CN103275060B - A kind of triaryl methane compounds and its preparation method and application - Google Patents
A kind of triaryl methane compounds and its preparation method and application Download PDFInfo
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- CN103275060B CN103275060B CN201310150401.0A CN201310150401A CN103275060B CN 103275060 B CN103275060 B CN 103275060B CN 201310150401 A CN201310150401 A CN 201310150401A CN 103275060 B CN103275060 B CN 103275060B
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- triarylmethane
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- cyanoacetic acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 12
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 11
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 11
- 229910019213 POCl3 Inorganic materials 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- -1 methoxy, ethoxy Chemical group 0.000 claims description 3
- 230000002165 photosensitisation Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 206010070834 Sensitisation Diseases 0.000 abstract description 4
- 230000008313 sensitization Effects 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000000975 dye Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000005457 ice water Substances 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000000434 metal complex dye Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 3
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 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 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FTBIGLZDAHQPCL-UHFFFAOYSA-N methane;thiophene-2-carbaldehyde Chemical compound C.O=CC1=CC=CS1 FTBIGLZDAHQPCL-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 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 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 210000002268 wool Anatomy 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
-
- 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
Landscapes
- Hybrid Cells (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of triaryl methane compounds and its preparation method and application; Preparation method is first by R
2-CHO and and R
1-H is obtained by reacting chemical compounds I; Again the chemical compounds I obtained and Vilsmeier reagent react are generated compound ii; The compound ii obtained and cyanoacetic acid after back flow reaction, obtain triaryl methane compounds in acetum; Or, first the chemical compounds I obtained and N-bromo-succinimide generation bromo-reaction are generated compound III; By gained compound III and (OH)
2b-R
3-CHO obtains compounds Ⅳ after back flow reaction in toluene or chloroform; By the compounds Ⅳ of acquisition and cyanoacetic acid back flow reaction in acetum, obtain triaryl methane compounds; The triaryl methane compounds that the method obtains is applied to as light-sensitive coloring agent prepares dye sensitization solar battery material; These triaryl methane compounds raw material sources are wide, low price, and preparation method is simple, and cost is low, can suitability for industrialized production; Be expected to become a kind of novel dye sensitization solar battery material.
Description
Technical Field
The invention relates to a triarylmethane compound and a preparation method and application thereof, belonging to the field of dye-sensitized solar cells.
Technical Field
A solar cell is a photoelectric device that converts solar energy into electrical energy according to the principle of photovoltaic generation. Dye Sensitized Solar Cells (DSSCs) were first proposed by the switzerland federal lossan gaol research group in 1991 and raised the hot leg of photovoltaic cell research. The cell has the advantages of low cost, simple structure, excellent photoelectric conversion efficiency (the highest photoelectric conversion efficiency reaches 12.3 percent (A. yellow, H. -W.Lee, M.Gratzel, Science,334,2011,629)), and the like, and becomes a photoelectric conversion device with application prospect.
The photosensitizing dye is an important part in the dye-sensitized solar cell, and the performance of the photosensitizing dye directly influences the photoelectric conversion efficiency of the DSSC. At present, the dyes applied to the DSSC mainly comprise two main types of metal complex dyes and organic dyes. The photoelectric conversion efficiency of part of metal complex dyes exceeds 10%, but the application of the metal complex dyes is limited due to high cost. Therefore, the synthesis of photosensitizers for high efficiency organic dyes has become a research hotspot in this field.
Triarylmethanes are widely used as coloring agents (r.muthyala, a.r.kattritzky, x.lan, dyespigmins, 25,1994,303) and thermosensitive materials (m.irie, j.am.chem.soc.105,1983, 2078), and have bright colors and simple synthetic processes. Currently, triarylmethane as a dye is mainly used for dyeing organic substances such as fibers, wool, leather and the like (such as triarylmethane dyes disclosed in chinese patent publication No. CN 101326244A), but the application of triarylmethane compounds as a dye photosensitizer in the field of solar cells is not reported in related patent technology, and never appears in publications at home and abroad.
Disclosure of Invention
Aiming at the defects that in the prior art, when metal complex dyes and organic dyes are used for dye-sensitized solar cells, the raw material cost is high, the preparation method is complex and the like, the invention aims to provide an organic triarylmethane compound with a novel structure, which is low in price and good in photoelectric conversion performance.
