CN112608617B - Triphenothiazinyl zinc porphyrin dye and preparation method thereof - Google Patents
Triphenothiazinyl zinc porphyrin dye and preparation method thereof Download PDFInfo
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- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 159
- 238000001035 drying Methods 0.000 claims description 130
- 238000006243 chemical reaction Methods 0.000 claims description 79
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 56
- 238000005303 weighing Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 40
- 238000004809 thin layer chromatography Methods 0.000 claims description 39
- 239000000376 reactant Substances 0.000 claims description 38
- 238000001291 vacuum drying Methods 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 34
- 239000012074 organic phase Substances 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 238000010898 silica gel chromatography Methods 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000013375 chromatographic separation Methods 0.000 claims description 7
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- -1 10- (3-isooctyl) -3, 7-dibromo-phenothiazine Chemical compound 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 239000000126 substance Substances 0.000 claims 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 claims description 4
- FKZSPBKGUNSVCV-UHFFFAOYSA-N 2-dodecoxybenzaldehyde Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C=O FKZSPBKGUNSVCV-UHFFFAOYSA-N 0.000 claims description 3
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 3
- RWVZVMMMBBHQIJ-UHFFFAOYSA-N CCC(CCC(C)C)N1C2=CC=CC=C2SC2=C1C=CC=C2 Chemical compound CCC(CCC(C)C)N1C2=CC=CC=C2SC2=C1C=CC=C2 RWVZVMMMBBHQIJ-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 3
- PBTPREHATAFBEN-UHFFFAOYSA-N dipyrromethane Chemical compound C=1C=CNC=1CC1=CC=CN1 PBTPREHATAFBEN-UHFFFAOYSA-N 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- REIZEQZILPXYKS-UHFFFAOYSA-N methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1B1OC(C)(C)C(C)(C)O1 REIZEQZILPXYKS-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 3
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- KVSDJJCSMYLSDB-UHFFFAOYSA-N CCC(CCC(C)C)N1C(C=CC(Br)=C2)=C2SC2=CC=CC=C12 Chemical compound CCC(CCC(C)C)N1C(C=CC(Br)=C2)=C2SC2=CC=CC=C12 KVSDJJCSMYLSDB-UHFFFAOYSA-N 0.000 claims description 2
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 2
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000010828 elution Methods 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004032 porphyrins Chemical group 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical class 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
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/12—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton
- C09B47/16—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton having alkyl radicals substituted by nitrogen atoms
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a triphenothiazinyl zinc porphyrin dye and a preparation method thereof. The method is characterized in that a triphenothiazine group is used as a D unit to be connected with a zinc porphyrin core, one benzene ring is used as a bridging (pi) unit, carboxylic acid is used as an electron-withdrawing (A) unit, diazosulfide containing triple bonds is inserted between the zinc porphyrin core and the pi unit and used as an auxiliary A unit, the transition energy level of electrons in molecules is adjusted, and the absorption spectrum is widened. According to the synthetic route of the triphenothiazinyl zinc porphyrin dye, the prepared triphenothiazinyl zinc porphyrin dye has good absorption on sunlight in a visible light region. Has good application potential in DSSC.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a triphenothiazinyl zinc porphyrin dye and a preparation method thereof.
Technical Field
Dyes, as key components in Sensitized Solar Cells (DSSC), play a decisive role in the performance of DSSCs. Among them, zinc porphyrin dyes are the most promising sensitizer in DSSCs in recent years. The zinc porphyrin structure is an aromatic macrocycle with an 18-pi electronic framework, which shows a stronger absorption soret band and a Q band in the range of 400-500nm to 500-600nm and has stronger molar extinction coefficient, so that the zinc porphyrin dye has stronger light capture capability in visible light and even near infrared regions. In addition, the porphyrin structure molecule has four meso-sites and eight beta-sites, which is convenient for modification of the structure. Since the pioneering use of chlorophyll derivatives and porphyrins as dye sensitizers in DSSC from group Gr ä tzel (Nature 1991,353: 737-. At present, the DSSC photoelectric conversion efficiency based on zinc porphyrin dye reaches 14.64% (Chemistry Commun 2015, 51, 15894-15897). In addition, phenothiazine is a D (donor) unit with good electron donating property, has wide application in zinc porphyrin and pure organic DSSC, and achieves better effect (Royal society of chemistry 2020, 13, 1617-1657). The triphenothiazine amine is a triphenylamine-like structure, and the triphenothiazine amine serving as a D unit is not reported in the research of zinc porphyrin-like DSSC.
Based on the analysis, the invention designs and prepares the zinc porphyrin dye containing the triphenothiazine group.
Disclosure of Invention
The invention aims to provide a triphenothiazinyl zinc porphyrin dye and a preparation method thereof.
