CN111718596B - Method for synthesizing novel phthalocyanine D-pi-A type solar cell dye through click reaction - Google Patents
Method for synthesizing novel phthalocyanine D-pi-A type solar cell dye through click reaction Download PDFInfo
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000012650 click reaction Methods 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 162
- 239000007787 solid Substances 0.000 claims abstract description 47
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 150
- 238000010438 heat treatment Methods 0.000 claims description 139
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 135
- 238000010992 reflux Methods 0.000 claims description 126
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 122
- 239000000243 solution Substances 0.000 claims description 102
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 90
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 90
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 90
- 239000011259 mixed solution Substances 0.000 claims description 90
- 239000002904 solvent Substances 0.000 claims description 90
- 239000003795 chemical substances by application Substances 0.000 claims description 75
- 239000012046 mixed solvent Substances 0.000 claims description 75
- 229910052786 argon Inorganic materials 0.000 claims description 61
- 230000001678 irradiating effect Effects 0.000 claims description 59
- 230000008569 process Effects 0.000 claims description 48
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 45
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 45
- 238000005286 illumination Methods 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 45
- 238000002390 rotary evaporation Methods 0.000 claims description 44
- -1 polytetrafluoroethylene Polymers 0.000 claims description 38
- 230000015572 biosynthetic process Effects 0.000 claims description 35
- 238000003786 synthesis reaction Methods 0.000 claims description 35
- 150000001345 alkine derivatives Chemical group 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims description 30
- 229940043279 diisopropylamine Drugs 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- 229910001220 stainless steel Inorganic materials 0.000 claims description 30
- 239000010935 stainless steel Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 15
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 15
- 238000009833 condensation Methods 0.000 claims description 15
- 230000005494 condensation Effects 0.000 claims description 15
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 15
- 229960002887 deanol Drugs 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- BYVLPDSFDKADOD-UHFFFAOYSA-N C(C=C)(=O)O.IC1=CC=C(C#N)C=C1 Chemical compound C(C=C)(=O)O.IC1=CC=C(C#N)C=C1 BYVLPDSFDKADOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000001540 azides Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- YIFLQBNCXIFWEL-KBXCAEBGSA-N 1-(7-methoxy-benzo[1,3]dioxol-5-yl)-1,2-bis-(2-methyl-but-2-enoyloxy)-propane Natural products COc1cc(cc2OCOc12)[C@H](OC(=O)C(=CC)C)[C@H](C)OC(=O)C(=CC)C YIFLQBNCXIFWEL-KBXCAEBGSA-N 0.000 claims 1
- YIFLQBNCXIFWEL-UHFFFAOYSA-N 2-epilaserine Natural products COc1cc(cc2OCOc12)C(OC(=O)C(=C/C)C)C(C)OC(=O)C(=C/C)C YIFLQBNCXIFWEL-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 10
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000005711 Benzoic acid Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 235000010233 benzoic acid Nutrition 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 60
- 238000001704 evaporation Methods 0.000 description 46
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 42
- 230000000694 effects Effects 0.000 description 15
- 125000002346 iodo group Chemical group I* 0.000 description 13
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 13
- 229920006391 phthalonitrile polymer Polymers 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 238000001308 synthesis method Methods 0.000 description 13
- GHICCUXQJBDNRN-UHFFFAOYSA-N 4-iodobenzoic acid Chemical compound OC(=O)C1=CC=C(I)C=C1 GHICCUXQJBDNRN-UHFFFAOYSA-N 0.000 description 7
- OMXUBCXAGLQCRX-UHFFFAOYSA-N 1-azido-4-butoxybenzene Chemical compound CCCCOC1=CC=C(N=[N+]=[N-])C=C1 OMXUBCXAGLQCRX-UHFFFAOYSA-N 0.000 description 4
- DUHHTLJHLAXGBN-UHFFFAOYSA-N [N-]=[N+]=[N-].C(CCC)C1=CC=CC=C1 Chemical compound [N-]=[N+]=[N-].C(CCC)C1=CC=CC=C1 DUHHTLJHLAXGBN-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- TWZLURXTNNLJGI-UHFFFAOYSA-N 1-azido-4-icosoxybenzene Chemical compound C(CCCCCCCCCCCCCCCCCCC)OC1=CC=C(C=C1)N=[N+]=[N-] TWZLURXTNNLJGI-UHFFFAOYSA-N 0.000 description 2
- JKDXJKOBJNVKJY-UHFFFAOYSA-N 1-azido-4-icosylbenzene Chemical compound C(CCCCCCCCCCCCCCCCCCC)C1=CC=C(C=C1)N=[N+]=[N-] JKDXJKOBJNVKJY-UHFFFAOYSA-N 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- NNGGQBFUEJTJTC-UHFFFAOYSA-N 1-azidopentoxybenzene Chemical compound O(C1=CC=CC=C1)C(CCCC)N=[N+]=[N-] NNGGQBFUEJTJTC-UHFFFAOYSA-N 0.000 description 1
- TXINVMFTFGIFBH-UHFFFAOYSA-N 4-iodo-2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=C(I)C=C1C1=CC=CC=C1 TXINVMFTFGIFBH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- GXXFHWLRFMKMLS-UHFFFAOYSA-N N(=[N+]=[N-])C1=CC=C(C=C1)CCCCC Chemical compound N(=[N+]=[N-])C1=CC=C(C=C1)CCCCC GXXFHWLRFMKMLS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 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
-
- 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
- Y02E10/542—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
The invention relates to a method for synthesizing novel phthalocyanine D-pi-A type solar cell dye by click reaction, belonging to the field of organic photoelectric materials. By the click reaction principle, branched alkyl, alkoxy and dialkyl aniline are introduced to the metal phthalocyanine element, and then the metal phthalocyanine element is accessed to a benzoic acid or cyanoacrylate-like receptor through Sonogashira coupling reaction to form the asymmetric D-pi-A type disc dye compound. The obtained novel phthalocyanine D-Pi-A solar cell dye has good dissolution, strong ultraviolet absorption and strong photoelectric conversion efficiency; the technical route adopts ultraviolet, Nd, YAG solid pulse laser, microwave combined technology and microwave hydrothermal technology, has the advantages of concentrated energy, high reaction rate, no secondary pollution, high product yield and wide application prospect.
