbide-5-Nitraes-of 3- bis-
Benzoquinones (DDQ), continues stirring reaction 12 hours, and reaction is quenched in rear plus 5mL triethylamine.After reaction terminates, with silica gel/(dichloro
Methane is eluant, eluent) column chromatography, crude product is obtained after being spin-dried for, then recrystallized with chloroform/methanol, obtain dark red solid.1H NMR
(300MHz,CDCl3)δ10.27(s,2H),9.35(q,8H),7.74(d,2H),7.20(d,2H),3.09(d,4H),1.93
(m,2H),1.61-1.25(m,48H),0.95-0.82(m,12H),-2.96(s,2H)。
Step 2：The synthesis of double (5- (the 2- hexyls decyl) thiophene) zinc protoporphyrins of the double bromo- 10,20- of 5,15-
Double (5- (the 2- hexyls decyl) thiophene) porphyrins (688mg, 0.7mmol) of 5,15- are dissolved in 700mL chloroform,
35mL pyridine is added, lucifuge, then adds bromo-succinimide (NBS) (274mg, 1.54mmol), reacts 30 points at 0 DEG C
Clock, after continue at room temperature reaction 4 hours, reaction finally is quenched with acetone.Reaction finishes, and adds water, is extracted with chloroform, anhydrous
Sodium sulphate is dried, and is dissolved in after being spin-dried for solvent in 50mL chloroformic solution, it is rear add 12mL zinc acetate methanol solution (243mg,
1.2mmol zinc acetate is dissolved in 12mL methanol solvate), lucifuge flows back 2 hours.Reaction finishes, washing, and with anhydrous sulphur
Sour sodium is dried, and is spin-dried for solvent, is obtained the solid of shiny red after purification using silica gel column chromatography.1H NMR(600MHz,CDCl3)δ
9.00(d,4H),8.51(d,4H),7.79(d,2H),7.23(d,2H),3.03(d,4H),1.85(m,2H),1.63-1.19
(m,48H),1.01-0.79(m,12H)。
The synthesis of double (5- (the 2- hexyls decyl) thiophene) zinc protoporphyrins of double (the trimethylsilyl acetylene) -10,20- of step 3,5,15-
In 100mL two mouthfuls of round-bottomed flasks, double (5- (the 2- hexyls decyl) thiophene) zinc of double bromo- 10, the 20- of 5,15- are added
Porphyrin (570mg, 0.5mmol), 25mL tetrahydrofurans and 12.5mL triethylamines, lead to nitrogen 30 minutes, then add double (triphenyls
Phosphine) palladium chloride (17.5mg, 0.025mmol), cuprous iodide (CuI) (5mg, 0.025mmol) and trimethylsilyl acetylene
Reaction three days is stirred at room temperature in (200mg, 2mmol), lucifuge, reaction.Reaction finishes, and washing, is extracted with dichloromethane, with nothing
Aqueous sodium persulfate is dried, then with silica gel/(dichloromethane/petroleum ether=1:1 is eluant, eluent) column chromatography, it is spin-dried for obtaining consolidating for green
Body.1H NMR(600MHz,CDCl3)δ9.61(d,4H),9.12(d,4H),7.67(d,2H),7.15(d,2H),3.05(d,
4H),1.87(m,2H),1.61-1.18(m,48H),0.93-0.87(m,12H),0.61(s,18H)。
The synthesis of double (5- (the 2- hexyls decyl) thiophene) zinc protoporphyrins of double (the acetylene) -10,20- of step 4,5,15-
By double (5- (the 2- hexyls decyl) thiophene) zinc protoporphyrins of double (the trimethylsilyl acetylene) -10,20- of 5,15- (411mg,
0.35mmol) it is dissolved in 20mL tetrahydrofuran solution, tetrabutyl ammonium fluoride (0.72mL, 1M in THF) is added, in room temperature
Lower stirring reaction 5 minutes, water quenching is added to go out reaction.Extracted, anhydrous sodium sulfate drying, be spin-dried for chloroform, with silica gel/(dichloromethane/