According to the invention, a triphenothiazine group is used as a D unit to be connected with a zinc porphyrin core, one benzene ring is a bridging (pi) unit, carboxylic acid is an electron-withdrawing (A) unit, and diazosulfide containing a triple bond is inserted between the zinc porphyrin core and the pi unit as an auxiliary A unit to adjust the transition energy level of electrons in molecules and broaden absorption spectra.
The molecular structure of the triphenothiazinyl zinc porphyrin dye provided by the invention is shown in figure 1; the specific synthetic route is shown in figure 2.
The preparation method of the triphenothiazinyl zinc porphyrin dye comprises the following specific steps:
(1) weighing 1 mol part of dipyrromethane and 1 mol part of dodecyloxybenzaldehyde, adding into dichloromethane, stirring strictly in the dark at room temperature for 10min under the protection of argon gas to fully dissolve; 0.6 molar part of trifluoroacetic acid is added into a needle head and stirred for 4 hours, and then 1.2 molar parts of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone are added and stirred for 1 hour. And tracking the reaction by using thin layer chromatography until the concentration of the reactant is basically unchanged, adding triethylamine to neutralize the mixed solution, and stopping the reaction. And (3) post-treatment: and (3) carrying out spin drying, carrying out silica gel column chromatography separation and purification, collecting a product, carrying out spin drying to obtain a dark purple solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 3.
(2) Weighing 1 molar part of the intermediate 3, adding the intermediate into dichloromethane, stirring at room temperature and dissolving; after 2 parts by mole of N-bromosuccinimide were sufficiently dissolved in 50mL of a methylene chloride solution, it was added to a two-necked flask and stirred at room temperature for 1 hour. The reaction was followed by thin layer chromatography until the concentration of the reactants remained essentially unchanged and quenched with acetone. And (3) post-treatment: and (4) performing spin drying, performing silica gel column chromatographic separation, collecting a product, performing spin drying to obtain a dark purple solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 4.
(3) Weighing 1 molar part of the intermediate 4, adding the intermediate into dichloromethane, stirring at room temperature and dissolving; weighing 20 molar parts of anhydrous zinc acetate, dissolving in a methanol solution, adding into a two-necked bottle, stirring and refluxing at room temperature for 12h, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: and (3) spin-drying, dissolving the dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, performing silica gel column chromatographic separation, collecting a product, spin-drying to obtain a light purple solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 5.
(4) Weighing 2 molar parts of 4, 7-dibromo-2, 1, 3-benzothiadiazole and 1 molar part of 4-methoxycarbonylphenylboronic acid pinacol ester, adding the mixture into tetrahydrofuran, stirring and dissolving, and protecting with argon. Adding 0.02 molar part of tetrakistriphenylphosphine palladium and 6mL of potassium carbonate with the concentration of 2M, heating and refluxing for 12h, tracking the reaction by using thin layer chromatography until the concentration of the reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain white powder, and drying in vacuum drying oven to constant weight to obtain intermediate 8.
(5) Weighing tetrahydrofuran and triethylamine with the volume ratio of 2: 1; 1 molar part of the intermediate 8, 0.05 molar part of palladium dichlorobis (triphenylphosphine) and 0.05 molar part of copper iodide were weighed into a two-necked flask, and stirred under reflux for 15min under the protection of argon. And (3) pumping 20 mol parts of trimethylsilylacetylene into a needle, stirring and refluxing for 12h, tracking the reaction by using a thin layer chromatography until the concentration of the reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying and collecting the crude product. Tetrahydrofuran and methanol with the volume ratio of 1:1 are weighed, potassium hydroxide is weighed, and all crude products are added into a two-mouth bottle. The mixture was stirred at room temperature for 1 hour, followed by thin layer chromatography until the concentration of the reaction mixture became substantially constant, and the reaction was stopped. And (3) post-treatment: and (3) spin-drying, dissolving the dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, performing silica gel column chromatographic separation, collecting a product, spin-drying to obtain light yellow powder, and drying in a vacuum drying oven to constant weight to obtain an intermediate 9. The amount of potassium hydroxide is required to be 1 eq and 1M aq.
(6) Weighing 1 mol part of intermediate 5, 0.8 mol part of intermediate 9, 0.4 mol part of tris (dibenzylideneacetone) dipalladium and 1.7 mol part of triphenylarsine, adding into a mixed solvent of tetrahydrofuran/triethylamine with the volume ratio of 3:1, stirring and dissolving, protecting with argon, heating and refluxing, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing, extracting, collecting an organic phase, spin-drying, performing silica gel column chromatographic separation, collecting a product, spin-drying to obtain a green solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 10.