Description
[ technical field ]: the invention belongs to the field of organic photoelectric materials, and particularly relates to a method for synthesizing a novel phthalocyanine D-pi-A type solar cell dye through a click reaction.
[ technical background ]: the dye-sensitized solar cell is a novel solar cell which is developed by simulating the photosynthesis principle, and has the main advantages that: the raw materials are rich, the cost is low, the process technology is relatively simple, the method has great advantages in large-area industrial production, all the raw materials and the production process are nontoxic and pollution-free, partial materials can be fully recovered, and the method has important significance for protecting the human environment. The variety of organic solar cell dyes is complex and diverse, and the research on the compounds of the D-Pi-A system as photosensitive dyes has been receiving more and more extensive attention in recent years (Ito S, Zakaeerudin 1S M, Humphry-Baker R, et al, high-efficiency organic-dye-sensitive solar cells, controlled and bynaocrystalline-TiO)2 electrode thickness[J].Advanced Materials,2006,18(9):1202-1205；Koumura N,Wang Z S,Mori S,et al.Alkyl-functionalized organic dyes for efficient molecular photovoltaics[J].Journal of the American Chemical Society,2006,128(44):14256-14257.)。
The phthalocyanine is a compound symmetrical complex which has 18 pi electrons and is completely synthesized artificially, is used as a novel organic photoconductive material, and has the advantages of high chemical and thermal stability, wide spectral response range, good near infrared absorptivity and the like. The phthalocyanine compound can modify or change the performance of the phthalocyanine by changing the substituent group on the phthalocyanine ring and the type of the central metal, and thus can be used as an organic functional dye. And has typical characteristics as a sensitizer: has better absorption in a visible light region, good light, heat and chemical stability, excellent optical and electrical properties and adjustability of a molecular structure. But solubility and film forming properties limit their use in research and applications.
And the click chemistry based on the synthesis of carbon-heteroatom bonds (C-X-C) is developed, so that not only can molecular diversity be simply and efficiently obtained, but also branched alkyl, alkoxy and dialkyl aniline can be introduced through click reaction, so that the compound has good solubility, and higher photoelectric conversion efficiency is obtained.
Based on the consideration, the invention relates to a method for synthesizing novel phthalocyanine D-pi-A type solar cell dye by click reaction. Using ultraviolet, Nd: YAG (Neodymium-doped yttrium aluminum garnet, Nd: Y3Al5O12) The novel phthalocyanine D-pi-A solar cell dye is prepared by a solid pulse laser and microwave combined technology, a microwave hydrothermal technology and a click reaction principle. The ultraviolet, laser and microwave combined technology and the microwave hydrothermal technology can greatly shorten the reaction time and improve the reaction efficiency; taking phthalocyanamide synthesized by modified phthalocyanamide as a matrix, introducing branched alkyl, alkoxy and dialkyl aniline on a metal phthalocyanine element through click reaction, and then accessing a benzoic acid or cyanoacrylate receptor through cross coupling reaction (Sonogashira coupling reaction) between aryl halide or alkenyl halide catalyzed by palladium/copper mixing and terminal alkyne to form a D-pi-A type asymmetric disc dye; the compound has good solubility, excellent ultraviolet absorption and photoelectric conversion efficiency and wide application prospect.
[ summary of the invention ]: the invention aims to provide a method for synthesizing a novel phthalocyanine D-pi-A type solar cell dye by a click reaction. By the click reaction principle, branched alkyl, alkoxy and dialkyl aniline are introduced to the metal phthalocyanine element, and then the metal phthalocyanine element is accessed to a benzoic acid or cyanoacrylate-like receptor through Sonogashira coupling reaction to form the asymmetric D-pi-A type disc dye compound. The ultraviolet, laser and microwave combined technology and the microwave hydrothermal technology adopted in the synthesis process can greatly shorten the reaction time and improve the reaction efficiency; the obtained novel phthalocyanine D-Pi-A solar cell dye has good dissolution, strong ultraviolet absorption and photoelectric conversion efficiency, can meet industrial requirements, and has novelty, practicability and novelty.