Petroleum ether=1:1 is eluant, eluent) column chromatography, it is spin-dried for obtaining the solid of green.1H NMR(300MHz,CDCl3)δ9.65(d,4H),
9.18(d,4H),7.68(d,2H),7.16(d,2H),4.11(s,2H),3.08(d,4H),1.92(m,2H),1.57-1.22
(m,48H),0.94-0.88(m,12H)。
The synthesis of step 5,5- bromothiophenes -2- (3- ethyls) rhodanine
By 5- bromothiophene -2- formaldehyde (546.7mg, 2.862mmol), 3- ethyls rhodanine (506.9mg, 3.1485mmol)
It is dissolved in 40mL glacial acetic acid, adds ammonium acetate (485mg, 6.3mmol), return stirring is overnight, adds water quenching to go out reaction.With two
Chloromethanes extracts, and anhydrous sodium sulfate drying, is spin-dried for, with silica gel/(dichloromethane/petroleum ether=1:2 be eluant, eluent) column chromatography, rotation
It is dry to obtain bright yellow solid.1H NMR(300MHz,CDCl3)δ7.75(s,1H),7.16(d,2H),4.18(q,2H),1.29
(t,3H)。
The synthesis of step 6,4- bromobenzenes -2- (3- ethyls) rhodanine
4- bromobenzene -2- formaldehyde (526.5mg, 2.862mmol), 3- ethyls rhodanine (506.9mg, 3.1485mmol) is molten
Solution adds ammonium acetate (485mg, 6.3mmol) in 40mL glacial acetic acid, and return stirring is overnight, adds water quenching to go out reaction.Use dichloro
Methane extracts, and anhydrous sodium sulfate drying, is spin-dried for, with silica gel/(dichloromethane/petroleum ether=1:2 be eluant, eluent) column chromatography, it is spin-dried for
Obtain yellow solid.Mass(MALDI-TOF):Obs.327.7；Calcd.for C12H10BrNO2S,328.2。
Step 7：C16TPTRD synthesis
Under the protection of argon gas, double (acetylene) -10, the 20- double (3,5- of 5,15- are added into 50mL two mouthfuls of round-bottomed flasks
Double (dodecyloxy) benzene) zinc protoporphyrin (262mg, 0.2mmol), 5- bromothiophenes -2- (3- ethyls) rhodanine (199.74mg,
0.6mmol), dry toluene (10mL), triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium
(24mg, 0,02mmol), lucifuge, stirring reaction three days at 80 DEG C.Reaction finishes, and is cooled to room temperature, washing, is extracted with toluene
Take, anhydrous sodium sulfate drying, be spin-dried for, cross post, obtain the solid of atropurpureus.Mass(MALDI-TOF):Obs.1818.2；
Calcd.for C104H103N6O6S6Zn,1817.9。
The C16TPPRD of embodiment 2 synthesis
Under the protection of argon gas, double (acetylene) -10, the 20- double (3,5- of 5,15- are added into 50mL two mouthfuls of round-bottomed flasks
Double (dodecyloxy) benzene) zinc protoporphyrin (262mg, 0.2mmol), 4- bromobenzenes -2- (3- ethyls) rhodanine (196.2mg,
0.6mmol), dry toluene (10mL), triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium
(24mg, 0,02mmol), lucifuge, stirring reaction three days at 80 DEG C.Reaction finishes, and is cooled to room temperature, washing, is extracted with toluene
Take, anhydrous sodium sulfate drying, be spin-dried for, cross post, obtain the solid of atropurpureus.Mass(MALDI-TOF):Obs.1806.3；
Calcd.for C108H134N6O6S4Zn,1805.9。
Embodiment 3PorEFDPP synthesis
Under the protection of argon gas, double (acetylene) -10, the 20- double (3,5- of 5,15- are added into 50mL two mouthfuls of round-bottomed flasks
Double (dodecyloxy) benzene) zinc protoporphyrin (262mg, 0.2mmol), single bromo Coumarin pyrrolo-pyrrole-dione (342mg,
0.6mmol), dry toluene (10mL), triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium
(24mg, 0,02mmol), lucifuge, stirring reaction three days at 80 DEG C.Reaction finishes, and is cooled to room temperature, washing, is extracted with toluene
Take, anhydrous sodium sulfate drying, be spin-dried for, cross post, obtain the solid of atropurpureus.Mass(MALDI-TOF):Obs.2013.6；
Calcd.for C124H156N8O8S2Zn,2013.2。
The synthesis of embodiment 4, PorESeDPP
Under the protection of argon gas, double (acetylene) -10, the 20- double (3,5- of 5,15- are added into 50mL two mouthfuls of round-bottomed flasks
Double (dodecyloxy) benzene) zinc protoporphyrin (262mg, 0.2mmol), the double selenium phenol pyrrolo-pyrrole-diones of single bromo (418mg,
0.6mmol), dry toluene (30mL), triethylamine (15mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium
(24mg, 0,02mmol), lucifuge, stirring reaction three days at 80 DEG C.Reaction finishes, and is cooled to room temperature, washing, is extracted with toluene
Take, anhydrous sodium sulfate drying, be spin-dried for, cross post, obtain the solid of atropurpureus.Mass(MALDI-TOF):Obs.2268.3；
Calcd.for C124H156N8O4S2Se4Zn,2268.8。
The synthesis of embodiment 5, PorETzDPP
Under the protection of argon gas, double (acetylene) -10, the 20- double (3,5- of 5,15- are added into 50mL two mouthfuls of round-bottomed flasks
Double (dodecyloxy) benzene) zinc protoporphyrin (262mg, 0.2mmol), single bromo double thiazole pyrrolo-pyrrole-dione (362mg,
0.6mmol), dry toluene (30mL), triethylamine (15mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium
(24mg, 0,02mmol), lucifuge, stirring reaction three days at 80 DEG C.Reaction finishes, and is cooled to room temperature, washing, is extracted with toluene
Take, anhydrous sodium sulfate drying, be spin-dried for, cross post, obtain the solid of atropurpureus.Mass(MALDI-TOF):Obs.2081.2；
Calcd.for C120H152N12O4S6Zn,2080.9。
Embodiment 6：
Preparation and performance using metallic aluminium as the organic photovoltaic battery device of negative electrode
Structure using metallic aluminium as the organic photovoltaic battery device of negative electrode is：ITO/PEDOT:PSS(40nm)/active
layer/PFN(10nm)/Al.Device fabrication processes are：Using the ito glass of pre-wash as anode, spin coating 40 on ito glass
The water-soluble polymer PEDOT of nanometer:It is prepared by PSS, the embodiment 1 for each continuing 80 nanometers of spin coating after drying on different slice, thin pieces
C16TPTRD and PC61C16TPPRD and PC prepared by BM, embodiment 261PorEFDPP and PC prepared by BM, embodiment 361BM、
PorESeDPP and PC prepared by embodiment 461PorETzDPP and PC prepared by BM, embodiment 561BM is done as photovoltaic active layers
Followed by spin coating 10nm PFN, the Al metallic cathodes of last 90 nanometers of vacuum evaporation.Apply just between ITO and Al metal electrodes
Bias, its battery behavior is measured under the irradiation of 100 milliwatts AM1.5 simulated solar irradiations every square centimeter, the battery device
Open-circuit voltage is respectively 0.93,0.90,0.80,0.73 and 0.69 volt, and short circuit current is respectively 11.4,10.6,7.6,6.5 and
5.7 milliamperes every square centimeter, fill factor, curve factor difference 44.2%, 41%, 37%, 35%, 32%, and energy conversion efficiency is respectively
4.69%th, 3.9%, 2.2%, 1.6%, 1.26%.