(7) Weighing 1 molar part of 10- (3-isooctyl) -phenothiazine, dissolving in acetic acid, and stirring and dissolving in an ice-water bath; 3 molar parts of nitric acid are weighed and reacted for 12 hours. And (3) post-treatment: adding ethanol/water with the volume ratio of 6:1 to quench the reaction, drying the reaction product by spinning, dissolving the reaction product by using dichloromethane, washing the reaction product by using water, extracting the reaction product, collecting an organic phase, drying the organic phase by using a vacuum drying oven to constant weight to obtain an intermediate 12.
(8) Weighing 1 mol part of intermediate 12, 1 mol part of reduced iron powder and 10 mol parts of ammonium chloride; weighing tetrahydrofuran/ethanol/water with a volume ratio of 4:4:2, adding the tetrahydrofuran/ethanol/water into a two-mouth bottle, stirring and dissolving, under the protection of argon, heating and refluxing, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with neutral alumina column chromatography, collecting product, and spin-drying to obtain intermediate 13.
(9) Weighing 1 mol part of intermediate 11, 2 mol parts of intermediate 13, 3 mol parts of sodium tert-butoxide, 0.05 mol part of palladium acetate and 0.1 mol part of 1, 1-bis (diphenylphosphine) ferrocene; measuring a toluene solution, adding the toluene solution into a two-mouth bottle, stirring and dissolving, under the protection of argon, heating and refluxing for 6 hours, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain light red oily substance, and vacuum drying to constant weight to obtain intermediate 14.
(10) Weighing 1 molar part of intermediate 14, 2 molar parts of 10- (3-isooctyl) -3, 7-dibromo-phenothiazine, 3 molar parts of sodium tert-butoxide and 0.05 molar part of palladium acetate; measuring a toluene solution, adding the toluene solution into a two-mouth bottle, stirring and dissolving, carrying out argon protection, heating and refluxing for 6 hours, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography, collecting a product, spin-drying to obtain a light yellow solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 16.
(11) Weighing 1 molar part of intermediate 16, 1.5 molar parts of pinacol diboron, 0.03 molar part of [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and 3 molar parts of potassium acetate; weighing tetrahydrofuran/methanol solution with a volume ratio of 4:1, adding the solution into a two-mouth bottle, stirring and dissolving, under the protection of argon, heating and refluxing for 6 hours, tracking the reaction by using thin-layer chromatography until the concentration of reactants is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain light yellow solid, and drying in vacuum drying oven to constant weight to obtain intermediate 17.
(12) Weighing 1 molar part of the intermediate 10, 2 molar parts of the intermediate 17, 3 molar parts of potassium acetate and 0.05 molar part of tetrakistriphenylphosphine palladium; weighing tetrahydrofuran and water with the volume ratio of 10:1, adding the tetrahydrofuran and the water into a two-mouth bottle, fully stirring and refluxing for 12 hours under the protection of argon, tracking the reaction by using thin layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, separating by silica gel column chromatography, collecting the product, spin-drying to obtain dark green solid, and drying in a vacuum drying oven to constant weight to obtain intermediate 18.
(13) Weighing 1 molar part of intermediate 18 and 10 molar parts of lithium hydroxide monohydrate, dissolving in water, weighing tetrahydrofuran, adding into a two-mouth bottle, stirring and refluxing the mixture for 12 hours under the protection of argon, tracking the reaction by using thin layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography to obtain a dark green solid product, and drying in a vacuum drying oven to constant weight to obtain the triphenothiazinyl zinc porphyrin dye.
The triphenothiazinyl zinc porphyrin dye provided by the invention has good absorption on sunlight in a visible light region, and has good application potential in DSSC.
Drawings
FIG. 1 is a molecular structural diagram of a triphenothiazinyl zinc porphyrin dye prepared according to an example of the present invention.
FIG. 2 is a diagram showing a synthesis scheme of a triphenothiazinyl zinc porphyrin dye T-4 in an example of the present invention.
FIG. 3 is a graph showing the UV-VIS absorption spectrum of a triphenothiazinyl zinc porphyrin dye in tetrahydrofuran according to an example of the present invention.
