CN107383080A - A kind of asymmetrical porphyrin organic molecule photovoltaic material and preparation method and application - Google Patents
A kind of asymmetrical porphyrin organic molecule photovoltaic material and preparation method and application Download PDFInfo
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- CN107383080A CN107383080A CN201710481644.0A CN201710481644A CN107383080A CN 107383080 A CN107383080 A CN 107383080A CN 201710481644 A CN201710481644 A CN 201710481644A CN 107383080 A CN107383080 A CN 107383080A
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- photovoltaic material
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- porphyrin
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 17
- -1 carbon nitrogen oxygen hydrogen Chemical class 0.000 claims description 13
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 10
- IICFMBOTAXCUNZ-UHFFFAOYSA-N C=1C=CSC=1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound C=1C=CSC=1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 IICFMBOTAXCUNZ-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- CJELDIUSJNERDX-UHFFFAOYSA-N [C].[S].[Si] Chemical compound [C].[S].[Si] CJELDIUSJNERDX-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 125000006575 electron-withdrawing group Chemical group 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 238000013086 organic photovoltaic Methods 0.000 abstract 1
- 238000010129 solution processing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 238000001291 vacuum drying Methods 0.000 description 4
- 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 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 150000003053 piperidines Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 0 BC#CC(C(CC1)**=C1CC([Al])=C1C=C2)C(CC3)C/C=C4/C([Al])=C(C=C5)N=C5C(C#C)=C=C2N1N(C)C3C4 Chemical compound BC#CC(C(CC1)**=C1CC([Al])=C1C=C2)C(CC3)C/C=C4/C([Al])=C(C=C5)N=C5C(C#C)=C=C2N1N(C)C3C4 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UVNPEUJXKZFWSJ-LMTQTHQJSA-N (R)-N-[(4S)-8-[6-amino-5-[(3,3-difluoro-2-oxo-1H-pyrrolo[2,3-b]pyridin-4-yl)sulfanyl]pyrazin-2-yl]-2-oxa-8-azaspiro[4.5]decan-4-yl]-2-methylpropane-2-sulfinamide Chemical compound CC(C)(C)[S@@](=O)N[C@@H]1COCC11CCN(CC1)c1cnc(Sc2ccnc3NC(=O)C(F)(F)c23)c(N)n1 UVNPEUJXKZFWSJ-LMTQTHQJSA-N 0.000 description 1
- IGQXORINWHZSBK-UHFFFAOYSA-N 2,3,5,5-tetramethylcyclohex-2-en-1-one Chemical compound CC1=C(C)C(=O)CC(C)(C)C1 IGQXORINWHZSBK-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- 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 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 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
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to organic molecule photovoltaic material field, discloses a kind of asymmetrical porphyrin organic molecule photovoltaic material and preparation method and application.The structure of the asymmetrical porphyrin organic molecule photovoltaic material such as formula I, wherein：B and C represents end group dye groups respectively, and B and C is different；M is metal ion or hydrogen；Ar is hydrogen, alkyl, alkoxy, substituted or unsubstituted aromatic group.The asymmetric Porphyrin organic small molecular photovoltaic material of the present invention have adjusted molecular energy level, improve the open-circuit voltage of device；The filming performance of material is improved, improves device performance.Using the material of the present invention, the organic photovoltaic battery prepared using Solution processing techniques has preferable device performance, on the solar cell with very important application prospect.
Description
Technical field
The invention belongs to organic molecule photovoltaic material field, more particularly to a kind of asymmetric porphyrin organic molecule photovoltaic
Material and preparation method and application.
Background technology
In effective utilization of solar energy, converted solar energy into electrical energy using photocell be it is with fastest developing speed in the last few years,
Most active research field.The organic polymer and organic small molecule material solar cell of solution-processible have it is low into
This, (such as can spin coating, inkjet printing) easy to process, suitable for preparing the potential advantage such as large area flexible device, not only can be with
Simplify the preparation process of device, preparation cost can also be greatly reduced, so as to of great interest.Battery active material
In donor material can be divided into conjugated polymer and organic molecule according to the size of molecular weight, the easy film forming of polymer, but produce
Thing is not allowed to be easily purified, and molecular weight distribution is wide, and the product that every batch is synthesized is because molecular weight and its distribution have differences and led
The efficiency of solar cell is caused to be usually present larger difference.And these problems are not present in organic molecule, thus it is organic small
Its unique advantage in organic solar batteries be present in molecule.
