CN105038293A - Indole [3,2-b] pyrrole dye, and preparation method and applications thereof - Google Patents
Indole [3,2-b] pyrrole dye, and preparation method and applications thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title abstract 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title abstract 12
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title abstract 6
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 239000000975 dye Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 150000002475 indoles Chemical class 0.000 claims description 19
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 230000004044 response Effects 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012044 organic layer Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 7
- 229940125898 compound 5 Drugs 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- OHOVBSAWJQSRDD-UHFFFAOYSA-N thiophen-2-yloxyboronic acid Chemical compound OB(O)OC1=CC=CS1 OHOVBSAWJQSRDD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical compound [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 claims description 3
- -1 iso-octyl Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-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
- WZVGCPYOPOZMLJ-UHFFFAOYSA-N C[n](cc1)c2c1[nH]c1cc(Br)ccc21 Chemical compound C[n](cc1)c2c1[nH]c1cc(Br)ccc21 WZVGCPYOPOZMLJ-UHFFFAOYSA-N 0.000 description 1
- RTDNXISQXVISQE-UHFFFAOYSA-N C[n]1c(-c(ccc(Br)c2)c2[N+]([O-])=O)ccc1 Chemical compound C[n]1c(-c(ccc(Br)c2)c2[N+]([O-])=O)ccc1 RTDNXISQXVISQE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos 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
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Indole Compounds (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses an indole [3,2-b] pyrrole dye, and a preparation method and applications thereof, and belongs to the field of photoelectric conversion material in fine chemical engineering. According to the indole [3,2-b] pyrrole dye, indole [3,2-b] pyrrole is taken as a core framework, and cyanoacetic acid is taken as a receptor group. The structure of indole [3,2-b] pyrrole contains two nitrogen atoms, electron cloud density is high, electron donating ability is high, relatively strong absorption can be observed in visible region, and the indole [3,2-b] pyrrole dye can be applied to dye-sensitized solar cells as a photosensitizer.
Description
Technical field
The present invention relates to the photoelectric conversion Material Field in fine chemistry industry, be specifically related to a class indoles [3,2-b] and pyrylium dyes and method for making thereof and application.
Technical background
Dye-sensitized solar cells (DSSCs) is a kind of novel device converted solar energy into electrical energy.This kind of battery has the advantages such as structure is simple, cost of manufacture is low compared with traditional silica-based solar cell, is the photoelectric conversion device that a class has wide application prospect.The structure design of dyestuff is most important for the photoelectric transformation efficiency of this kind of battery.At present, what electricity conversion was the highest is Ru-polypyridine complex.But ruthenium belongs to rare precious metals, the separating-purifying of Ru-polypyridine complex also has suitable difficulty, and its DSSCs cost is higher, limits that it is practical on a large scale.For this reason, develop metal-free organic photosensitive dyestuff most important to development DSSCs, become the important research direction in this field.With Ru-polypyridine complex dyestuff (as N3, N719 etc.) compare, the plurality of advantages such as organic photosensitive dyestuff has various structures, preparation is purified relatively easily, molar extinction coefficient is high, rapidly, organic dye numerous in variety obtains development and application in organic photosensitive dyestuff development in recent years.
Indoles [3,2-b] pyrroles contains two nitrogen-atoms, cloud density is large, electron donation is strong.There is indoles [3,2-b] and the organic dye of pyrrole structure has stronger absorption in visible region.But also there is no indoles [3,2-b] and the report of pyrylium dyes at present.In order to develop high-performance organic dye and be applied to dye-sensitized solar cells, the present invention designs and synthesizes the indoles [3 that a class contains electron rich, 2-b] and pyrrole structure unit, take cyanoacetic acid as the new dye of acceptor--indoles [3,2-b] pyrylium dyes.It is simple that this dyestuff has structure, and synthesis easily, has stronger absorption in visible region, can be used in dye-sensitized solar cells as efficient photosensitizers.