Detailed Description
Example (b):
(1) and (3) synthesis of an intermediate 3: weighing (3.07 g, 21.00 mmol) dipyrromethane and (9.98 mL, 21.00 mmol) dodecyloxybenzaldehyde into a three-necked flask; weighing 500mL of dichloromethane, adding the dichloromethane into a three-necked bottle with 1000mL, protecting with argon, and stirring strictly in the dark at room temperature for 10min to fully dissolve the dichloromethane; adding (0.92 mL, 12.60 mmol) trifluoroacetic acid into a needle, and stirring for 4 h; then 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (5.72g, 25.20mmol) was weighed out and added to a three-necked flask and stirred for 1 hour. The reaction was followed by thin layer chromatography until the concentration of the reactant was substantially unchanged, and 4mL of triethylamine was measured to neutralize the mixed solution and the reaction was stopped. And (3) post-treatment: spin-drying, gradient eluting with silica gel column chromatography (dichloromethane: petroleum ether elution = 5: 1), collecting product 3, spin-drying to obtain dark purple solid, and oven-drying in vacuum drying oven to constant weight to obtain intermediate 3 (3.78 g, yield 15%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 10.24-10.10 (s，2H)，9.34-9.27 (d，4H)，9.06-8.99 (d，4H)，7.80-7.69 (t，2H)，7.10-7.03 (d，4H)，3.90-3.83 (t，8H)，1.34-1.26 (m，20H)，1.09-1.00(m，10H)，0.96-0.87 (m，30H)，0.79-0.72 (m，8H)，0.66-0.55(m，16H)，0.54-0.45 (m，8H)，-3.06(s，2H). MS:m/z =1199
(2) Synthesis of intermediate 4: weighing 200mL of dichloromethane, and adding the dichloromethane into a 500mL two-mouth bottle; weighing intermediate 3 (1.80 g, 1.50 mmol), stirring at room temperature for dissolving; after N-bromosuccinimide (0.54 g, 3.00 mmol) was sufficiently dissolved in 50mL of a dichloromethane solution, it was added to a two-necked flask and stirred at room temperature for 1 hour. Tracking the reaction by thin layer chromatography until the concentration of the reactant is basically unchanged, and quenching the reaction by acetone (15 mL); and (3) post-treatment: spin-drying, gradient eluting with silica gel column chromatography (dichloromethane: petroleum ether elution = 5: 1), collecting product 4, spin-drying to obtain dark purple solid, and vacuum drying to constant weight to obtain intermediate 4 (1.80 g, product)Rate: 90%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 9.57-9.51 (d，4H)，8.86-8.81 (d，4H)，7.77-7.69 (t，2H)，7.05-7.00 (d，4H)，3.90-3.84 (t，8H)，1.36-1.07 (m，20H)，1.03-0.95(m，16H)，0.94-0.82 (t，24H)，0.75-0.65 (m，8H)，0.62-0.51 (m，16H)，0.48-0.40 (m，8H) -2.57 (s，2H) . MS:m/z =1357
(3) Synthesis of intermediate 5: weighing 300mL of dichloromethane, adding the dichloromethane into a 1000mL two-neck bottle, weighing intermediate 4 (1.80 g, 1.35 mmol), and stirring at room temperature for dissolving; after zinc acetate (6.00 g, 27.00 mmol) was weighed out and dissolved in 100mL of methanol solution, it was put into a two-necked flask, stirred at room temperature under reflux for 12 hours, followed by thin layer chromatography until the concentration of the reactant was substantially unchanged, and the reaction was stopped. And (3) post-treatment: spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting the organic phase, spin-drying, separating with silica gel column chromatography (dichloromethane: petroleum ether elution = 5: 1), collecting product 5, spin-drying to obtain a light purple solid, and drying in a vacuum drying oven to constant weight to obtain intermediate 5 (1.66 g, yield 87%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 9.72-9.66 (d，4H)，8.99-8.90 (d，4H)，7.79-7.70 (t，2H)，7.08-7.01 (d，4H)，3.94-3.85 (t，8H)，1.37-1.06 (m，20H)，1.05-0.93(m，20H)，0.91-0.81 (m，20H)，0.70-0.63 (m，8H)，0.59-0.51(m，8H)，0.51-0.44 (m，8H)，0.42-0.35(m，8H) . MS:m/z =1418
(4) Synthesis of intermediate 8: weighing 50mL of tetrahydrofuran, and adding into a 100mL two-mouth bottle; weighing 4, 7-dibromo-2, 1, 3-benzothiadiazole (2.20 g, 7.60 mmol) and 4-methoxycarbonylphenylboronic acid pinacol ester (1.00 g, 3.80 mmol), adding into a two-neck bottle, stirring and dissolving, and protecting with argon. Tetratriphenylphosphine palladium (86.60 mg, 0.08 mmol) and potassium carbonate (6 mL, 2M) were added, the mixture was refluxed at elevated temperature for 12h, and the reaction was stopped by following the reaction with thin layer chromatography until the concentration of the reactant was substantially constant. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting the organic phase, spin-drying, separating with silica gel column chromatography (dichloromethane/petroleum ether = 1:1, gradient elution), collecting the product 8, spin-drying to obtain white powder, and drying in a vacuum drying oven to constant weight to obtain the intermediate 8 (0.53 g, 40%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 8.27-8.19（d，2H），8.04-7.95（m，3H），7.69-7.64（d，1H），4.03-3.95（s，3H）. MS:m/z =348