The invention also aims to provide a method for preparing the triarylmethane compound at low cost, which has the advantages of cheap raw materials, wide sources, simple preparation method and industrial production.
The invention also aims to provide an application of the triarylmethane compound, wherein the triarylmethane compound is used as a photosensitive dye to prepare dye-sensitized solar cell materials, and the materials are low in cost, simple in preparation method, good in photoelectric conversion performance and have the potential of being widely applied to dye-sensitized solar cells.
The invention provides a triarylmethane compound which has a structure shown in a formula 1 or a formula 2:
wherein,
R1is selected fromOne of (1);
R2is selected fromOne of (1);
R3is selected fromOne of (1);
R4、R5、R6、R7and R8Each independently selected from C3～9One of alkyl groups of (1), or C1～6One of alkoxy groups of (2), or a hydrogen atom
Preferred triarylmethane compounds, R2Is selected fromOne of (1); r3Is selected fromOne of (1); r1Is selected from One of (1); wherein R is4、R5、R6、R7And R8Each independently selected from C3～9One of the straight chain alkyl groups of (1), or C1～6One of the linear alkoxy groups of (1), or a hydrogen atom.
More preferred triarylmethane compounds, R2Is selected fromOne of (1); r3Is selected fromOne of (1); r1Is selected from One of (1); wherein R is4、R5、R6、R7And R8Each independently selected from C3～9One of the straight-chain alkyl groups of (1), or one of methoxy, ethoxy and propoxy, or a hydrogen atom.
The invention also provides a preparation method of the triarylmethane compound, which comprises the step of firstly preparing R under the protection of inert gas2-CHO with and R1reacting-H at 80-100 ℃ to obtain a compound I; reacting the obtained compound I with a Vilsmeier reagent at 25-120 ℃ to generate a compound II; carrying out reflux reaction on the obtained compound II and cyanoacetic acid in an acetic acid solution to obtain a triarylmethane compound with a structure shown in a formula 2;
or, firstly, carrying out bromination reaction on the obtained compound I and N-bromosuccinimide at the temperature of-5 ℃ to generate a compound III; the resulting compounds III and (OH)2B-R3-CHO is refluxed in toluene or chloroform to obtain a compound IV; and carrying out reflux reaction on the obtained compound IV and cyanoacetic acid in an acetic acid solution to obtain the triarylmethane compound with the structure of the formula 1.
In the above preparation method R2-CHO and R1The molar ratio of-H is 1: 8-12.
In the above preparation method, the compound I and POCl3The molar ratio of (A) to (B) is 1: 1-8.
In the preparation method, the molar ratio of the compound II to the cyanoacetic acid is 1: 6-10.
In the preparation method, the molar ratio of the compound IV to the cyanoacetic acid is 1: 6-10.
In the preparation method, the molar ratio of the compound I to the N-bromosuccinimide is 1: 1.
Compounds III and (OH) of the above preparation2B-R3-CHO molar ratio of 1: 1.
Compounds III and (OH) of the above preparation2B-R3K with the molar weight 8-10 times that of the compound III is added in the CHO reaction2CO3。
The Vilsmeier reagent is POCl3Wherein the N, N-dimethylformamide is POCl3The molar ratio of (A) to (B) is 5-1: 1; the Vilsmeier reagent is prepared by adding POCl in ice water bath3And (3) dropwise adding the mixture into N, N-Dimethylformamide (DMF), and stirring for 1-2 h to obtain the composite material.
In the above preparation method R2-CHO with and R1The reaction time of-H is 4-8H.
In the preparation method, the reaction time of the compound I and the Vilsmeier reagent is 8-24 h.
In the preparation method, the reaction time of the compound II and the cyanoacetic acid is 8-12 h.
In the preparation method, the bromination reaction time of the compound I and the N-bromosuccinimide is 2-4 h.
Compounds III and (OH) of the above preparation2B-R3The reaction time of-CHO is 8-16 h.
In the preparation method, the reaction time of the compound IV and the cyanoacetic acid is 8-12 h.