[ technical solution of the present invention ]:
the invention provides a method for synthesizing a novel phthalocyanine D-pi-A type solar cell dye by a click reaction, wherein the novel phthalocyanine D-pi-A type solar cell dye is an asymmetric disc-shaped dye molecule, and the structural general formula of the compound is as follows:
wherein R is1Is any one of alkyl, alkoxy and dialkyl amine, and has the following structural general formula:
n is an integer of 4-20;
R2is any one of benzoic acid and cyanoacrylate, and has the following structural formula:
m is any one of Cu, Co, Ni, Zn, Mg and Fe;
the invention provides a method for synthesizing a novel phthalocyanine D-pi-A type solar cell dye by a click reaction, which is realized by the following technical scheme:
A. click reaction
Dissolving 1-10 g of 1, 2-dibromo-4, 5-dialkynylbenzene in 80-150 mL of N, N-dimethylformamide, placing in a 50-500 mL flask, adding 1-10 g of azide reagent and 50-250 mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal-pressure backflow device, under the condition of introducing 0.1-10L/min of argon protection, firstly starting a backflow condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz and the microwave power is 300-1000W, heating the system to 50-200 ℃, heating for 1-720 min, when the temperature in the microwave reactor exceeds a set temperature, closing the microwave generator to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, opening the microwave generator to increase the temperature; after the reaction is finished, carrying out rotary evaporation at a rotating speed of 80-100 r/min for 10-200 min at a pressure of-0.09 MPa and a temperature of 30-120 ℃ to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 1:1 to obtain a click product;
B. modification of Diethylcyanide phthalate
Dissolving 2-8 g of click product in 50-150 mL of N, N-dimethylformamide at room temperature, adding 1-5 g of cuprous cyanide, transferring the mixed solution into 100-500 mL of polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a stainless steel reaction kettle, sealing, transferring the stainless steel reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature is 100-150 ℃, the microwave frequency is 2450MHz, the microwave power is 500-1000W, the reaction time is 1-10 h, and continuously performing magnetic stirring at the speed of 100-1000 r/min in the synthesis process; after the reaction is finished, performing rotary evaporation at the temperature of 60-120 ℃ and the pressure of-0.09 MPa for 10-120 min at the rotating speed of 80-100 r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 1:1 to obtain a modified o-diethylcyanide product;
C. synthesis of phthalocyanines
Dissolving 1-5 g of modified phthalocyanamide and 400-700 mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing in a 50-500 mL flask, and adding 1-3 g of M source under the protection of argon introduced at 0.1-10L/min; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level; after the solution is irradiated by the laser for 1-30 min, starting an ultraviolet lamp for irradiation, wherein the wavelength of the ultraviolet light is 190-400 nm, and the illumination intensity is 5-300 mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 500-1000W while irradiating laser and ultraviolet to heat the system to 60-210 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 1-60 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 30-120 ℃ and the pressure of-0.09 MPa for 10-200 min at the rotating speed of 80-100 r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction
Dissolving 500-1500 mg of phthalocyanine in 10-300 mL of mixed solution with a volume ratio of tetrahydrofuran to diisopropylamine of 1:1, placing the mixed solution in a 50-500 mL single-neck flask with a four-neck glass connecting pipe, adding 1-500 mg of alkynyl trimethyl silicon, 1-60 mg of triphenylphosphine palladium dichloride and 1-50 mg of cuprous iodide under the protection of argon gas introduced at 0.1-10L/min, controlling the temperature at 80-120 ℃, and performing condensation reflux for 6-12 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution by Nd: YAG solid pulse laser for 1-60 min, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-2 mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 5-30 mW/cm2(ii) a Simultaneously, the laser and the ultraviolet irradiation are performed, the microwave heating is synchronously started, the microwave frequency is 2450MHz, the microwave power is 500-1000W, the system is heated to 60-210 ℃, and when the temperature in the microwave reactor exceeds the set temperature, the microwave generator is closed to reduce the temperature, so that the temperature is lowWhen the temperature is set, the microwave generator is turned on to heat up; after the reaction is finished, performing rotary evaporation at the temperature of 40-120 ℃ and the pressure of-0.09 MPa for 10-240 min at the rotating speed of 80-100 r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction
At room temperature, dissolving the D product in a mixed solution of 1-250 mL of methanol and 1-250 mL of tetrahydrofuran, placing the mixed solution in a flask with the volume of 50-1000 mL, then adding 0.01-5 g of potassium carbonate, and stirring at the speed of 200-1000 r/min for 3-8 h; then, carrying out rotary evaporation at a rotating speed of 80-100 r/min for 10-240 min under-0.09 MPa and at a temperature of 40-120 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3-5 times, drying at a temperature of 30-80 ℃ for 6-72 h to obtain the phthalocyanine derivative with the terminal alkyne, and storing in a nitrogen environment;
F. reaction with acceptor iodide
Dissolving 500-1500 mg of phthalocyanine derivative with alkyne in 10-300 mL of mixed solution with volume ratio of tetrahydrofuran to diisopropylamine being 1:1, placing the mixed solution in a 30-1000 mL single-neck flask connected with a four-neck glass connecting pipe, adding 100-1000 mg of p-iodobenzonitrile acrylic acid under the protection of 0.1-2L/min argon, then moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, starting the reflux condensing device, firstly starting microwave heating for 1-30 min, microwave frequency of 2450MHz and microwave power of 500-1000W, heating the system to 50-200 ℃, closing the microwave generator to cool when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to heat when the temperature is lower than the set temperature; then, Nd-YAG solid pulse laser is used for irradiating the solution for 1-40 min, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 106W/cm in power density2The light spot of the laser focus is 1-3 mm below the liquid level; in the laser irradiation process, the microwave heating is synchronously started, the microwave frequency is 2450MHz, the microwave power is 500-1000W, the system is heated to 50-200 ℃, the laser irradiation and the microwave heating are simultaneously started, the ultraviolet lamp irradiation is started, the ultraviolet wavelength is 365nm, and the illumination intensity is 5E30mW/cm2(ii) a Then continuing microwave heating for 1-30 min; and adding 1-100 mg of triphenylphosphine palladium dichloride and 1-100 mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the rotation speed of 80-100 r/min for 10-240 min under the pressure of-0.09 MPa and at the temperature of 30-120 ℃ to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in a volume ratio of 2:1 to obtain a novel phthalocyanine D-pi-A type solar cell dye sample product.
In the click reaction, an azide reagent R1The alkyl, alkoxy and dialkyl amine can be any one of p-pentylphenylazide, p-butylbenzene azide, 1-azido-4-eicosylbenzene, 1-azido-4-butoxybenzene, 1-azido-4-pentyloxyphenyl, 1-azido-4-eicosyloxybenzene, N-dibutyl-p-phenylazide, N-dipentyl-p-phenylazide and N, N-docosyl-p-phenylazide.
In the synthesis of the phthalocyanine, the M source is any one of Cu, Co, Ni, Zn, Mg and Fe, and can be ferric acetate, magnesium acetate, nickel acetate, cobalt acetate, zinc acetate, copper acetate, magnesium chloride, zinc chloride, copper chloride and ferrous chloride.