Summary of the invention
The object of the invention is synthesis one class indoles [3,2-b] and pyrylium dyes.The present invention synthesizes the novel metal-free pure organic photosensitive dyestuff of a class, this kind of dyestuff with the indoles of electron rich [3,2-b] and pyrroles for core skeleton, cyanoacetic acid is as electron acceptor(EA).This kind of dyestuff can be applied to dye-sensitized solar cells as efficient photosensitizer.
The invention provides indoles [3,2-b] and pyrylium dyes, the general structure of this kind of dyestuff is as follows:
Wherein: R
1, R
2for C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20amide group, R
1, R
2identical or different; Ar
1, Ar
2for aromatic nucleus, Ar
1, Ar
2identical or different, and there is the aromatic nucleus of following structure:
Wherein, X
1~ X
4for hydrogen, C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl, C
1~ C
20amide group or C
1~ C
20alkoxyl group, X
1~ X
4identical or different; X
5and X
6for hydrogen, C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group, X
5and X
6identical or different; X
7and X
8for hydrogen, C
1~ C
20straight chained alkyl or C
1~ C
20branched-chain alkyl, X
7and X
8identical or different.
Indoles of the present invention [3,2-b] pyrylium dyes synthetic method are simple, and raw material is cheap and easy to get, and synthetic route is as follows:
Work as R
1for methyl, R
2for iso-octyl, Ar
1for thiphene ring, Ar
2during for CH, indoles [3,2-b] the synthesis step of pyrylium dyes is as follows:
(1) take orthodichlorobenzene as solvent, first add 1 part of compound 1, then add 3.0 ~ 5.0 parts of triphenylphosphines, heated and stirred is to backflow, and question response is complete, removal of solvent under reduced pressure, and in impouring water, aftertreatment obtains compound 2;
(2) be solvent with DMF, add 1 part of compound 2, then add KOH, NaOH, K
2cO
3in one, stirring at room temperature 0.5h ~ 2h, slowly adds 1.2 ~ 2.0 parts of 1-bromine octane-iso, be warming up to 100 DEG C ~ 130 DEG C reaction 4h ~ 24h, after question response liquid cooling but, pour in cold water, aftertreatment obtains compound 3;
(3) be solvent with DMF, add 1.0 parts of compounds 3, under ice bath, slowly drip 3.0 parts of phosphorus oxychloride of dissolving with DMF, wait to dropwise, stirring at room temperature 0.5h ~ 1h, be more slowly warming up to 80 DEG C of reactions and spend the night, cooling, pour in frozen water, add NaOH, NaHCO
3in one neutralization, aftertreatment obtains compound 4;
(4) be solvent with DMF, add 1 part of compound 4, then add KOH, NaOH, K
2cO
3in one, slowly add 1.2 ~ 2.0 parts of 2-thienyl boric acid, be warming up to 100 DEG C ~ 130 DEG C reaction 12h ~ 24h, after question response liquid cooling but, pour in cold water, aftertreatment obtains compound 5;
(5) be solvent with acetonitrile, add 1 part of compound 5, then add piperidines, one in acetic acid-ammonium acetate, slowly adds 3.0 ~ 5.0 parts of cyanoacetic acids, is warming up to 80 DEG C of reaction 12h ~ 24h, after question response liquid cooling but, pour in cold water, aftertreatment obtains compound TX-1.