(5) Synthesis of intermediate 9: measuring tetrahydrofuran/triethylamine (24 mL/12 mL); intermediate 8 (0.53 g, 1.50 mmol), bis (triphenylphosphine) dichloropalladium (53 mg, 0.08 mmol) and copper iodide (14.20 mg, 0.08 mmol) were weighed into a 100mL two-necked flask, stirred under reflux at 50 ℃ for 15min under argon. Injecting (2.5mL, 30.00mmol) trimethylsilylacetylene into a needle, stirring and refluxing for 12h, tracking the reaction by thin layer chromatography until the concentration of the reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, silica gel column chromatography (dichloromethane/petroleum ether = 1:1, gradient elution) and collecting the crude product. Tetrahydrofuran/methanol (20 mL/20 mL) and potassium hydroxide (1 eq, 1M aq) were measured. And adding the crude product into the mixed solution, stirring for 1h at room temperature, tracking the reaction by using thin layer chromatography until the concentration of the reactant is basically unchanged, and stopping the reaction. And (3) post-treatment: spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting the organic phase, spin-drying, separating with silica gel column chromatography (dichloromethane/petroleum ether = 1:1, gradient elution), collecting product 9, spin-drying to obtain light yellow powder, and drying in a vacuum drying oven to constant weight to obtain intermediate 9 (0.22 g, 50%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 8.26-8.20（d，2H），8.07-8.02（d，2H），7.95-7.91（d，1H），7.78-7.74（d，1H），4.02-3.98（s，3H），3.70-3.66（s，1H）. MS:m/z =294
(6) Synthesis of intermediate 10: measuring tetrahydrofuran/triethylamine (60 mL/20 mL); weighing intermediate 5 (0.75 g, 0.53 mmol), intermediate 9 (0.12 g, 0.42 mmol), dichlorobis (triphenylphosphine) palladium (0.19 g, 0.2 mmol) and triphenylarsine (0.28 g, 0.90 mmol), adding into a two-neck flask, stirring and dissolving, under the protection of argon, refluxing at 50 ℃ for 12h, tracking the reaction by thin layer chromatography until the reactant concentration is basically unchanged, and stopping the reaction. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography (dichloromethane/petroleum ether = 1: 2, gradient elution), collecting product 10, and spin-drying to obtain the final productThe green solid was oven dried to constant weight in a vacuum oven to afford intermediate 10 (69 mg, 10%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 10.03-10.01（d，2H），9.63-9.60（d，2H），9.00-8.98（d，2H），8.88-8.87（d，2H），8.18-8.16（d，1H），8.09-8.06（d，2H），7.99-7.95（d，2H），7.76-7.73（s，3H），7.08-7.04（d，4H），4.01-3.98（s，3H），3.92-3.89（m，8H），1.35-1.02 (m，28H)，1.01-0.88(m，18H)，0.86-0.74 (m，20H)，0.65-0.35 (m，26H). MS:m/z =1634
(7) Synthesis of intermediate 12: weighing 10- (3-isooctyl) -phenothiazine (11.06 g, 35.65 mmol) and 50mL acetic acid, adding into a 250mL two-mouth bottle, and stirring in an ice-water bath for dissolving; nitric acid (5.78 mL, 128.35 mmol) was measured and reacted for 12 h. And (3) post-treatment: adding 70mL of ethanol/water with the volume ratio of 6:1 to quench the reaction, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying to obtain an orange oily liquid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 12 (11.41 g, 89.4%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 8.82-8.79（s，1H），8.84-8.37（d，1H），7.71-7.64（t，1H），7.60-7.50（m，2H），7.41-7.35（t，1H），2.10-2.00（m，1H），1.44-1.20（m，10H），0.95-0.81（t，6H）. MS:m/z =356.16
(8) Synthesis of intermediate 13: weighing intermediate 12 (11.40 g, 31.86 mmol), reduced iron powder (8.96 g, 159.32 mmol) and ammonium chloride (17.31 g, 318.65 mmol); 100mL of tetrahydrofuran/ethanol/water with the volume ratio of 4:4:2 is measured and added into a 250mL two-port bottle to be stirred and dissolved, argon is used for protection, temperature is increased for reflux, thin layer chromatography is used for tracking the reaction until the concentration of a reactant is basically unchanged, and the reaction is stopped. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with neutral alumina column chromatography, collecting product, spin-drying to obtain black oily substance, and oven-drying in vacuum drying oven to constant weight to obtain intermediate 13 (7.10 g, 67.90%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 7.18-7.07（m，2H），6.95-6.80（m，2H），6.75-6.69（d，1H），6.48-6.42（d，2H），5.03-4.66（s，2H），1.85-1.73（m，1H），1.43-1.14（m，10H），0.89-0.74（t，6H）. MS:m/z =326.5。