[ advantages and effects of the invention ]: the invention provides a method for synthesizing a novel phthalocyanine D-pi-A type solar cell dye by a click reaction, which has the following advantages and effects: (1) phthalocyanine is taken as a matrix, different alkyl or alkoxy phenylacetylene and dialkyl aniline donors are accessed through click reaction, and dendritic or asymmetric groups are favorable for relieving molecular aggregation caused by pi-pi accumulation, so that the injection efficiency of electrons is improved, and the short-circuit current is further improved; (2) the benzoic acid or cyanoacrylate-like receptor is accessed through Sonogashira coupling reaction to form a D-pi-A type asymmetric disc dye, and target products with diversified performances can be simply and efficiently prepared through different reaction raw materials; (3) the synthesis route relates to the application of ultraviolet, laser and microwave combined technology and microwave hydrothermal technology, the method has the advantages of more concentrated energy, capability of greatly shortening reaction time, strong process controllability and capability of effectively improving productivity; (4) the synthesized novel phthalocyanine D-Pi-A type solar cell dye has good solubility, excellent ultraviolet absorption and photoelectric conversion efficiency and wide application prospect.
[ description of the accompanying drawings ]:
FIG. 1 is a scheme for synthesizing molecules synthesized by the present invention
FIG. 2 is a UV spectrum of the molecule described in example 1 of the present invention
FIG. 3 is a UV spectrum of the molecule described in example 2 of the present invention
FIG. 4 is a J-V curve of the molecule described in example 2 of the present invention
FIG. 5 is a UV spectrum of the molecule described in example 3 of the present invention
FIG. 6 is a J-V curve of the molecule described in example 3 of the present invention
FIG. 7 is a drawing of one type of molecule synthesized according to the present invention, R1Is composed of
FIG. 8 is a drawing of one class of molecules synthesized by the present invention, wherein R2Is composed of
FIG. 9 is a schematic view of the structure of the laser, UV and microwave combination device used in the present invention (with reflux condenser)
FIG. 10 is a schematic diagram showing the structure of the combined laser, UV and microwave apparatus used in the present invention (glass four-port connecting tube, one of which is connected to a flask, and the other three ports are connected to a reflux condenser, a stirring paddle, a separating funnel, an argon tube or used for evacuation and vacuum evacuation as required)
[ embodiments ] of the present invention:
for clearly explaining the technical characteristics of the scheme, the patent of the invention is explained in detail by the following detailed description and the attached drawings:
example 1: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 1
With R1Has the structure of
R2Has the structure of
And the M source is Zn as an example, the synthesis method of the novel phthalocyanine D-pi-A type solar cell dye sample 1 is introduced:
and (A) click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 2.8g of p-pentylbenzene azide and 191mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal-pressure backflow device, under the condition of introducing 1L/min of argon protection, firstly starting a backflow condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 700W, heating the system to 100 ℃, heating for 120min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the set temperature; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into 250mL of polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2.5h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 65 ℃ under-0.09 MPa for 100min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: 3.2g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and 1L/mi is introducedUnder the protection of n argon, adding 1.22g of zinc acetate; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 10min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 20mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 700W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave act on the reactant for 120min simultaneously; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 10 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 20mW/cm2(ii) a Simultaneously, the laser and the ultraviolet irradiation synchronously start the microwave heating with the microwave frequency of 2450MHzThe microwave power is 700W, the temperature of the system is raised to 90 ℃, when the temperature in the microwave reactor exceeds the set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to raise the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying the product at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with the terminal alkyne, and storing the phthalocyanine derivative in a nitrogen environment;
F. reaction with iodo acceptor: 746.40mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodobenzoic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, a reflux condensing device is started, firstly, microwave heating is started for 10min, the microwave frequency is 2450MHz, the microwave power is 600W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 20Hz, and power density of 1.0 × 10 for 15min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 700W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; then 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide are added for reactionAnd after that, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent to be a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 1 with the yield of 54 percent and good effect.
Example 2: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 2
With R1Has the structure of
R2Has the structure of
And the M source is Zn as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 2 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 2.6g of p-butylbenzene azide and 191mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal-pressure backflow device, under the condition of introducing 1L/min of argon protection, firstly starting a backflow condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 700W, heating the system to 100 ℃, heating for 180min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the preset temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.7g of cuprous cyanide is added, then the mixed solution is transferred into 250mL of polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 700W, the reaction time is 3h, and the synthesis process is continuously stirred by magnetic force at the speed of 500 r/min; after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80-100 r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 1:1 to obtain modified phthalocynide;
C. synthesis of phthalocyanine: 3.2g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and added with 1.22g of zinc acetate under the protection of 1L/min argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by the laser for 10min, starting an ultraviolet lamp for irradiation, wherein the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 700W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave act on the reactant for 120min simultaneously; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 3 hours; then moving the material into a normal pressure zone reflux device with laser and ultraviolet irradiationThe microwave reactor is internally provided with a reflux condensing device, then Nd: YAG solid pulse laser is used for irradiating the solution for 15min, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 80 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 300mg of p-iodobenzonitrile acrylic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, the microwave heating is started for 10min, the microwave frequency is 2450MHz, the microwave power is 900W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a preset temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the preset temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd: YAG solid pulse laser with wave as laser parameter for 10minLength 1.06 μm, pulse width 1.2ms, spot diameter 0.3mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 900W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 15mW/cm2(ii) a Then continuing microwave heating for 25 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 50 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 2 with the yield of 54 percent and good effect.
Example 3: preparation of novel phthalocyanyl D-pi-A type solar cell dye sample 3
With R1Has the structure of
R2Has the structure of
And the M source is Cu as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 3 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 2.6g of p-butylbenzene azide and 191mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal-pressure backflow device, under the condition of introducing 1L/min of argon protection, firstly starting a backflow condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, heating the system to 100 ℃, heating for 10min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the preset temperature; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: dissolving 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 250mL flask, and adding 1.3g of copper acetate under the protection of 1L/min of argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1,to obtain the product phthalocyanine with the molecular formula C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the temperature of 60 ℃ under the pressure of-0.09 MPa to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying the product at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with the terminal alkyne, and storing the phthalocyanine derivative in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution of tetrahydrofuran and diisopropylamine with the volume ratio of 1:1 and placed in a 100mL single-neck flaskUnder the protection of argon gas at the rate of 1L/min, 248mg of p-iodobenzoic acid is added, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to heat; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain a novel phthalocyanine D-pi-A type solar cell dye sample 3 with the yield of 54 percent and good effect.