The structure of porphyrin is similar with chlorophyll, has big pi-conjugated system and high molar absorption coefficient, electronics can be fast
Fast ground is transferred to acceptor from donor, changes its physicochemical properties, porphin easily by the modification of peripheral groups and cavity metal
Quinoline and its derivative are to be applied to one of material of organic solar batteries as light active material earliest.However, based on non-
The rare report of solar cell of symmetrical small molecule donor material, and efficiency photoelectric transformation efficiency is relatively 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 asymmetric more porphyrins
Organic molecule photovoltaic material, the pi-conjugated system and Intramolecular electron transfer (ICT) of molecule are effectively increased, has widened material
The absorption spectrum of material, improve the carrier mobility of material；Simultaneously by changing the electron-withdrawing power of electron withdraw group, effectively
Ground have adjusted the HOMO of molecule, lumo energy.
It is a further object of the present invention to provide the preparation method of above-mentioned asymmetrical porphyrin organic molecule photovoltaic material.
It is still another object of the present invention to provide the application of above-mentioned asymmetrical porphyrin organic molecule photovoltaic material.The light
Volt material is used to prepare solar cell.
The purpose of the present invention is achieved through the following technical solutions：
A kind of asymmetrical porphyrin organic molecule photovoltaic material, its structural formula such as formula I：
Wherein：B and C represents end group dye groups respectively, and B and C is different；M is metal ion or hydrogen；Ar is hydrogen, alkyl, alkane
Epoxide, substituted or unsubstituted aromatic group.(M can be connected with two N in 4 N in structural formula, and M can also be with other 2 N
Connection)
The Ar is hydrogen, and alkyl, alkoxy is substituted or unsubstituted by the hydrocarbon aromatic rings formed, substitutes or unsubstituted
The aromatic heterocycle being made up of hydrocarbon oxygen, the substituted or unsubstituted aromatic heterocycle being made up of carbon nitrogen oxygen hydrogen, substitution or it is unsubstituted
The aromatic heterocycle being made up of carbon sulphur hydrogen atom, the substituted or unsubstituted aromatic heterocycle being made up of carbon silicon hydrogen atom, substitution or
The unsubstituted aromatic heterocycle being made up of carbon nitrogen sulphur hydrogen, the substituted or unsubstituted aromatic heterocycle being made up of carbon silicon sulphur hydrogen, substitution
Or the unsubstituted aromatic heterocycle being made up of carbon silicon sulphur hydrogen, one kind in the aromatic heterocycle that substituted or unsubstituted hydrocarbon selenium is formed
More than.
Substituted radical is one kind in alkyl, fluoro-alkyl, alkoxy, ester group, carbonyl in the substituted aromatic group
More than.
The Ar is preferably one kind in structural formula 1~12：
Wherein, R1And R2It is containing the alkyl or alkoxy that carbon number is 0-20, when carbon number is 0, R1And R2It is hydrogen or hydroxyl.
When the M is metal ion, metal ion is zinc ion, copper ion, magnesium ion or nickel ion.
The B and C are respectively preferably one kind in structural formula 13~30 and B is different from C：
Wherein, R1And R2It is containing the alkyl or alkoxy that carbon number is 0-20；When carbon number is 0, R is hydrogen, OH.