The synthesis route of the triarylmethane compound comprises the following steps:
the specific synthetic steps of the triarylmethane compound are as follows:
the synthesis process of the triarylmethane compound is carried out in an inert atmosphere;
(1) r is to be2-CHO with and R1mixing-H with the mol ratio of 1: 8-12, and adding a small amount of NaHSO4·SiO2As a catalyst, stirring and refluxing for 4-8 h at 80-100 ℃, and cooling to room temperature; carrying out suction filtration, washing the filtrate with an organic solvent, and spin-drying the solvent; drying the obtained solid, and then performing column chromatography separation to obtain a compound I;
(2) under ice-water bath, POCl was added3Adding dropwise into N, N-Dimethylformamide (DMF), and reacting DMF with POCl3Stirring for 1-2 h to obtain a Vilsmeier reagent, wherein the molar ratio of the Vilsmeier to the Vilsmeier is 5-1: 1; then the obtained Vilsmeier reagent is dripped into a compound I dissolved in a solvent, the compound I and POCl3The molar ratio of (1: 1) - (8), stirring and reacting at 25-120 ℃ for 8-24 hours, pouring the product into ice water, and adjusting the pH value to be neutral by using a NaOH aqueous solution; separating the crude product by column chromatography to obtain a compound II;
(3) dissolving a compound I in DMF, placing the mixture in an ice water bath at the temperature of-5 ℃, slowly adding N-bromosuccinimide into the compound I in a molar ratio of 1:1, stirring for 10-30 min, and stirring at room temperature for reaction for 2-4 h; pouring the reaction product into crushed ice, extracting with ethyl acetate, combining organic phases, removing the solvent under reduced pressure, and performing column chromatography separation to obtain a compound III;
(4) reacting compound III, (OH)2B-R3-CHO，K2CO3Adding the mixture into a reaction kettle according to the molar ratio of 1:1: 8-12, taking tetratriphenylphosphine palladium as a catalyst, and taking toluene or chloroform as a solvent for reflux stirring; pouring the product into water, extracting with dichloromethane, separating liquid, combining organic phases, drying to remove the solvent, and separating by column chromatography to obtain a compound IV;
(5) adding a compound II or IV and cyanoacetic acid into a flask according to a molar ratio of 1: 6-10, adding a small amount of ammonium acetate, taking acetic acid as a solvent, heating, stirring and refluxing for 8-12 h; pouring into ice water, extracting with chloroform, separating liquid, and drying organic phase; and (4) carrying out column chromatography on the rotary evaporation solvent to obtain the triarylmethane compound.
The invention also provides an application of the triarylmethane compound, which is characterized in that the triarylmethane compound with the structure shown in the formula 1 or the formula 2 is used as a photosensitive dye for preparing a dye-sensitized solar cell material.
The application is that the FTO conductive glass coated with the titanium dioxide nanocrystals is soaked in the tetrahydrofuran solution of the triarylmethane compound to prepare the photoanode of the dye-sensitized solar cell.
The preparation steps and the battery performance test of the solar battery are as follows:
(1) preparation of the photo-anode: washing FTO conductive glass (3.5 cm x 10 cm) with deionized water and absolute ethyl alcohol in sequence, and drying for later use; screen-printing titanium dioxide transparent layer slurry on cleaned FTO substrate, and drying at 130 deg.C for 6min on temperature-controlled titanium heating plate to obtain TiO2A film; then calcining the printed titanium dioxide film under the condition of flowing air, sintering at the high temperature of 500 ℃ for 30min, and then slowly returning to the room temperature; it was then placed in 40mM TiCl4Treating in water solution at constant temperature of 70 deg.C for 40min, sequentially washing with deionized water and ethanol, blow-drying, and baking at 500 deg.C for 25 min;
(2) sensitization of the photo-anode: heat treating the prepared mesoporous titanium dioxide film at 500 ℃ for 30min, naturally cooling to 80 ℃, and then adding a dye solution (5 x 10)-4mol.L-1THF solution of (a), sensitizing for 12-24 h; cleaning with acetonitrile after sensitization and drying for later use;
(3) preparing a counter electrode: plating Pt as a catalyst layer on the pretreated FTO conductive glass substrate, and then drilling large and small holes on a non-conductive surface for later use;
(4) assembling the battery: the sensitized sunlight is exposedPlaced on a hot press in a polar upward direction on TiO2Covering a Surlyn ring with the thickness of 30 mu m around the film, covering the counter electrode, and then carrying out heat sealing at 100 ℃ for 2 min;
(5) electrolyte injection: dripping 1 drop of electrolyte on the small hole of the counter electrode, vacuumizing by using a diaphragm pump to ensure that no bubbles exist between the two electrodes, and sealing to prepare the dye-sensitized solar cell;
(6) and (3) testing the battery performance: leads are respectively led out from a working electrode and a counter electrode of the battery and are connected to a battery performance testing device; the effective illumination area of the battery is as follows: 0.16cm2: the test light source is: solar simulator (model LS 1000-4S-AM1.5G-1000W) provides 100mWcm-2The radiant light of (a); data acquisition: keithley2602 digital source table.