Example 4: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 4
With R1Has the structure of
R2Has the structure of
And the M source is Zn as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 4 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 2.6g of p-butylbenzene azide and 191mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal-pressure backflow device, under the condition of introducing 1L/min of argon protection, firstly starting a backflow condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, heating the system to 100 ℃, heating for 10min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the preset temperature; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: dissolving 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 250mL flask, and adding 1.3g of copper acetate under the protection of 1L/min of argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a The laser and the ultraviolet irradiation are the sameWhen the temperature is high, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz and the microwave power is 800W, and heating the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, carrying out rotary evaporation at the rotation speed of 80r/min for 120min at the temperature of 60 ℃ under the pressure of-0.09 MPa to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodophenylbenzoic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain a novel phthalocyanine D-pi-A type solar cell dye sample 4 with the yield of 54 percent and good effect.
Example 5: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 5
With R1Has the structure of
R2Has the structure of
And the M source is Co as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 5 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 6g of 1-azido-4-eicosylbenzene and 191mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal-pressure belt reflux device, under the condition of introducing 1L/min of argon protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, the temperature of a system is increased to 100 ℃, the system is heated for 10min, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, dissolving 5.08g of click product in 100mL of N, N-dimethylformamide, adding 2.70g of cuprous cyanide, transferring the mixed solution into 250mL of polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a stainless steel reaction kettle, sealing, transferring the stainless steel reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 120 ℃, the microwave frequency of 2450MHz, the microwave power of 800W and the reaction time of 2h, and continuously carrying out magnetic stirring at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and 1.06g of cobalt acetate is added under the protection of 1L/min argon gas(ii) a Then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Simultaneously starting microwave heating with microwave frequency of 2450MHz and microwave power of 700W to heat the system to 90 deg.C while irradiating with laser and ultraviolet,when the temperature in the microwave reactor exceeds the set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodobenzoic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, a reflux condensing device is started, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, and after the reaction is finished, controlling the temperature to be 60 ℃ at-0.09 MPa and 80 r-And (3) carrying out rotary evaporation at the rotating speed of min for 120min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain a novel phthalocyanine D-pi-A type solar cell dye sample 5 with the yield of 54 percent and good effect.
Example 6: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 6
With R1Has the structure of
R2Has the structure of
And the M source is Co as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 6 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the obtained solution in a 250mL flask, adding 2.9g of 1-azido-4-butoxybenzene and 191mg of cuprous iodide, then transferring the obtained product into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon gas for protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz and the microwave power is 800W, so that the temperature of the system is raised to 100 ℃, heating is carried out for 10min, when the temperature in the microwave reactor exceeds a preset temperature, a microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: dissolving 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 250mL flask, and adding 1.06g of cobalt acetate under the protection of argon introduced at 1L/min; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the mixture into a microwave reactor with a laser and ultraviolet irradiation normal pressure reflux device, starting the reflux condensing device, and then using Nd: YAG solid pulseIrradiating the solution with laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 20Hz, and power density of 1.0 × 10 for 10min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 300mg of p-iodobenzonitrile acrylic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density for 8min1.0×106W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 6 with the yield of 54 percent and good effect.
Example 7: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 7
With R1Has the structure of
R2Has the structure of
And the M source is Ni, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 7 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the obtained solution in a 250mL flask, adding 2.9g of 1-azido-4-butoxybenzene and 191mg of cuprous iodide, then transferring the obtained product into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon gas for protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz and the microwave power is 800W, so that the temperature of the system is raised to 100 ℃, heating is carried out for 10min, when the temperature in the microwave reactor exceeds a preset temperature, a microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and 1.49g of nickel acetate is added under the protection of 1L/min argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. grafting iodo receptor reaction: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution of tetrahydrofuran and diisopropylamine with the volume ratio of 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodobenzoic acid is added under the protection of 1L/min argon, and then the flask is moved into a laser-charged single-neck flaskStarting a reflux condensing device in a microwave reactor with an ultraviolet irradiation normal pressure and a reflux device, firstly starting microwave heating for 15min, wherein the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to heat; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain a novel phthalocyanine D-pi-A type solar cell dye sample 7, wherein the yield is 53%, and a good effect is achieved.
Example 8: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 8
With R1Has the structure of
R2Has the structure of
And the M source is Ni, the synthesis method of the novel phthalocyanine D-pi-A type solar cell dye sample 8 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the obtained solution in a 250mL flask, adding 2.9g of 1-azido-4-butoxybenzene and 191mg of cuprous iodide, then transferring the obtained product into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon gas for protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz and the microwave power is 800W, so that the temperature of the system is raised to 100 ℃, heating is carried out for 10min, when the temperature in the microwave reactor exceeds a preset temperature, a microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and 1.49g of nickel acetate is added under the protection of 1L/min argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser,Simultaneously performing ultraviolet and microwave treatment on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 300mg of p-iodobenzonitrile acrylic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain a novel phthalocyanine D-pi-A type solar cell dye sample 8, wherein the yield is 54%, and a good effect is achieved.