The preparation method of the asymmetrical porphyrin organic molecule photovoltaic material, comprises the following steps：
When the middle-end radical dye group of formula I of asymmetrical porphyrin organic molecule photovoltaic material contains α, β-unsaturated electrophilic
During group, prepared using Knoevenagel condensation reactions：In organic solvent, using weak base as catalyst system and catalyzing, by containing aldehyde radical
Thiophene porphyrin carries out condensation reaction with the compound containing active methylene group, subsequent treatment, obtains asymmetrical porphyrin organic molecule
Photovoltaic material；
The structure of the thiophene porphyrin containing aldehyde radical is(A is organic group,
It is consistent in the formula I of Ar, M, B and asymmetrical porphyrin organic molecule photovoltaic material), the knot of the compound containing active methylene group
Structure is(Rm, Rn are electron withdraw group), the aldehyde radical in the thiophene porphyrin containing aldehyde radical and the chemical combination containing active methylene group
Ripple methylene living, which reacts, in the structure of thing causes the structure of product to includeGroup, this group have with asymmetrical porphyrin
C groups are consistent in the formula I of machine small molecule photovoltaic material.
Such as：The structure of the thiophene porphyrin containing aldehyde radical isIt is described to contain
The structure of the compound of active methylene group is(Rm, Rn are electron withdraw group), the structure of product are
The organic solvent is chloroform, tetrahydrofuran, dichloromethane and toluene, and weak base is triethylamine, piperidines, the reaction
Temperature be 60~80 DEG C, time of reaction is 12~24 hours；The subsequent treatment refers to that reaction finishes, reaction solution chloroform
Extraction, washing, is spin-dried for solvent, is purified through silica gel column chromatography and gel permeation chromatography, vacuum drying, it is organic to obtain asymmetrical porphyrin
Small molecule photovoltaic material.
The mole of the compound containing active methylene group is 5~10 times of the mole of the thiophene porphyrin containing aldehyde radical.
When the middle-end radical dye group of formula I of asymmetrical porphyrin organic molecule photovoltaic material does not contain α, β-unsaturation inhales electricity
During subbase group, prepared using Sonagashira coupling reactions：In organic solvent, by porphyrin Terminal Acetylenes with bromo compound by urging
Change system is reacted, subsequent treatment, obtains asymmetrical porphyrin organic molecule photovoltaic material；
The structure of the porphyrin Terminal Acetylenes isThe structure of the bromo compound is Br-C, knot
Ar, M, B, C in structure and in the formula I of asymmetrical porphyrin organic molecule photovoltaic material it is consistent.
The organic solvent is tetrahydrofuran and the mixture or toluene of triethylamine and the mixture of triethylamine, the catalysis
System is that four (triphenyl phosphorus) close palladium and cuprous iodide, and the condition of the reaction is small for 60-80 DEG C of heating stirring reaction 48-72
When, after the subsequent treatment refers to reaction solution cooling, extracted with chloroform, dichloromethane or chlorobenzene, washing, solvent is spin-dried for, through silicon
Plastic column chromatography and gel permeation chromatography purifying, vacuum drying, obtain asymmetrical porphyrin organic molecule photovoltaic material.
The mole of the bromide is 3~6 times of the mole of double ethynyl porphyrins, and four (triphenyl phosphorus) close palladium
Mole be the 10~12% of double ethynyl porphyrins moles, the mole of the cuprous iodide is double ethynyl porphyrins mole
The 10~12% of amount.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) asymmetric Porphyrin organic small molecular photovoltaic material of the invention is by two electric end groups of different suctions and a porphyrin
Ring is linked up by conjugated bridge, and whole intramolecular can be made effectively to be conjugated, effectively increase molecule pi-conjugated system and
Intramolecular electron transfer (ICT), has widened the absorption spectrum of material；
(2) present invention is by changing the electron-withdrawing power of molecule one end electron withdraw group, effectively adjust molecule HOMO,
Lumo energy, the donor material with larger open-circuit voltage and short circuit current can be designed；
(3) Porphyrin organic small molecular photovoltaic material of the invention by introduced in the cavity of porphyrin different metals from
Son, because different metal ions has different outer shell electron distributions, further adjust HOMO, LUMO energy of synthetic material
Level, and material is to the absorbent properties of light, final short circuit current, the open-circuit voltage for influenceing device.Therefore, can be by selecting to close
Suitable metal, to obtain efficient porphyrin donor material；
(4) Porphyrin organic small molecular photovoltaic material of the invention is by introducing different virtues in two meso positions of porphyrin ring
Introduce different alkyl or oxyalkyl chain on fragrant (miscellaneous) ring and donor monomer, the solubility of optimum synthesis material, film forming with
And the intermolecular bulk property under filminess.