Further optimally, described preparation method comprises the steps:
Under inert atmosphere, take orthodichlorobenzene as solvent, first add 1 part of compound 1, then add 3.0 parts of triphenylphosphines, question response is complete, removal of solvent under reduced pressure, in impouring water, adds dichloromethane extraction, organic layer is washed, drying, concentrated, crude product to be purified to obtain compound 2 by recrystallization or column chromatography for separation;
Under inert atmosphere, take DMF as solvent, add 1 part of compound 2, add KOH, NaOH, K
2cO
3in one, stirring at room temperature 0.5h, slowly adds 1.2 parts of 1-bromine octane-iso, be warming up to 130 DEG C reaction 24h.After question response liquid cooling but, pour in cold water, add dichloromethane extraction, organic layer is washed, dry, concentrated, and crude product to be purified to obtain compound 3 by recrystallization or column chromatography for separation;
Under Ar gas shielded, be solvent with DMF, add 1.0 parts of compounds 3.3.0 parts of phosphorus oxychloride of dissolving with DMF are slowly dripped under ice bath.Wait to dropwise, stirring at room temperature 0.5h, be warming up to 80 DEG C of reactions and spend the night.Cooling, pours in frozen water, adds dichloromethane extraction, and organic layer is washed, dry, concentrated, and crude product to be purified to obtain compound 4 by recrystallization or column chromatography for separation;
Under inert atmosphere, take DMF as solvent, add 1 part of compound 4, add KOH, NaOH, K
2cO
3in one, slowly add 1.2 parts of 2-thienyl boric acid, be warming up to 130 DEG C reaction 24h.After question response liquid cooling but, pour in cold water, add dichloromethane extraction, organic layer is washed, dry, concentrated, and crude product to be purified to obtain compound 5 by recrystallization or column chromatography for separation;
Under inert atmosphere, take acetonitrile as solvent, add 1 part of compound 5, add the one in piperidines, acetic acid-ammonium acetate, slowly add 5.0 parts of cyanoacetic acids, be warming up to 80 DEG C of reaction 24h.After question response liquid cooling but, pour in cold water, add dichloromethane extraction, organic layer is washed, dry, concentrated, and crude product to be purified to obtain compound TX-1 by recrystallization or column chromatography for separation.
An above-mentioned class indoles [3,2-b] pyrylium dyes can be applied preparing in dye-sensitized solar cells.
Compared with prior art, tool of the present invention has the following advantages and technique effect:
The present invention fills up at present about indoles [3,2-b] and pyrylium dyes is applied to the blank of dye-sensitized solar cells aspect, design and synthesize the indoles [3 that a class contains electron rich, 2-b] and pyrrole structure unit, take cyanoacetic acid as the new dye of acceptor--indoles [3,2-b] pyrylium dyes.It is simple that this dyestuff has structure, and synthesis easily, has stronger absorption in visible region, can be used in dye-sensitized solar cells as efficient photosensitizers.
Accompanying drawing explanation
Fig. 1 is dyestuff (concentration 2 × 10 in dichloromethane solvent synthesized in embodiment 1 and embodiment 2
-5m) ultraviolet/visible absorbance spectrogram, what wherein X-coordinate represented is absorbing wavelength, and what ordinate zou represented is photon absorbing intensity.
Fig. 2 is photoelectric current and the photovoltage curve of the dye-sensitized solar cells device of embodiment 3, and what wherein X-coordinate represented is voltage, and what ordinate zou represented is current density.
Embodiment
Below in conjunction with embodiment the present invention done and describe in detail further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Indoles [3,2-b] the synthesis of pyrylium dyes TX-2
Below reaction is all carried out in the dry environment under argon shield.
(1) synthesis of compound 2
The compound 1 of 1.41g (5mmol) is dissolved in the orthodichlorobenzene of 50mL drying, then adds the backflow of 3.94g (15mmol) triphenylphosphine vigorous stirring.Question response is complete, removal of solvent under reduced pressure.In impouring water, add methylene dichloride (3 × 30ml) extraction.Organic layer is washed, dry, concentrated.Crude product is slightly purified by the silicagel pad that a 10cm is high, obtains khaki color solid 0.63g, yield 50%.
1HNMR(CDCl
3,400MHz,ppm):δ7.48-7.53(m,3H),7.18-7.21(m,1H),6.74(d,J＝2.8Hz,1H),6.03(d,J＝2.8Hz,1H),3.96(s,3H).
13CNMR(CDCl
3,100MHz,ppm):δ141.4,132.4,126.0,122.3,121.7,116.8,115.3,114.4,113.7,90.42,35.4.