Example 9: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 9
With R1Has the structure of
R2Has the structure of
And the M source is Mg as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 9 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 3.0g of 1-azido pentyloxy benzene and 191mg of cuprous iodide, then transferring the solution into a microwave reactor of a normal pressure belt reflux device, starting a reflux condenser with a rubber plug under the condition of introducing 1L/min of argon gas for protection, starting microwave heating, wherein the microwave frequency is 2450MHz and the microwave power is 800W, heating the system to 100 ℃, heating for 10min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the preset temperature; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: dissolving 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 250mL flask, and adding 1.28g of magnesium acetate under the protection of 1L/min of argon; then the flask is moved into a microwave reactor with a reflux device under normal pressure and laser and ultraviolet irradiation, the reflux condensing device is started, and N is used firstlyYAG solid pulse laser irradiation solution, wherein the laser parameters are wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 20Hz, and power density of 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, carrying out rotary evaporation at the rotation speed of 80r/min for 120min at the temperature of 60 ℃ under the pressure of-0.09 MPa to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N；
D. Sonogashira coupling reaction: dissolving 984mg of green phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; the reaction is finishedThen, carrying out rotary evaporation at the rotating speed of 80r/min for 130min at the temperature of 60 ℃ under the pressure of-0.09 MPa to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the mixture in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodobenzoic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, a reflux condensing device is started, microwave heating is started for 15min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane with the volume ratio of 2:1 to obtain the novel phthalocyanineThe yield of the D-Pi-A-like solar cell dye sample 9 is 53 percent, and a good effect is achieved.
Example 10: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 10
With R1Has the structure of
R2Has the structure of
And the M source is Mg as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 10 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 6.23g of 1-azido-4-eicosyloxybenzene and 191mg of cuprous iodide, then transferring the solution into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, heating the system to 100 ℃, heating for 10min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the set temperature; after the reaction is finished, carrying out rotary evaporation for 130min at the rotating speed of 80r/min under the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.08g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into a 250mL polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: dissolving 3.20g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 250mL flask, and adding 1.28g of magnesium acetate under the protection of 1L/min of argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 984mg of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency, work and workRate density 1.0X 106W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 746.4mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 300mg of p-iodobenzonitrile acrylic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, the microwave heating is synchronously started and is microThe wave frequency is 2450MHz, the microwave power is 800W, the system is heated to 90 ℃, the ultraviolet lamp is started to irradiate while the laser irradiation and the microwave heating are carried out, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 10 with the yield of 54 percent and good effect.
Example 11: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 11
With R1Has the structure of
R2Has the structure of
And the M source is Fe as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 11 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the obtained solution in a 250mL flask, adding 3.9g of N, N-dibutyl-p-phenyl azide and 191mg of cuprous iodide, then transferring the obtained product into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon gas for protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, the temperature of the system is raised to 100 ℃, the heating is carried out for 10min, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed for cooling, and when the temperature is lower than the set temperature, the microwave generator is opened for heating; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.33g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into 250mL of polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: 3.43g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and added with 1.15g of iron acetate under the protection of 1L/min argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 1:1 to obtain the product phthalocyanine with the molecular formula of C32H18N8；
D. Sonogashira coupling reaction: dissolving 1.24g of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1Placing the mixture into a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 950.80mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution of tetrahydrofuran and diisopropylamine with the volume ratio of 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodobenzoic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with laser and ultraviolet irradiation, a reflux condensing device is started, microwave heating is started for 5min, and the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds the set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 11 with the yield of 53 percent and good effect.
Example 12: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 12
With R1Has the structure of
R2Has the structure of
And the M source is Fe as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 12 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the obtained solution in a 250mL flask, adding 4.1g of N, N-dipentyl-p-phenyl azide and 191mg of cuprous iodide, then transferring the obtained product into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon gas for protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, the temperature of the system is raised to 100 ℃, the heating is carried out for 10min, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed for cooling, and when the temperature is lower than the set temperature, the microwave generator is opened for heating; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.33g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into 250mL of polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: dissolving 3.43g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 250mL flask, and adding 1.15g of iron acetate under the protection of 1L/min argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperatureWhen the temperature is lower than the set temperature, the microwave generator is started to heat up; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain the product phthalocyanine;
D. sonogashira coupling reaction: dissolving 1.24g of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 950.80mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 300mg of p-iodobenzonitrile acrylic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, the reflux condensing device is started, firstly, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 12 with the yield of 51 percent and good effect.