(9) Synthesis of intermediate 14: 10- (3-isooctyl) -3-bromo-phenothiazine (5.23 g, 13.42 mmol), intermediate 13 (8.80 g, 26.84 mmol), sodium tert-butoxide (3.87 g, 40.26 mmol), palladium acetate (0.15 g, 0.67 mmol), 1-bis (diphenylphosphino) ferrocene (0.74 g, 1.34 mmol) were weighed; 100mL of toluene solution is measured and added into a two-mouth bottle to be stirred and dissolved, the mixture is heated and refluxed for 6 hours at 110 ℃ under the protection of argon, the reaction is tracked by thin layer chromatography until the concentration of reactants is basically unchanged, and the reaction is stopped. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain light red oily substance, and oven-drying in vacuum drying oven to constant weight to obtain intermediate 14 (5.15 g, 67.90%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 7.24-7.17（m，4H），6.98-6.90（m，5H），6.90-6.85（s，2H），6.85-6.78（d，4H），2.04-1.97（m，2H），1.58-1.30（m，20H），1.02-0.92（t，14H）. MS:m/z =639.4。
(10) Synthesis of intermediate 16: intermediate 14 (2.10 g, 3.13 mmol), 10- (3-isooctyl) -3, 7-dibromo-phenothiazine (7.33 g, 15.63 mmol), sodium tert-butoxide (0.90 g, 9.38 mmol), palladium acetate (0.035 g, 0.16 mmol) were weighed; 100mL of toluene solution is measured and added into a two-mouth bottle, the mixture is stirred and dissolved, the mixture is heated and refluxed for 6 hours at the temperature of 110 ℃ under the protection of argon, the reaction is tracked by thin layer chromatography until the concentration of reactants is basically unchanged, and the reaction is stopped. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain light yellow solid, and oven-drying in vacuum drying oven to constant weight to obtain intermediate 16 (3.06 g, 95%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 7.36-7.24（m，3H），7.22-7.13（m，4H），6.98-6.88（m，4H），6.88-6.80（d，5H），6.80-6.70（m，4H），2.03-1.90（m，3H），1.69-1.38（m，4H），1.37-1.13（s，16H），1.05-0.79（m，21H）.MS:m/z =1026。
(11) Synthesis of intermediate 17: weighing intermediate 16 (2.00 g, 1.95 mmol), pinacol ester diboron (0.74 g, 2.93 mmol) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (0.08 g, 0.11 mmol), potassium acetate (0.57 g, 5.86 mmol); 50mL of tetrahydrofuran/methanol solution with the volume ratio of 4:1 is weighed and added into a two-mouth bottle, stirred and dissolved, the mixture is heated and refluxed for 6 hours at 50 ℃ under the protection of argon, the reaction is tracked by thin layer chromatography until the concentration of a reactant is basically unchanged, and the reaction is stopped. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain light yellow solid, and oven-drying in vacuum drying oven to constant weight to obtain intermediate 17 (1.09 g, 52%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 7.66-7.58（t，2H），7.23-7.13（m，4H），6.97-6.72（m，14H），2.05-1.94（m，3H），1.59-1.39（m，15H），1.38-1.24（d，27H），1.01-0.85（m，21H）. MS:m/z =1075。
(12) Synthesis of intermediate 18: intermediate 10 (73 mg, 0.025 mmol), intermediate 17 (54 mg, 0.05 mmol), potassium acetate (7 mg, 0.075 mmol), tetrakistriphenylphosphine palladium (1.40 mg, 0.00125 mmol) were weighed; 55mL of tetrahydrofuran and water with the volume ratio of 10:1 are weighed and added into a two-mouth bottle, the mixture is fully stirred under the protection of argon, the mixture is refluxed for 12 hours at 70 ℃, the reaction is tracked by thin layer chromatography until the concentration of reactants is basically unchanged, and the reaction is stopped. And (3) post-treatment: cooling, spin-drying, separating with silica gel column chromatography, collecting the product, spin-drying to obtain dark green solid, and oven-drying in vacuum drying oven to constant weight to obtain intermediate 18 (42 mg, 75%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 10.15-10.05（d，2H），9.06-9.01（d，2H），8.91-8.86（d，2H），8.85-8.81（d，2H），8.34-8.30（d，1H），8.30-8.25（d，2H），8.22-8.17（d，2H），7.99-7.96（d，1H），7.76-7.70（t，2H），7.58-7.55（t，1H），7.39-7.37（d，1H），7.19-7.13（d，5H），7.06-7.01（d，5H），6.99-6.86（m，8H），6.81-6.76（d，2H），6.73-6.68（d，2H），4.05-4.00（s，3H），3.91-3.82（t，8H），2.01-1.92（m，3H），1.34-1.27（d，40H），1.04-0.98（t，20H），0.94-0.87（m，31H），0.82-0.75（m，20H），0.70-0.61（m，8H），0.59-0.46（m，16H），0.45-0.37（m，8H）. MS:m/z =2495.3。
(13) Weighing intermediate 18 (95 mg, 0.038 mmol) and lithium hydroxide monohydrate (637 mg, 1.52 mmol) and dissolving in 5mL of water; 30mL of tetrahydrofuran is measured and added into a two-mouth bottle, the mixture is stirred and refluxed for 12 hours under the protection of argon, and the reaction is stopped after the concentration of reactants is basically unchanged by tracking the reaction by thin layer chromatography. And (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography to obtain dark green solid product, and oven-drying in vacuum drying oven to constant weight to obtain triphenothiazinyl zinc porphyrin dye (42 mg, 44.7%). 1 H NMR (CDCl 3 ，500MHz) δ (TMS，ppm): 10.18-10.13（d，1H），10.12-10.06（d，1H），9.10-9.02（d，2H），8.95-8.86（d，2H），8.85-8.76（d，2H），8.35-8.24（t，3H），8.22-8.16（d，2H），7.99-7.93（d，2H），7.78-7.67（t，3H），7.19-7.12（t，3H），7.09-6.99（t，5H），6.94-6.87（d，8H），6.82-6.67（d，2H），3.95-3.80（t，8H），1.31-1.27（s，40H），1.05-0.96（t，21H），0.95-0.86（m，30H），0.84-0.76（m，20H），0.70-0.61（m，8H），0.61-0.47（m，16H），0.47-0.39（m，8H）. MS:m/z =2481.3。