(5) Porphyrin organic small molecular photovoltaic material of the invention has wider spectral absorption scope, can with spin-coating film,
Possess the potentiality as solar cell active layer donor material.
Brief description of the drawings
Fig. 1 be embodiment 4,5 prepare asymmetrical porphyrin organic molecule photovoltaic material tetrahydrofuran solution it is ultraviolet-
Visible absorption spectra.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
Embodiment 1
The synthesis of compound 3：
The equation of reaction is as follows：
Under the protection of argon gas, into 100mL two mouthfuls of round-bottomed flasks add 5- acetylene -15- (triisopropyl silico acetylene) -
10,20- double (5- (2- ethylhexyls) thiophene) zinc protoporphyrins (compound 1) (762mg, 0.79mmol), the bromo- 3- n-octyls -2- of 5-
Thiophene aldehyde (compound 2) (476mg, 1.58mmol), anhydrous THF (40mL), triethylamine (20mL), four (triphenylphosphines) close palladium
(90mg, 0.079mmol) and cuprous iodide (15mg, 0.079mmol), lucifuge, stirring reaction two days at 65 DEG C；React
Finish, be cooled to room temperature, wash, extracted, anhydrous sodium sulfate drying, be spin-dried for chloroform, using silicagel column separation product, then use gel
Permeation chromatography column chromatography, obtain the solid of purple, as compound 3.1H NMR (500MHz, deuterochloroform) δ/ppm 9.85
(s, 1H), 9.73 (d, J=4.5Hz, 2H), 9.53 (d, J=5.0Hz, 2H), 9.20 (q, 4H), 7.70 (d, J=3.0Hz,
2H), 7.60 (s, 1H), 7.17 (d, J=3.0Hz, 2H), 3.10 (d, J=6.5Hz, 8H), 3.02 (m, 2H), 1.88 (m, 4H),
1.67-1.39 (m, 47), 1.12-0.97 (dt, 12H), 0.78 (t, 3H)
Embodiment 2
The synthesis of compound 4：
The equation of reaction is as follows：
The addition compound 3 (680mg, 0.57mmol) into 100mL single necked round bottom flask, THF (35mL), then slowly
(1 drop/sec) tetrabutyl ammonium fluoride (0.68mmol) is added dropwise；Reaction is finished, and adds water quenching to go out, and is extracted with chloroform, and anhydrous sodium sulfate is done
It is dry, it is spin-dried for, obtains brown solid i.e. compound 4, without being further purified, is directly used in after drying and reacts in next step.
Embodiment 3
The synthesis of compound 6 (the thiophene porphyrin containing aldehyde radical)：
The equation of reaction is as follows：
By compound 4 (492mg, 0.47mmol) and 2,5- bis- (2- ethylhexyls) -3,6- two (2'- thienyls)-pyrroles
And [3,4-c] pyrroles -1,4 (2H, 5H)-diketone (compound 5) (425mg, 0.71mmol) be dissolved in 32mL tetrahydrofuran and
In 16mL triethylamines, then add four (triphenylphosphines) close palladium (54mg, 0.047mmol) and cuprous iodide (9mg,
0.047mmol), react and reacted 48 hours at 65 DEG C；Reaction finishes, and adds water into reaction bulb, is extracted with chloroform, and washing is several
Secondary, solvent evaporated, obtained crude product are purified organic phase by silicagel column on a rotary evaporator, and chemical combination is obtained after vacuum drying
Thing 6.1H NMR (500 MHz, deuterochloroform):δ 9.85 (s, 1H), 9.52 (d, J=4.5Hz, 2H), 9.48 (d, J=4.5Hz,
2H), 9.17 (d, J=4.5Hz, 4H), 8.92 (d, J=4.5Hz, 1H), 8.72 (m, 1H), 7.74 (d, J=3.0Hz, 2H),
7.57 (d, J=6.0Hz, 2H), 7.41 (s, 2H), 7.23 (m, 2H), 7.21 (d, J=3.0Hz, 1H), 3.97 (m, 2H), 3.13
(d, J=6.5Hz, 4H), 2.90 (m, 4H), 1.91 (m, 4H), 1.75 (m, 2H), 1.71-1.16 (m, 42H) 1.14-1.00 (m,
12H),0.95-0.78(m,15H).