Foregoing PC61BM is English " [6,6]-phenyl C61- butyric acid methyl ester " letter
Claim.
Embodiment 7：
Preparation and performance using ITO as the organic photovoltaic battery device of negative electrode
Structure using ITO as the organic photovoltaic battery device of negative electrode is：ITO/ZnO/PEIE/active layer/MoO3/
Al.Device fabrication processes are：Using the ito glass of pre-wash as negative electrode, on ito glass spin coating 40nm ZnO and
10nmPEIE, continue the embodiment 7 and PC of 120 nanometers of spin coating after drying61BM, 8 and PC61BM, 9 and PC61BM, 10 and PC61BM、
11 and PC61BM is as photovoltaic active layers, the MoO that 10 nanometers of vacuum evaporation afterwards3, then the Al metals sun of 90 nanometers of vacuum evaporation
Pole.Apply back bias voltage between ITO and Al metal electrodes, under the irradiation of 100 milliwatts AM1.5 simulated solar irradiations every square centimeter
Its battery behavior is measured, the open-circuit voltage of the battery device is respectively 0.92,0.91,0.81,0.72 and 0.68 volt, short circuit electricity
Stream is respectively 11.8,10.9,8.1,7.6 and 6.5 milliamperes every square centimeter, and fill factor, curve factor is respectively 45%, 40%, 38%,
36%th, 33%, energy conversion efficiency is respectively 4.9%, 4.0%, 2.5%, 2.0%, 1.4%.
Except the organic molecule photoelectric functional material in embodiment, organic molecule photoelectric functional material of the invention also wraps
Include the organic molecule photoelectric functional material with following chemical structure characteristic:
Wherein：A is the aromatic rings conjugated bridge being substituted or unsubstituted；B is end group dye groups, and M is metal ion or hydrogen
Element；Ar is the aromatic group being substituted or unsubstituted；M is 0 or 1；
The Ar can be the aromatic rings being made up of ethene support group, acetylene support group, hydrocarbon atom；It is made up of carbon nitrogen hydrogen atom
Aromatic heterocycle, the aromatic heterocycle that is made up of carbon nitrogen oxygen hydrogen atom；The aromatic heterocycle being made up of carbon sulphur hydrogen atom；It is former by carbon silicon hydrogen
The aromatic heterocycle that son is formed；The aromatic heterocycle being made up of carbon nitrogen sulphur hydrogen atom；In the aromatic heterocycle be made up of carbon silicon sulphur hydrogen atom
More than one.
The A can be that aromatic heterocycle, carbon nitrogen oxygen hydrogen that aromatic rings, the carbon nitrogen hydrogen atom being made up of hydrocarbon atom are formed are former
Aromatic heterocycle, the carbon nitrogen sulphur hydrogen that aromatic heterocycle, the carbon silicon hydrogen atom that aromatic heterocycle, the carbon sulphur hydrogen atom of son composition are formed are formed are former
The conjugation emigrant that one or more of the aromatic heterocycle that the aromatic heterocycle and carbon silicon sulphur hydrogen atom that son is formed are formed aromatic heterocycle is formed,
The elementary cell number of construction conjugation emigrant is 0,1,2,3 or 4；
In substituted aromatic group substituted radical be alkyl, fluoro-alkyl, alkoxy, ester group, in carbonyl it is a kind of with
On.
Substituted radical is one in alkyl, fluoro-alkyl, alkoxy, ester group, carbonyl in substituted aromatic rings conjugated bridge
More than kind.
The M is zinc ion, copper ion, magnesium ion or nickel ion.