The ultraviolet spectrogram in FIG. 3 shows that the spectral response interval of T-4 is 350-700 nm, and the maximum absorption wavelength reaches 646nm, which indicates that the ultraviolet spectrum has better absorption for sunlight in a visible light region.
Claims (2)
1. A triphenothiazinyl zinc porphyrin dye is characterized in that the molecular structure of the triphenothiazinyl zinc porphyrin dye is as follows:
2. a method for preparing a triphenothiazinyl zinc porphyrin dye according to claim 1, comprising the following steps:
(1) weighing 1 mol part of dipyrromethane and 1 mol part of dodecyloxybenzaldehyde, adding into dichloromethane, stirring at room temperature in a strict dark place for 10min under the protection of argon gas to fully dissolve; 0.6 molar part of trifluoroacetic acid is added into a needle head and then stirred for 4 hours, and then 1.2 molar parts of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone are added and stirred for 1 hour; tracking the reaction by using thin-layer chromatography until the concentration of the reactant is basically unchanged, adding triethylamine to neutralize the mixed solution, and stopping the reaction; and (3) post-treatment: performing spin drying, performing silica gel column chromatography separation and purification, collecting a product, performing spin drying to obtain a dark purple solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 3;
(2) weighing 1 molar part of the intermediate 3, adding the intermediate into dichloromethane, stirring at room temperature and dissolving; weighing 2 molar parts of N-bromosuccinimide, fully dissolving in 50mL of dichloromethane solution, adding the solution into a two-neck flask, and stirring at room temperature for 1 h; tracking the reaction by using thin-layer chromatography until the concentration of the reactant is basically unchanged, and quenching the reaction by using acetone; and (3) post-treatment: performing spin drying, performing silica gel column chromatographic separation, collecting a product, performing spin drying to obtain a dark purple solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 4;
(3) weighing 1 molar part of the intermediate 4, adding the intermediate into dichloromethane, stirring at room temperature and dissolving; weighing 20 molar parts of anhydrous zinc acetate, dissolving in a methanol solution, adding into a two-mouth bottle, stirring and refluxing at room temperature for 12h, tracking the reaction by using a thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: spin-drying, dissolving dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography, collecting a product, spin-drying to obtain a light purple solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 5;
(4) weighing 2 molar parts of 4, 7-dibromo-2, 1, 3-benzothiadiazole and 1 molar part of 4-methoxycarbonylphenylboronic acid pinacol ester, adding the mixture into tetrahydrofuran, stirring and dissolving, and protecting with argon; adding 0.02 molar part of tetrakistriphenylphosphine palladium and 6mL of potassium carbonate with the concentration of 2M, heating and refluxing for 12h, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain white powder, and drying in vacuum drying oven to constant weight to obtain intermediate 8;
(5) weighing tetrahydrofuran and triethylamine with the volume ratio of 2: 1; weighing 1 molar part of the intermediate 8, 0.05 molar part of palladium dichlorobis (triphenylphosphine) and 0.05 molar part of copper iodide, adding into a two-mouth bottle, stirring and refluxing for 15min under the protection of argon; stirring and refluxing for 12h after 20 mol parts of trimethylsilylacetylene is injected into the needle, tracking the reaction by using thin-layer chromatography until the concentration of the reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying and collecting a crude product; weighing tetrahydrofuran and methanol with the volume ratio of 1:1, weighing potassium hydroxide, and adding all crude products into a two-mouth bottle; stirring for 1h at room temperature, tracking the reaction by using thin layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: spin-drying, dissolving dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography, collecting a product, spin-drying to obtain light yellow powder, and drying in a vacuum drying oven to constant weight to obtain an intermediate 9; the dosage of the potassium hydroxide is required to be 1 eq and 1M aq;
(6) weighing 1 mol part of intermediate 5, 0.8 mol part of intermediate 9, 0.4 mol part of tris (dibenzylideneacetone) dipalladium and 1.7 mol part of triphenylarsine, adding into a tetrahydrofuran/triethylamine mixed solvent with a volume ratio of 3:1, stirring and dissolving, protecting with argon, heating and refluxing, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography, collecting a product, spin-drying to obtain a green solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 10;