(2) synthesis of compound 3
By 1.25g (5mmol) compound 2 and 1.38g (10mmol) K
2cO
3join in the DMF of 50ml drying, in stirring at room temperature reaction 1.0h under argon shield.Then slowly inject the 1-bromine octane-iso that 1.15g (6mmol) is dissolved in the DMF of 5ml drying, after adding, be warming up to 130 DEG C of reaction 24h.Reaction terminates rear leaving standstill and is cooled to room temperature, and reaction solution is poured in 200ml water, extracts with methylene dichloride (3 × 30ml).Organic layer washed with water is for several times to remove DMF completely.Drying, concentrated, crude product is purified (sherwood oil and methylene dichloride (1:1) are as moving phase) by column chromatography for separation, and obtain 1.54g light yellow liquid, yield is 85%.
1HNMR(400MHz,CDCl
3)δ7.54–7.52(d,1H),7.42(s,1H),7.17–7.15(d,1H),6.76–6.75(d,1H),6.02–6.01(d,1H),4.03–3.91(m,5H),2.06–2.00(m,1H),1.39–1.27(m,8H),0.93–0.87(m,6H).
13CNMR(101MHz,CDCl
3)δ141.58,135.43,125.80,120.84,120.38,116.83,114.46,113.36,112.22,89.72,49.01,39.55,35.39,30.75,28.67,24.14,23.06,14.06,10.72.
(3) synthesis of compound 4
Under Ar protection, with the DMF of drying (30ml) for solvent, add 0.72g compound 3.The phosphorus oxychloride that 0.9g is dissolved in the dry DMF dissolving of 5ml is slowly dripped under condition of ice bath.Wait to dropwise, be warming up to 80 DEG C of reactions and spend the night.Cooling, pours in frozen water, and hydro-oxidation sodium neutralizes, and adds methylene dichloride (3 × 20ml) extraction, organic layer is washed, dry, concentrated, crude product is purified (methylene dichloride is as moving phase) by column chromatography for separation, and obtain 0.62g glassy yellow oily matter, yield is 80%.
1HNMR(400MHz,CDCl
3)δ9.58(s,1H),7.63–7.58(m,1H),7.40(s,1H),7.20–7.18(m,1H),6.61(s,1H),4.27(s,3H),3.92-3.85(m,2H),2.05–1.91(m,1H),1.34–1.27(m,8H),0.92–0.85(m,6H).
13CNMR(101MHz,CDCl
3)δ179.91,144.86,134.35,134.03,130.00,121.54,119.84,118.24,112.95,112.79,102.13,48.97,39.39,34.66,30.72,28.63,24.14,23.02,14.04,10.71.
(4) synthesis of compound 5
By 0.39g (1.0mmol) compound 4 and 0.28g (2mmol) K
2cO
3join in 15mlDMF, in stirring at room temperature reaction 0.5h under nitrogen protection.Then slowly inject the 2-thienyl boric acid that 0.15g (1.2mmol) is dissolved in 5mlDMF, after adding, be warming up to 130 DEG C of reaction 24h.Reaction terminates rear leaving standstill and is cooled to room temperature, and reaction solution is poured in 200ml water, uses CH
2cl
2(3 × 25ml) extracts.Organic layer washed with water is for several times to remove DMF completely.Drying, concentrated, crude product is purified (sherwood oil and methylene dichloride (1:1) are as moving phase) by column chromatography for separation, and obtain the yellow floss of 0.12g, yield is 30%.
1HNMR(400MHz,CDCl
3)δ9.57(s,1H),7.77-7.75(m,1H),7.48(s,1H),7.38-7.36(m,2H),7.29-7.28(m,1H),7.11-7.09(m,1H),6.60(s,1H),4.30(s,3H),4.02-3.92(m,2H),2.09-1.95(m,1H),1.39-1.27(m,8H),0.94-0.86(m,6H).
13CNMR(101MHz,CDCl
3)δ179.69,145.44,144.82,134.66,134.30,130.98,130.67,128.15,124.66,122.99,119.29,117.11,113.37,106.94,48.78,39.61,34.69,30.88,28.78,24.29,23.03,14.06,10.80.