The B is one kind in following structure：
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. a kind of organic molecule photoelectric functional material, it is characterised in that its chemical constitution is selected from following (1), (2), (3), (4)
Or (5):
(1)
(2)
(3)
(4)
(5)
2. the preparation method of the organic molecule photoelectric functional material described in claim 1, it is characterised in that including following step
Suddenly：
Prepared using Suzuki coupling reactions：The double borate porphyrins of 5,10- and bromide are dissolved under argon gas atmosphere protection
In the reaction bulb for filling 1,2- dimethoxy-ethanes, add four (triphenyl phosphorus) and close palladium, stirred under 95~105 DEG C of heating conditions
Two days two nights of reaction are mixed, room temperature is cooled to, is extracted with chloroform, be spin-dried for solvent, are purified by silica gel column chromatography and GPC HPLC, most
After be spin-dried for solvent, recrystallize again, product is dried under vacuum, and obtains organic molecule photoelectric functional material；
The mol ratio of the double borate porphyrins of the 5,10- and bromide is 1：(2.5~3.5)；The 1,2- dimethoxy-ethanes
90~110 times for the double borate porphyrins of 5,10- with bromide integral molar quantity of mole；Four (triphenyl phosphorus) close palladium
Mole is the double borate porphyrins of 5,10- and the 9%~11% of bromide integral molar quantity.
3. the preparation method of the organic molecule photoelectric functional material described in claim 1, it is characterised in that including following step
Suddenly：
Prepared using Sonogashira coupling reactions：The double ethynyl porphyrins of 5,10-, bromide are dissolved under an argon atmosphere
In the reaction bulb for filling toluene and triethylamine, add four (triphenyl phosphorus) and close palladium, cuprous iodide, heating stirring is anti-at 75~85 DEG C
At the nights of Ying Santian tri-, room temperature is cooled to, is extracted with chloroform, be spin-dried for solvent, purified by silica gel column chromatography and GPC, HPLC, finally revolved
Dry solvent, is recrystallized again, and product is dried under vacuum；
The mol ratio of the double ethynyl porphyrins of the 5,10- and bromide is 1：(2.5~3.5)；The mole of the toluene is 5,
90~110 times of the double ethynyl porphyrins of 10- and bromide integral molar quantity；The mole of the triethylamine is the double acetenyls of 5,10-
40~60 times of porphyrin and bromide integral molar quantity；The mole that four (triphenyl phosphorus) close palladium is the double ethynyl porphyrins of 10-
With the 9%~11% of bromide integral molar quantity；The mole of the cuprous iodide is that the double ethynyl porphyrins of 10- and bromide are total
The 9%~11% of mole.
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| US10236457B2 (en) * | 2016-06-29 | 2019-03-19 | Hong Kong Baptist University | Synthesis of porphyrin materials for highly efficient organic photovoltaics |
| CN106243116B (en) * | 2016-07-28 | 2018-09-14 | 华南理工大学 | A kind of trans-A2B2Type derivatives of porphyrin and the preparation method and application thereof |
| CN107312021A (en) * | 2017-06-22 | 2017-11-03 | 华南理工大学 | A kind of many Porphyrin organic small molecular photovoltaic materials and preparation method thereof |
| CN107344948A (en) * | 2017-06-22 | 2017-11-14 | 华南理工大学 | Porphyrin organic molecule photovoltaic material and preparation method and application |
| CN107383080A (en) * | 2017-06-22 | 2017-11-24 | 华南理工大学 | A kind of asymmetrical porphyrin organic molecule photovoltaic material and preparation method and application |
| CN108440546A (en) * | 2018-05-10 | 2018-08-24 | 重庆新康意安得达尔新材料有限公司 | A kind of organic photoelectrical material and preparation method thereof |
| CN113929879B (en) * | 2021-10-18 | 2023-06-30 | 湘潭大学 | Double-alkyne bridged one-dimensional linear or two-dimensional reticular organic energy storage material, and preparation method and application thereof |
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| WO2015005869A1 (en) * | 2013-07-08 | 2015-01-15 | Agency For Science, Technology And Research | Perylene functionalized porphyrin dyes for dye-sensitized solar cells |
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| WO2015005869A1 (en) * | 2013-07-08 | 2015-01-15 | Agency For Science, Technology And Research | Perylene functionalized porphyrin dyes for dye-sensitized solar cells |
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