Example 13: preparation of novel phthalocyanine D-pi-A type solar cell dye sample 13
With R1Has the structure of
R2Has the structure of
And the M source is Fe as an example, a synthesis method of a novel phthalocyanine D-pi-A type solar cell dye sample 13 is introduced:
A. click reaction: dissolving 3.41g of 1, 2-dibromo-4, 5-dialkynylbenzene in 100mL of N, N-dimethylformamide, placing the solution in a 250mL flask, adding 11.1g of N, N-docosyl p-phenyl azide and 191mg of cuprous iodide, then transferring the solution into a microwave reactor of a normal pressure belt reflux device, under the condition of introducing 1L/min of argon protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, heating the system to 100 ℃, heating for 10min, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the set temperature; after the reaction is finished, rotationally evaporating at the temperature of 50 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain a click product;
B. modification of phthalonitrile: at room temperature, 5.33g of click product is dissolved in 100mL of N, N-dimethylformamide, 2.70g of cuprous cyanide is added, then the mixed solution is transferred into 250mL of polytetrafluoroethylene lining, the stainless steel reaction kettle is placed in a sealed state, and then the stainless steel reaction kettle is moved into a microwave hydrothermal synthesizer, the conditions of the synthesizer are set to be that the heating temperature is 120 ℃, the microwave frequency is 2450MHz, the microwave power is 800W, the reaction time is 2h, and the magnetic stirring is continuously carried out at the speed of 500r/min in the synthesis process; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in the volume ratio of 1:1 to obtain the modified phthalocynide;
C. synthesis of phthalocyanine: 3.43g of modified phthalocyanamide and 516mg of 4-iodophthalocyanin are dissolved in 100mL of dimethylaminoethanol, placed in a 250mL flask, and added with 1.15g of iron acetate under the protection of 1L/min argon; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is firstly used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2Laser focusThe light spot of the point is 2mm below the liquid level; after the solution is irradiated by laser for 5min, starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W while irradiating laser and ultraviolet to heat the system to 160 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 180 min; particularly, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, carrying out rotary evaporation at the rotation speed of 80r/min for 120min at the temperature of 60 ℃ under the pressure of-0.09 MPa to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 1:1 to obtain the product phthalocyanine;
D. sonogashira coupling reaction: dissolving 1.24g of phthalocyanine in 50mL of mixed solution of tetrahydrofuran and diisopropylamine in a volume ratio of 1:1, placing the mixed solution in a 100mL single-neck flask, adding 196mg of alkynyl trimethyl silicon, 35mg of triphenylphosphine palladium dichloride and 35mg of cuprous iodide under the protection of 1L/min of argon, controlling the temperature at 80 ℃, and carrying out condensation reflux for 6 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution with Nd: YAG solid pulse laser for 10min, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.3mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 25mW/cm2(ii) a Synchronously starting microwave heating at 2450MHz and 700W under the irradiation of laser and ultraviolet to heat the system to 90 deg.C, turning off the microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature, and turning on the microwave generator to heat when the temperature is lower than the predetermined temperature; after the reaction is finished, rotationally evaporating at the temperature of 60 ℃ and the pressure of-0.09 MPa for 130min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in the volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction: dissolving the D product in a mixed solution of 50mL of methanol and 50mL of tetrahydrofuran at room temperature, placing the solution in a 250mL flask, adding 2.7g of potassium carbonate, and stirring at the speed of 500r/min for 4 hours; then, carrying out rotary evaporation at the rotating speed of 80r/min for 120min at the pressure of-0.09 MPa and the temperature of 50 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3 times respectively, drying at the temperature of 60 ℃ for 36h to obtain the phthalocyanine derivative with terminal alkyne, and storing in a nitrogen environment;
F. reaction with iodo acceptor: 950.8mg of phthalocyanine derivative with terminal alkyne is dissolved in 50mL of mixed solution with the volume ratio of tetrahydrofuran to diisopropylamine being 1:1, the mixed solution is placed in a 100mL single-neck flask, 248mg of p-iodobenzoic acid is added under the protection of 1L/min argon, then the flask is moved into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, a reflux condensing device is started, microwave heating is started for 5min, the microwave frequency is 2450MHz, the microwave power is 800W, the system is heated to 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; then irradiating the solution with Nd-YAG solid pulse laser with wavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.3mm, repetition frequency of 30Hz, and power density of 1.0 × 10 for 8min6W/cm2The light spot of the laser focus is 2mm below the liquid level; in the laser irradiation process, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 800W to heat the system to 90 deg.C, and simultaneously starting ultraviolet lamp irradiation with ultraviolet wavelength of 365nm and illumination intensity of 20mW/cm2(ii) a Then continuing microwave heating for 10 min; and adding 35mg of triphenylphosphine palladium dichloride and 10mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 60 ℃ and the pressure of-0.09 MPa for 120min at the rotating speed of 80r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the novel phthalocyanine D-pi-A type solar cell dye sample 13 with the yield of 52 percent and good effect.
Table 1 results of electrical property testing of molecules described in some examples, wherein
Table 2 results of electrical property testing of molecules described in part of the examples, wherein
Claims (2)
1. A method for synthesizing phthalocyanine D-pi-A type solar cell dye by click reaction is disclosed, the phthalocyanine D-pi-A type solar cell dye is an asymmetric disk-shaped dye molecule, and the structural general formula of the compound is as follows:
wherein R is1The structural general formula is as follows:
n is an integer of 4-20;
R2the structural general formula is as follows:
m is any one of Cu, Co, Ni, Zn, Mg and Fe;
the phthalocyanine D-pi-A type solar cell dye is realized by the following technical scheme:
A. click reaction
Dissolving 1-10 g of 1, 2-dibromo-4, 5-diynylbenzene in 80-150 mL of N, N-dimethylformamide, placing in a 50-500 mL flask, adding 1-10 g of azide reagent and 50-250 mg of cuprous iodide, moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal pressure reflux device, under the condition of introducing 0.1-10L/min of argon protection, firstly starting a reflux condensing device with a rubber plug, then starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, the temperature of the system is increased to 50-200 ℃, the heating is carried out for 1-720 min, when the temperature in the microwave reactor exceeds a preset temperature, the microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; after the reaction is finished, performing rotary evaporation at a temperature of 30-120 ℃ and a pressure of-0.09 MPa for 10-200 min at a rotating speed of 80-100 r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 1:1 to obtain a click product;