(5) indoles [3,2-b] the synthesis of pyrylium dyes TX-1
By 0.10g compound 5 (0.25mmol), 0.106g cyanoacetic acid (1.25mmol), 0.3mL piperidines (3mmol) is mixed in 30mL acetonitrile, N
2reflux under protection 8h.After cooling, reaction solution is poured in HCl (2M, the 100mL) aqueous solution.After stirring 15min, methylene dichloride (3 × 20ml) extracts, organic layer deionized water wash twice (at every turn using deionized water 100mL).Anhydrous Na
2sO
4drying, concentrated, crude product is by silica gel column chromatography separating-purifying (first use dichloromethane eluent, then use methylene dichloride/and methyl alcohol (20:1) wash-out).Obtain 0.06g dark red powder shape dyestuff TX-2, yield is 50%.
1HNMR(DMSO-d
6,400MHz,ppm):δ8.15(s,1H),7.99(d,J＝8.0Hz,1H),7.70(s,1H),7.63-7.64(m,1H),7.56-7.57(m,1H),7.40(d,J＝8.0Hz,1H),7.34(s,1H),7.17-7.19(m,1H),4.08-4.11(m,5H),1.87-1.98(m,1H),1.20-1.30(m,8H),0.81-0.90(m,6H).
13CNMR(DMSO-d
6,100MHz,ppm):δ165.0,145.3,144.2,138.8,136.3,131.0,130.6,130.5,128.5,125.6,123.8,120.0,118.3,116.7,112.2,106.5,95.0,90.3,47.4,32.1,30.0,27.9,23.5,22.4,13.8,10.6.
(6) synthesis of compound 6
Under argon gas atmosphere protection, in the oblique two mouthfuls of bottles of 50mL, add compound 3 (0.361g, 1.00mmol) successively; di-boric acid gneissic suite ester (0.510g, 2.00mmol), Glacial acetic acid potassium (0.196g; 2.00mmol), Pd (dppf) Cl
2(0.037g, 0.05mmol) and dry Isosorbide-5-Nitrae-dioxane 20mL.After reflux 24h, TLC monitoring reacts completely.Question response thing is cooled to room temperature, and decompress filter gets filtrate.Organic solvent through the removing of water pump decompression rotary evaporation, crude product with sherwood oil and ethyl acetate (v/v=20/1) for developping agent is through 200-300 order silica gel column chromatography purifying, after vacuum-drying colourless viscous liquid 0.368g, productive rate: 90%.
1HNMR(CDCl
3,400MHz,ppm):δ7.78(s,1H),7.68(d,J＝7.6Hz,1H),7.51(d,J＝8.0Hz,1H),6.76(s,1H),6.01(s,1H),4.02-4.09(m,2H),3.99(s,3H),2.06-2.11(m,1H),1.38(s,12H),1.23-1.34(m,8H),0.86-0.91(m,6H)。
13CNMR(CDCl
3,100MHz,ppm):δ140.6,136.2,126.3,123.8,121.5,117.6,115.8,115.1,89.6,83.4,48.7,39.5,35.4,30.7,28.7,25.0,24.9,24.2,23.1,14.1,10.8。
(7) synthesis of compound 7
Intermediate 60.330g (0.8mmol) is added successively in the oblique two mouthfuls of reaction flasks of 50mL; 2-bromo-5-formylthien 0.120g (0.64mmol); tetra-triphenylphosphine palladium 0.074g (0.064mmol); 0.5M wet chemical 2.6mL and Isosorbide-5-Nitrae-dioxane 20mL.After adding, pass into nitrogen in reaction solution 30 minutes, under reflux argon shield, lucifuge reacts 24 hours.After TLC detection reaction is complete, by in reaction solution impouring 50mL deionized water, with 3 × 20mL dichloromethane extraction, merge organic phase, organic phase is use saturated aqueous common salt and deionized water wash successively, anhydrous sodium sulfate drying, vacuum rotary steam removing methylene dichloride, resistates with sherwood oil and ethyl acetate (v/v=25/1) for eluent is through silica gel column chromatography (300-400 order) separation and purification, orange/yellow solid 0.120g is obtained after vacuum-drying, productive rate: 85%, fusing point 121-123 DEG C.