Embodiment 4
The synthesis of compound 8 (Porphyrin organic small molecular photovoltaic material)：
The equation of reaction is as follows：
Compound 6 (300mg, 0.19mmol), 2- ethyl rhodanines are sequentially added in 100mL single necked round bottom flask
(compound 7) (310mg, 1.9mmol), 40mL chloroforms and 5 drop piperidines, reaction are reacted 48 hours under reflux conditions；React
Finish, reaction solution is extracted with chloroform, washing, is spin-dried for solvent, and crude on silica gel column chromatography and gel permeation chromatography purifying, vacuum are done
Porphyrin organic small molecular photovoltaic material i.e. compound 8 is obtained after dry.Substance assistant laser desorpted flight time mass spectrum：Experiment value is
1696.08；Calculated value C96H108N7O3S7Zn,1696.59。
Porphyrin organic small molecular photovoltaic material manufactured in the present embodiment is dissolved in tetrahydrofuran solution, obtained tetrahydrofuran
The uv-visible absorption spectra of solution is shown in Fig. 1.
The photovoltaic cell prepared using the Porphyrin organic small molecular photovoltaic material of the present embodiment, device architecture：ITO/
PEDOT:PSS/ active layers/PFN/Al, made battery device photoelectric transformation efficiency are 3.53%, open-circuit voltage 0.84V,
Short circuit current is 9.96mA/cm2, fill factor, curve factor 42.25%.
Embodiment 5
The synthesis of compound 10 (Porphyrin organic small molecular photovoltaic material)：
The equation of reaction is as follows：
Compound 6 (240mg, 0.15mmol), 2- ethyls-dicyanogen methyl isophorone are sequentially added in 100mL single necked round bottom flask
Rhodanine (compound 9) (298mg, 1.5mmol), 40mL chloroforms and 5 drop piperidines, reaction are reacted 48 hours under reflux conditions,
Reaction is finished, and reaction solution is extracted with chloroform, washing, is spin-dried for solvent, crude on silica gel column chromatography and gel permeation chromatography purifying,
Porphyrin organic small molecular photovoltaic material i.e. compound 10 is obtained after vacuum drying.Substance assistant laser desorpted flight time mass spectrum：
Experiment value is 1726.79；Calculated value is C99H109N7O3S6Zn,1727.62。
Porphyrin organic small molecular photovoltaic material manufactured in the present embodiment is dissolved in tetrahydrofuran solution, obtained tetrahydrofuran
The uv-visible absorption spectra of solution is shown in Fig. 1.
The photovoltaic cell prepared using the Porphyrin organic small molecular photovoltaic material of the present embodiment, device architecture：ITO/
PEDOT:PSS/ active layers/PFN/Al, made battery device photoelectric transformation efficiency are 1.22%, open-circuit voltage 0.81V,
Short circuit current is 5.12mA/cm2, fill factor, curve factor 29.42%.
In the following chemical constitution of small molecule photovoltaic material of the present invention：
B, C can also be other dye groups, and M can also be copper ion, magnesium ion, nickel ion etc., and Ar can also be other virtues
Fragrant substituted radical, its preparation principle and performance and the embodiment that the present invention provides are similar, will not be repeated here.
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 (9)
- A kind of 1. asymmetrical porphyrin organic molecule photovoltaic material, it is characterised in that：Its structural formula such as formula I：Wherein：B and C represents end group dye groups respectively, and B and C is different；M is metal ion or hydrogen；Ar is hydrogen, alkyl, alcoxyl Base, substituted or unsubstituted aromatic group.