(7) weighing 1 molar part of 10- (3-isooctyl) -phenothiazine, dissolving in acetic acid, and stirring in an ice-water bath to dissolve; weighing 3 molar parts of nitric acid, and reacting for 12 hours; and (3) post-treatment: adding ethanol/water with a volume ratio of 6:1 to carry out quenching reaction, drying by spinning, dissolving by using dichloromethane, washing by using water, extracting, collecting an organic phase, drying by using a vacuum drying oven to constant weight to obtain an intermediate 12;
(8) weighing 1 mol part of intermediate 12, 1 mol part of reduced iron powder and 10 mol parts of ammonium chloride; weighing tetrahydrofuran/ethanol/water with a volume ratio of 4:4:2, adding the tetrahydrofuran/ethanol/water into a two-mouth bottle, stirring and dissolving, carrying out argon protection, heating and refluxing, tracking the reaction by using a thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, performing neutral alumina column chromatographic separation, collecting product, and spin-drying to obtain intermediate 13;
(9) weighing 1 molar part of 10- (3-isooctyl) -3-bromo-phenothiazine, 2 molar parts of intermediate 13, 3 molar parts of sodium tert-butoxide, 0.05 molar part of palladium acetate and 0.1 molar part of 1, 1-bis (diphenylphosphine) ferrocene; measuring a toluene solution, adding the toluene solution into a two-mouth bottle, stirring and dissolving, heating and refluxing for 6 hours under the protection of argon, tracking the reaction by using a thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, performing silica gel column chromatographic separation, collecting a product, spin-drying to obtain a light red oily substance, and drying in a vacuum drying oven to constant weight to obtain an intermediate 14;
(10) weighing 1 molar part of intermediate 14, 2 molar parts of 10- (3-isooctyl) -3, 7-dibromo-phenothiazine, 3 molar parts of sodium tert-butoxide and 0.05 molar part of palladium acetate; measuring a toluene solution, adding the toluene solution into a two-mouth bottle, stirring for dissolving, carrying out argon protection, heating for refluxing for 6 hours, tracking the reaction by using a thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting organic phase, spin-drying, separating with silica gel column chromatography, collecting product, spin-drying to obtain light yellow solid, and drying in vacuum drying oven to constant weight to obtain intermediate 16;
(11) weighing 1 molar part of intermediate 16, 1.5 molar parts of pinacol diboron, 0.03 molar part of [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and 3 molar parts of potassium acetate; weighing tetrahydrofuran/methanol solution with a volume ratio of 4:1, adding the solution into a two-mouth bottle, stirring for dissolving, carrying out argon protection, heating for refluxing for 6 hours, tracking the reaction by using a thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography, collecting a product, spin-drying to obtain a light yellow solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 17;
(12) weighing 1 molar part of the intermediate 10, 2 molar parts of the intermediate 17, 3 molar parts of potassium acetate and 0.05 molar part of tetratriphenylphosphine palladium; measuring tetrahydrofuran and water with a volume ratio of 10:1, adding into a two-mouth bottle, stirring and refluxing for 12h under the protection of argon, tracking the reaction by using thin-layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, separating by silica gel column chromatography, collecting the product, spin-drying to obtain dark green solid, and drying in a vacuum drying oven to constant weight to obtain an intermediate 18;
(13) weighing 1 molar part of intermediate 18 and 10 molar parts of lithium hydroxide monohydrate, dissolving in water, weighing tetrahydrofuran, adding into a two-mouth bottle, stirring and refluxing the mixture for 12 hours under the protection of argon, tracking the reaction by using thin layer chromatography until the concentration of a reactant is basically unchanged, and stopping the reaction; and (3) post-treatment: cooling, spin-drying, dissolving with dichloromethane, washing with water, extracting, collecting an organic phase, spin-drying, separating by silica gel column chromatography to obtain a dark green solid product, and drying in a vacuum drying oven to constant weight to obtain the triphenothiazinyl zinc porphyrin dye.
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Application publication date: 20210406 Assignee: Guangxi Laoma Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000069 Denomination of invention: A zinc porphyrin dye with triphenothiazinyl group and its preparation method Granted publication date: 20220923 License type: Common License Record date: 20221118 |
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