The invention has the beneficial effects that: the triarylmethane compound with a novel structure is synthesized by repeated tests, and the triarylmethane compound has the advantages of wide raw material source, low price, simple preparation method, low cost and industrial production; the triarylmethane compound is found to have good photoelectric conversion performance for the first time, can be used as a photosensitive dye for preparing dye-sensitized solar cell materials, widens the material selection range for the dye-sensitized solar cells, reduces the cost of the dye-sensitized solar cells, and is expected to become a novel dye-sensitized solar cell material.
Drawings
Fig. 1 is a schematic diagram showing a basic structure of a dye-sensitized solar cell in which a triarylmethane compound according to the present invention is used as a sensitizing dye: 1 is an electrolyte; 2 is a triarylmethane compound of the invention; 3 is a counter electrode; 4 is titanium dioxide; and 5, a photo anode.
FIG. 2 shows triarylmethane compounds synthesized in examples 1-4 in tetrahydrofuran (2 x 10)-5M) ultraviolet-visible absorption spectrum: 1 is triarylmethane compound 3 synthesized in example 1; 2 is true2, synthesis of triarylmethane compound 6; triarylmethane compound 10 synthesized in example 3; 4 is triarylmethane compound 13 synthesized in example 1.
Detailed Description
The invention will now be illustrated in detail by the following examples, which are intended only for a better understanding of the invention and are not intended to be limiting
Making the scope of the invention.
Example 1
Synthesis of triarylmethane Compound 3
(1) Synthesis of trithiophene methane 1:
1.12g of 2-thiophenecarboxaldehyde, 20mL of thiophene, 2g of NaHSO4·SiO2Placing the mixture into a three-neck flask, and stirring and refluxing at 85 ℃; after 6h, cool to room temperature. Carrying out suction filtration on the reactant, washing with dichloromethane, and spin-drying the solvent; petroleum ether is used as eluent, and the pure product is obtained through chromatographic purification and separation by 200-300-mesh silica gel and is a white solid, and the yield is 41%. Melting point: 51-53 ℃.