- 2. asymmetrical porphyrin organic molecule photovoltaic material according to claim 1, it is characterised in that：The Ar is hydrogen, alkane Base, alkoxy is substituted or unsubstituted by the hydrocarbon aromatic rings formed, it is substituted or unsubstituted be made up of hydrocarbon oxygen it is fragrant miscellaneous Ring, the substituted or unsubstituted aromatic heterocycle being made up of carbon nitrogen oxygen hydrogen, the substituted or unsubstituted virtue being made up of carbon sulphur hydrogen atom Fragrant heterocycle, the substituted or unsubstituted aromatic heterocycle being made up of carbon silicon hydrogen atom are substituted or unsubstituted to be made up of carbon nitrogen sulphur hydrogen Aromatic heterocycle, the substituted or unsubstituted aromatic heterocycle being made up of carbon silicon sulphur hydrogen is substituted or unsubstituted by carbon silicon sulphur hydrogen structure Into one or more of aromatic heterocycle, the aromatic heterocycle that substituted or unsubstituted hydrocarbon selenium is formed；Substituted radical is one or more of alkyl, fluoro-alkyl, alkoxy, ester group, carbonyl in the substituted aromatic group.
- 3. asymmetrical porphyrin organic molecule photovoltaic material according to claim 2, it is characterised in that：The Ar is structural formula One kind in 1~12：Wherein, R1And R2It is containing the alkyl or alkoxy that carbon number is 0-20.
- 4. asymmetrical porphyrin organic molecule photovoltaic material according to claim 1, it is characterised in that：The M be metal from The period of the day from 11 p.m. to 1 a.m, metal ion are zinc ion, copper ion, magnesium ion or nickel ion.
- 5. asymmetrical porphyrin organic molecule photovoltaic material according to claim 1, it is characterised in that：The B and C are respectively One kind and B in structural formula 13~30 is different from C：Wherein, R1And R2It is containing the alkyl or alkoxy that carbon number is 0-20；When carbon number is 0, R is hydrogen, OH.
- 6. according to the preparation method of any one of Claims 1 to 5 asymmetrical porphyrin organic molecule photovoltaic material, its feature It is：It is divided into two kinds：First method is：When the middle-end radical dye group of formula I of asymmetrical porphyrin organic molecule photovoltaic material contains α, β-no During saturation electron withdraw group, prepared using Knoevenagel condensation reactions：In organic solvent, using weak base as catalyst system and catalyzing, Thiophene porphyrin containing aldehyde radical and the compound containing active methylene group are subjected to condensation reaction, subsequent treatment, obtain asymmetrical porphyrin Organic molecule photovoltaic material；Second method is：When the middle-end radical dye group of formula I of asymmetrical porphyrin organic molecule photovoltaic material does not contain α, β-unsaturated electron-withdrawing group During group, prepared using Sonagashira coupling reactions：In organic solvent, porphyrin Terminal Acetylenes and bromo compound are passed through into catalytic body System is reacted, and subsequent treatment, obtains asymmetrical porphyrin organic molecule photovoltaic material.
- 7. the preparation method of asymmetrical porphyrin organic molecule photovoltaic material according to claim 6, it is characterised in that：The structure of the thiophene porphyrin containing aldehyde radical isWherein A is organic group It is consistent in the formula I of group, Ar, M, B and asymmetrical porphyrin organic molecule photovoltaic material；The compound containing active methylene group Structure isRm, RnFor electron withdraw group；Aldehyde radical in thiophene porphyrin containing aldehyde radical and the chemical combination containing active methylene group Ripple methylene living, which reacts, in the structure of thing causes the structure of product to includeGroup, this group have with asymmetrical porphyrin C is consistent in the formula I of machine small molecule photovoltaic material.
- 8. the preparation method of asymmetrical porphyrin organic molecule photovoltaic material according to claim 6, it is characterised in that：It is described The structure of porphyrin Terminal Acetylenes isThe structure of the bromo compound is Br-C, Ar, M, B in structure, It is consistent in the formula I of C and asymmetrical porphyrin organic molecule photovoltaic material.
- 9. according to the application of any one of Claims 1 to 5 asymmetrical porphyrin organic molecule photovoltaic material, its feature exists In：The asymmetrical porphyrin organic molecule photovoltaic material is used to prepare solar cell.
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