B. modification of phthalocyanamide
Dissolving 2-8 g of click product in 50-150 mL of N, N-dimethylformamide at room temperature, adding 1-5 g of cuprous cyanide, transferring the mixed solution into 100-500 mL of polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a stainless steel reaction kettle, sealing, transferring the stainless steel reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature is 100-150 ℃, the microwave frequency is 2450MHz, the microwave power is 500-1000W, the reaction time is 1-10 h, and continuously performing magnetic stirring at the speed of 100-1000 r/min in the synthesis process; after the reaction is finished, performing rotary evaporation at the temperature of 60-120 ℃ and the pressure of-0.09 MPa for 10-120 min at the rotating speed of 80-100 r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 1:1 to obtain a modified o-diethylcyanide product;
C. synthesis of phthalocyanines
Dissolving 1-5 g of modified phthalocyanamide and 400-700 mg of 4-iodophthalocyanin in 100mL of dimethylaminoethanol, placing the mixture in a 50-500 mL flask, and adding 1-3 g of M under the protection of argon introduced at 0.1-10L/minA source; then the flask is moved into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, the reflux condensing device is started, and Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level; after the solution is irradiated by the laser for 1-30 min, starting an ultraviolet lamp for irradiation, wherein the wavelength of the ultraviolet light is 190-400 nm, and the illumination intensity is 5-300 mW/cm2(ii) a Synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 500-1000W while irradiating laser and ultraviolet to heat the system to 60-210 ℃; wherein, the laser, the ultraviolet and the microwave simultaneously act on the reactant for 1-60 min; when the temperature in the microwave reactor exceeds the set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, carrying out rotary evaporation at a temperature of 30-120 ℃ and a pressure of-0.09 MPa for 10-200 min at a rotating speed of 80-100 r/min to remove the solvent, and passing the product through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 1:1 to obtain a phthalocyanine compound;
D. sonogashira coupling reaction
Dissolving 500-1500 mg of phthalocyanine in 10-300 mL of mixed solution with a volume ratio of tetrahydrofuran to diisopropylamine of 1:1, placing the mixed solution in a 50-500 mL single-neck flask with a four-neck glass connecting pipe, adding 1-500 mg of alkynyl trimethyl silicon, 1-60 mg of triphenylphosphine palladium dichloride and 1-50 mg of cuprous iodide under the protection of argon gas introduced at 0.1-10L/min, controlling the temperature at 80-120 ℃, and performing condensation reflux for 6-12 hours; then moving the solution into a microwave reactor with a normal pressure reflux device and laser and ultraviolet irradiation, starting the reflux condensing device, and then irradiating the solution by Nd: YAG solid pulse laser for 1-60 min, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-2 mm below the liquid level; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 5-30 mW/cm2(ii) a Synchronously starting microwave heating while irradiating by laser and ultraviolet, wherein the microwave frequency is 2450MHz, the microwave power is 500-1000W, the temperature of the system is raised to 60-210 ℃, the microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and the microwave generator is opened to raise the temperature when the temperature is lower than the preset temperature; after the reaction is finished, performing rotary evaporation at the temperature of 40-120 ℃ and the pressure of-0.09 MPa for 10-240 min at the rotating speed of 80-100 r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 1:1 to obtain a product D;
E. removing trimethyl silicon reaction
At room temperature, dissolving the D product in a mixed solution of 1-250 mL of methanol and 1-250 mL of tetrahydrofuran, placing the mixed solution in a flask with the volume of 50-1000 mL, then adding 0.01-5 g of potassium carbonate, and stirring at the speed of 200-1000 r/min for 3-8 h; then, carrying out rotary evaporation at a rotating speed of 80-100 r/min for 10-240 min under-0.09 MPa and at a temperature of 40-120 ℃ to remove the solvent, washing the obtained product with deionized water and methanol for 3-5 times, drying at a temperature of 30-80 ℃ for 6-72 h to obtain the phthalocyanine derivative with the terminal alkyne, and storing in a nitrogen environment;
F. reaction with acceptor iodide
Dissolving 500-1500 mg of phthalocyanine derivative with alkyne in 10-300 mL of mixed solution with volume ratio of tetrahydrofuran to diisopropylamine being 1:1, placing the mixed solution in a 30-1000 mL single-neck flask connected with a four-neck glass connecting pipe, adding 100-1000 mg of p-iodobenzonitrile acrylic acid under the protection of 0.1-2L/min argon, then moving the flask into a microwave reactor with a laser and ultraviolet irradiation normal pressure and a reflux device, starting the reflux condensing device, firstly starting microwave heating for 1-30 min, microwave frequency of 2450MHz and microwave power of 500-1000W, heating the system to 50-200 ℃, closing the microwave generator to cool when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to heat when the temperature is lower than the set temperature; then, Nd-YAG solid pulse laser is used for irradiating the solution for 1-40 min, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level; laserIn the light irradiation process, microwave heating is synchronously started, the microwave frequency is 2450MHz, the microwave power is 500-1000W, the system is heated to 50-200 ℃, an ultraviolet lamp is started for irradiation while laser irradiation and microwave heating are carried out, the wavelength of ultraviolet light is 365nm, and the illumination intensity is 5-30 mW/cm2(ii) a Then continuing microwave heating for 1-30 min; and adding 1-100 mg of triphenylphosphine palladium dichloride and 1-100 mg of cuprous iodide, after the reaction is finished, carrying out rotary evaporation at the temperature of 30-120 ℃ and the pressure of-0.09 MPa for 10-240 min at the rotating speed of 80-100 r/min to remove the solvent, and enabling the product to pass through a column developing agent which is a mixed solvent of ethyl acetate and n-hexane in the volume ratio of 2:1 to obtain the phthalocyanine D-pi-A type solar cell dye sample product.
2. The method for synthesizing phthalocyanine D-pi-A type solar cell dye by click reaction according to claim 1, characterized in that: in the synthesis of the phthalocyanine, the M source is any one of ferric acetate, magnesium acetate, nickel acetate, cobalt acetate, zinc acetate, copper acetate, magnesium chloride, zinc chloride, copper chloride and ferrous chloride.
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| CN102449795A (en) * | 2009-05-26 | 2012-05-09 | 巴斯夫欧洲公司 | Use of phthalocyanine compounds with aryl or hetaryl substituents in organic solar cells |
| CN102898431A (en) * | 2012-11-08 | 2013-01-30 | 北京理工大学 | Self-assembly zinc phthalocyanine and synthetic method thereof |
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| CN102449795A (en) * | 2009-05-26 | 2012-05-09 | 巴斯夫欧洲公司 | Use of phthalocyanine compounds with aryl or hetaryl substituents in organic solar cells |
| CN102898431A (en) * | 2012-11-08 | 2013-01-30 | 北京理工大学 | Self-assembly zinc phthalocyanine and synthetic method thereof |
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| Synthesis and photodynamic activities of integrin-targeting silicon(IV) phthalocyanine-cRGD conjugates;Zheng,BiYuan et al.;《European Journal of Medicinal Chemistry》;20180715;第155卷;24-33 * |
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