(2) Synthesis of trithiophene methane-carboxaldehyde 2:
under the protection of argon, under the ice-water bath, 2.45g of POCl3Dropwise adding the mixture into 1, 2-dichloroethane solution of 1.17g of DMF, stirring, and continuously reacting for 1 hour; adding compound 1 (1.04 g) dissolved in 1, 2-dichloroethane, stirring at room temperature for 2h, and heating and refluxing for 12 h; cooling to room temperature, pouring into crushed ice, adding a sodium acetate solution (1 mol/L), extracting twice with dichloromethane, drying, spinning out the solvent, and performing column chromatography to obtain a product 2 with the yield of 45%;1HNMR(CDCl3)(ppm):6.14(s,1H)，6.96-6.98(m,4H)，7.04(d,1H)，7.26-7.27(m,2H)，7.63(d,1H)，9.85(s,1H)。
(3) synthesis of triarylmethane compound 3:
0.435g of intermediate 2, 0.88g of cyanoacetic acid, 0.03g of ammonium acetate and 20mL of acetic acid are added into a 100mL three-neck flask, and stirred and refluxed at 120 ℃ for 8 hours; and cooling to room temperature, pouring the crude product into ice water, extracting with chloroform, combining organic phases, drying, and performing column chromatography to obtain the triarylmethane compound 3 with the yield of 58.7%. (ii) a1HNMR([D6]DMSO)(ppm):6.52(s,1H)，6.99-7.00(m,4H)，7.33(d,1H)，7.47-7.49(m,2H)，7.55(d,1H)，8.03(s,1H)。
Example 2
Synthesis of triarylmethane Compound 6
(1) Synthesis of bromotrithiophene methane 4:
placing 0.5g of DMF solution of the compound 1 in an ice water bath at the temperature of-5 ℃, dropwise adding 0.338g of DMF solution of NBS, stirring for 20min, and stirring for 2h at room temperature; then pouring the crude product into ice water, extracting with ethyl acetate, combining organic phases, drying, decompressing, distilling the solvent by rotary evaporation and carrying out column chromatography (petroleum ether) to obtain pink oily matter, wherein the yield is 45%;1HNMR(CDCl3)(ppm):6.03(s,1H)，6.68(d,1H)，6.9(d,1H)，6.96-6.97(m,4H)，7.25(d,2H)。
(2) synthesis of trithiophene methane thiophene carboxaldehyde 5:
in a three-necked flask, 1g of Compound 4, 0.45g of 5-carboxaldehyde-2-thiopheneboronic acid was dissolved in 30mL of toluene, and 5mL of potassium carbonate solution and Pd (PPh3)4 (0.15 g) were added to replace argon; refluxing at 90 ℃, and stirring for 10 h; cooling and spin-drying the toluene; washing with water, extracting, mixing organic phases, and dryingDrying, removing the solvent by spinning, and performing silica gel chromatography to obtain a light red solid 5 with the yield of 34.3%;1HNMR(CDCl3)(ppm):6.09(s,1H)，6.88-6.89(m,2H)，6.97-6.98(m,4H),，7.17(d,1H)，7.21(d,1H)，7.27(d,1H)，7.640(d,1H)，9.84(s,1H)。
(3) synthesis of triarylmethane compound 6:
the synthesis method was the same as (3) in example 1 except that the starting materials were changed;1HNMR([D6]DMSO)(ppm):6.47(s,1H)，6.96-6.97(m,2H)，7.01-7.03(m,3H)，7.34(d,1H)，7.38(d,1H)，7.49(d,1H)，7.65(d,1H)，8.07(s,1H)。
example 3
Synthesis of triarylmethane Compound 10
(1) Synthesis of hexyltrithiophene methane thiophene carboxaldehyde 9:
the synthesis method is the same as that of (2) in example 2, except that raw materials are replaced;1HNMR(CDCl3)(ppm):5.91(s,1H)，6.61(d,2H)，6.75(d,2H)，6.89(d,1H)，7.17(d,1H)，7.20(d,1H)，7.63(d,1H)，9.83(s,1H)。
(2) synthesis of triarylmethane compound 10:
the synthesis method is the same as (3) in example 1, except that the raw materials are replaced;1HNMR([D6]DMSO)(ppm):6.24(s,1H)，6.68(d,2H)，6.79(d,2H)，6.94(d,1H)，7.31(d,1H)，7.36(d,1H)，7.63(d,1H)，8.05(s,1H)。
example 4
Synthesis of triarylmethane Compound 13
(1) Synthesis of triarylmethane thiophene carboxaldehyde 12:
the synthesis method is the same as that of (2) in example 2, except that raw materials are replaced;1HNMR(CDCl3)(ppm):5.90(s,1H)，6.86(d,2H)，6.96-6.97(m,2H)，7.24-7.25(m,2H)，7.37-7.40(m,3H)，7.65(d,2H)，7.74(s,1H)，9.89(s,1H)。
(2) synthesis of triarylmethane compound 13:
the synthesis method is the same as (3) in example 1, except that the raw materials are replaced;1HNMR([D6]DMSO)(ppm):6.16(s,1H)，6.90-6.91(m,2H)，6.99-7.01(m,2H)，7.43-7.47(m,4H)，7.75(d,1H)，7.79(d,2H)，8.01(d,1H)，8.47(s,1H)，13.78(s,1H)。
example 5
The four triarylmethane compounds of examples 1-4 were tested for uv-vis absorption and fluorescence and the data is summarized in the following table:
TABLE 1 comparison of maximum UV-visible absorption and maximum fluorescence emission wavelengths (nm) data for the dyes of examples 1-4
| Dye material | Maximum ultraviolet visible absorption wavelength (nm) | Maximum fluorescence emission wavelength (nm) |
| 3 (example 1) | 343 | 430 |
| 6 (example 2) | 404 | 497 |
| 10 (example 3) | 405 | 504 |
| 13 (example 4) | 392 | 449 |
Example 6
The triarylmethane compounds synthesized in the examples 1-4 are respectively assembled into batteries according to the preparation steps of the dye-sensitized solar battery in the specification, and leads are respectively led out from the photo-anode and the photo-cathode and connected to a battery performance testing device; the effective illumination area of the cell was 0.16cm2, and 100mWcm was provided by a solar simulator (model LS 1000-4S-AM1.5G-1000W)-2The radiant light of (a); table 2 summarizes the photovoltaic parameters of the assembled cells under standard solar am1.5g illumination.