1HNMR(CDCl
3,400MHz,ppm):δ9.86(s,1H),7.72-7.73(m,1H),7.66-7.68(m,1H),7.59-7.60(m,1H),7.39-7.41(m,1H),6.79(d,J＝2.8Hz,1H),6.02(d,J＝2.8Hz,1H),4.00-4.07(m,2H),3.98(s,3H),2.02-2.08(m,1H),1.28-1.41(m,8H),0.86-0.95(m,6H)。
13CNMR(CDCl
3,100MHz,ppm):δ182.6,157.3,141.0,140.9,137.9,137.1,127.0,124.8,122.7,121.3,116.4,116.3,116.2,107.3,89.8,48.9,39.8,35.4,30.9,28.7,24.2,23.1,14.1,10.8。
(8) indoles [3,2-b] the synthesis of pyrylium dyes TX-2
With intermediate 7 for raw material, synthetic method is with reference to dyestuff TX-1.Dyestuff is TX-2 rust solid, fusing point: 236-238 DEG C.
1HNMR(DMSO-d
6,400MHz,ppm):δ8.47(s,1H),8.02-8.03(m,1H),7.83(s,1H),7.78-7.81(m,2H),7.41-7.44(m,1H),7.03(d,J＝2.8Hz,1H),6.07(d,J＝2.8Hz,1H),4.12-4.14(m,2H),3.97(s,3H),1.94-2.03(m,1H),1.21-1.31(m,8H),0.81-0.90(m,6H)。
13CNMR(CDCl
3,100MHz,ppm):δ164.0,156.2,146.6,141.9,140.4,136.8,132.9,128.2,123.8,123.6,120.6,116.8,116.5,116.1,115.8,107.1,96.3,89.6,47.7,34.9,30.0,27.9,23.5,22.5,13.8,10.6。
Embodiment 2
Uv-visible absorption spectra test is carried out to dyestuff TX-1 and TX-2 prepared by embodiment 1.Its uv-visible absorption spectra as shown in Figure 1.
Solvent: methylene dichloride
Concentration: 2 × 10
-5m
Temperature: room temperature
Instrument: ShimadzuUV-2450 ultraviolet-visible pectrophotometer
As can be seen from Figure 1, dyestuff TX-1 and TX-2 prepared by embodiment 1 has stronger absorption to sunlight in visible-range, and its maximum absorption wavelength is respectively 479nm, 476nm.
Embodiment 3
Dye-sensitized solar cells device is made: immerse the nanometer titanium dioxide Ti electrode baked containing 3 × 10 with embodiment 1 dyestuff
-4in the tetrahydrofuran solution of mol/L dyestuff TX-1 or TX-2 12 hours; Then take out, rinse with dehydrated alcohol, dry up.By the glass electrode of this sensitization electrode and platinum plating and electrolytic solution composition dye-sensitized solar cells.At 100mW/cm
2light intensity under record dyestuff TX-1 open circuit voltage be 0.69V, short-circuit current density is 9.54mA/cm
2, packing factor is 0.77, and electricity conversion is 5.04%.Under equal conditions, the open circuit voltage of dyestuff TX-2 is 0.54V, and short-circuit current density is 3.21mA/cm only
2, packing factor is 0.66, electricity conversion only 1.16%.Their photoelectric current and photovoltage curve are shown in Fig. 2.