Table 2 photovoltaic parameters of cells assembled from triarylmethane compounds in examples 1 to 4 under standard sunlight am1.5g irradiation
Claims (7)
1. A triarylmethane compound having the structure of formula 1 or formula 2:
wherein,
R1is selected fromOne of (1);
R2is selected fromOne of (1);
R3is selected fromOne of (1);
R4、R5、R6and R8Each independently selected from C3～9One of the straight-chain alkyl groups of (1), or one of methoxy, ethoxy and propoxy, or a hydrogen atom.
2. A process for preparing a triarylmethane compound according to claim 1 wherein R is first reacted under an inert gas atmosphere2-CHO with and R1reacting-H at 80-100 ℃ to obtain a compound I; reacting the obtained compound I with a Vilsmeier reagent at 25-120 ℃ to generate a compound II; carrying out reflux reaction on the obtained compound II and cyanoacetic acid in an acetic acid solution to obtain a triarylmethane compound with a structure shown in a formula 2;
or, firstly, carrying out bromination reaction on the obtained compound I and N-bromosuccinimide at the temperature of-5 ℃ to generate a compound III; the resulting compounds III and (OH)2B-R3-CHO is refluxed in toluene or chloroform to obtain a compound IV; carrying out reflux reaction on the obtained compound IV and cyanoacetic acid in an acetic acid solution to obtain a triarylmethane compound with the structure of the formula 1;
compound I
Compound II
Compound III
And (3) a compound IV.
3. The method of claim 2, wherein R is2-CHO and R1The molar ratio of-H is 1: 8-12; compound I and POCl3The molar ratio of (A) to (B) is 1: 1-8; the molar ratio of the compound II to the cyanoacetic acid is 1: 6-10; the molar ratio of the compound IV to the cyanoacetic acid is 1: 6-10; the Vilsmeier reagent is POCl3And (3) a solution of N, N-dimethylformamide.
4. The process of claim 2 wherein said Vilsmeier reagent is POCl3Wherein the N, N-dimethylformamide is POCl3The molar ratio of (A) to (B) is 5-1: 1.
5. The method of claim 2, wherein R is2-CHO with and R1The reaction time of-H is 4-8H; the reaction time of the compound I and the Vilsmeier reagent is 8-24 h; the reaction time of the compound II and cyanoacetic acid is 8-12 h; the bromination reaction time of the compound I and N-bromosuccinimide is 2-4 h; compounds III and (OH)2B-R3The reaction time of-CHO is 8-16 h; the reaction time of the compound IV and the cyanoacetic acid is 8-12 h.
6. Use of the triarylmethane compound according to claim 1, wherein the triarylmethane compound having the structure of formula 1 or 2 is used as a photosensitizing dye in the preparation of a dye-sensitized solar cell material.
7. The application as claimed in claim 6, wherein the FTO conductive glass coated with the titanium dioxide nanocrystals is soaked in the tetrahydrofuran solution of the triarylmethane compound to prepare the photoanode of the dye-sensitized solar cell.
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