Claims (4)
1. a class indoles [3,2-b] pyrylium dyes, is characterized in that general structure is as follows:
Wherein: R
1, R
2for C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20amide group, R
1, R
2identical or different; Ar
1, Ar
2for aromatic nucleus, Ar
1, Ar
2identical or different, and
Wherein, X
1~ X
4for hydrogen, C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl, C
1~ C
20amide group or C
1~ C
20alkoxyl group, X
1~ X
4identical or different; X
5and X
6for hydrogen, C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group, X
5and X
6identical or different; X
7and X
8for hydrogen, C
1~ C
20straight chained alkyl or C
1~ C
20branched-chain alkyl, X
7and X
8identical or different.
2. prepare a class indoles [3,2-b] described in claim 1 and the method for pyrylium dyes, it is characterized in that working as R
1for methyl, R
2for iso-octyl, Ar
1for thiphene ring, Ar
2during for CH, synthesis step is as follows:
(1) take orthodichlorobenzene as solvent, first add 1 part of compound 1, then add 3.0 ~ 5.0 parts of triphenylphosphines, heated and stirred is to backflow, and question response is complete, removal of solvent under reduced pressure, and in impouring water, aftertreatment obtains compound 2;
(2) be solvent with DMF, add 1 part of compound 2, then add KOH, NaOH, K
2cO
3in one, stirring at room temperature 0.5h ~ 2h, slowly adds 1.2 ~ 2.0 parts of 1-bromine octane-iso, be warming up to 100 DEG C ~ 130 DEG C reaction 4h ~ 24h, after question response liquid cooling but, pour in cold water, aftertreatment obtains compound 3;
(3) be solvent with DMF, add 1.0 parts of compounds 3, under ice bath, slowly drip 3.0 parts of phosphorus oxychloride of dissolving with DMF, wait to dropwise, stirring at room temperature 0.5h ~ 1h, be more slowly warming up to 80 DEG C of reactions and spend the night, cooling, pour in frozen water, add NaOH, NaHCO
3in one neutralization, aftertreatment obtains compound 4;
(4) be solvent with DMF, add 1 part of compound 4, then add KOH, NaOH, K
2cO
3in one, slowly add 1.2 ~ 2.0 parts of 2-thienyl boric acid, be warming up to 100 DEG C ~ 130 DEG C reaction 12h ~ 24h, after question response liquid cooling but, pour in cold water, aftertreatment obtains compound 5;
(5) be solvent with acetonitrile, add 1 part of compound 5, then add piperidines, one in acetic acid-ammonium acetate, slowly adds 3.0 ~ 5.0 parts of cyanoacetic acids, is warming up to 80 DEG C of reaction 12h ~ 24h, after question response liquid cooling but, pour in cold water, aftertreatment obtains compound TX-1.
3. preparation method according to claim 2, is characterized in that step (1)-(5) described reaction process is carried out all under an inert atmosphere; Described aftertreatment all refers to add dichloromethane extraction, and organic layer is washed, dry, concentrated, and crude product is purified by recrystallization or column chromatography for separation.
4. a class indoles [3,2-b] described in claim 1 pyrylium dyes is preparing the application in dye-sensitized solar cells.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527517A (en) * | 1965-09-01 | 1970-09-08 | Kalle Ag | Bis-indolyl-aryl-methane light sensitive compositions |
| CN103554958A (en) * | 2013-11-08 | 2014-02-05 | 天津理工大学 | Dithiophene pyrrole bridge-indoline organic dyes as well as preparation method and application thereof |
-
2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527517A (en) * | 1965-09-01 | 1970-09-08 | Kalle Ag | Bis-indolyl-aryl-methane light sensitive compositions |
| CN103554958A (en) * | 2013-11-08 | 2014-02-05 | 天津理工大学 | Dithiophene pyrrole bridge-indoline organic dyes as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| KAI-LI ZHU ET AL.: ""Screening novel candidates and exploring design strategies for organic dye sensitizers with rigid π-linker:A theoretical study"", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| 戴学新 等: ""1,4-二氢吡咯[3,2-b]并吲哚染料的合成及其光电转换性能研究"", 《中国化学会第八届有机化学学术会议暨首届重庆有机化学国际研讨会论文摘要集（5）》 * |
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