CN115612310B - Porphyrin photosensitive dye and application thereof - Google Patents

Porphyrin photosensitive dye and application thereof Download PDF

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CN115612310B
CN115612310B CN202211209405.7A CN202211209405A CN115612310B CN 115612310 B CN115612310 B CN 115612310B CN 202211209405 A CN202211209405 A CN 202211209405A CN 115612310 B CN115612310 B CN 115612310B
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porphyrin
benzodithiophene
sensitizer
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compound
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CN115612310A (en
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韩明亮
单昱东
汪鹏飞
刘鑫
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Hangzhou Zhongmei Huadong Pharmaceutical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention provides a benzodithiophene porphyrin photosensitizer, a preparation method and application thereof, wherein the benzodithiophene porphyrin photosensitizer has a D-pi-A structure, and a main donor is a benzodithiophene compound. The novel sulfur-containing fused heteroaromatic compound provided by the invention is used as the benzodithiophene porphyrin sensitizer of the electron donor, so that the organic solar cell device containing the benzodithiophene porphyrin sensitizer has higher photoelectric conversion efficiency.

Description

Porphyrin photosensitive dye and application thereof
Technical Field
The invention belongs to the field of application of organic photoelectric materials and the technical field of dye sensitized solar cells, and particularly relates to a benzo dithiophene porphyrin photosensitizer and a preparation method and application thereof.
Background
Photovoltaic technology for converting sunlight into electrical energy has long been considered as one of the most important ways of utilizing solar energy. Photovoltaic technology has evolved rapidly over the last decades with remarkable results. In 1991, michaelAnd its co-workers reported for the first time organic Dye Sensitized Solar Cell (DSSCs) technology. DSSCs mainly comprise a semiconductor thin film attached to transparent conductive glass, an organic photosensitive dye anchored to the semiconductor surface, a counter electrode, and an electrolyte filled between the two electrodes. The DSSCs have the advantages of simple manufacturing process, low cost, transparency, capability of being prepared into flexible devices, good stability and excellent photovoltaic performance in weak light environmentDifferent, etc. DSSCs mimic the photosynthesis process of plants, which allows us to independently study and optimize the light absorption and charge transfer processes of DSSCs. Photosensitizing dyes are the core of DSSCs, and dyes are typically adsorbed on the surface of semiconductors, responsible for capturing photons, generating charge-hole pairs, and finally converting solar energy to electrical energy through their charge separation.
In recent years, porphyrin and pure organic photosensitive dyes have been intensively and widely studied due to the characteristics of cheap raw materials, easy purification, high molar extinction coefficient, various molecular structures, strong modifiable property, controllable photophysical and photochemical properties and the like.
The selection of a proper electron donor structure is the key for designing and synthesizing novel high-efficiency porphyrin photosensitive dye.
The evolution of electron donor structures from bare diphenylamines in porphyrin dyes YD2, to hexyl-modified diphenylamines in YD2-o-C8 (Science 2011, 334, 629.) to dihexoxybenzene-modified diphenylamines in SM315 (nat. Chem.2014,6, 242.) is one of the important reasons for the ever-increasing photoelectric conversion efficiency of porphyrin dyes. To date, almost all electron donors used in porphyrin-based photosensitizing dyes are aza-aromatic rings or diphenylamine derivatives, and in practical applications, porphyrin dye sensitizers still have three major problems: (1) weak absorption intensity in the near infrared region; (2) The anchoring group is easy to desorb, so that the energy conversion efficiency is reduced, and the service life of the battery is shortened; (3) Porphyrin is in a ring-shaped plane structure, is easy to self-polymerize, and causes dye fluorescence quenching or dye sensitizer desorption.
Oligothiophenes and polythiophenes have received attention over the last decade and are widely used as organic semiconductor materials in photovoltaic cells. Because of the defect of low hole mobility of the materials, the research on novel molecular structures rich in thiophene units is promoted continuously, and sulfur-containing condensed heteroaromatic compounds are also attracting attention. Benzo [1,2-b:4,5-b' ] dithiophene is representative thereof. The planar and symmetrical rigid aromatic ring structure enables the dithienobenzene to have more excellent performance than other polythiophene compounds. The compound has high field effect mobility, conductivity, band gap easy to adjust and controllable molecular energy level, and is easy to synthesize and good in chemical stability. Materials based on dithienobenzene have been widely used in organic electronic devices such as organic light emitting diodes since the nineties of the last century; the polymer or copolymer based on the dithienylbenzene is also used as a photovoltaic material for polymer batteries and heterojunction batteries, and excellent photovoltaic performance is obtained. CN104640902B discloses a copolymer comprising a combination of a plurality of thieno [3,4-B ] thiophene frameworks and a benzo [1,2-B:4,5-B' ] dithiophene frameworks, which has a narrow bandgap, high carrier mobility, and compatibility with an electron-accepting material, and provides a photovoltaic element having high photoelectric conversion efficiency.
The electron donor for porphyrin photosensitive dye is almost nitrogen heteroaromatic ring or diphenylamine derivative, the electron-rich benzodithiophene derivative is used as electron donor for the first time, a porphyrin photosensitive dye is designed and synthesized, and a new thought and a new opportunity for designing and synthesizing a novel high-efficiency porphyrin dye can be provided.
Disclosure of Invention
The benzodithiophene porphyrin sensitizer disclosed by the invention has a D-pi-A structure, wherein D is an electron donor, pi is a bridge, and A is an electron acceptor; the electron donor D contains three parts: zinc porphyrin ZnP, primary donor MD and auxiliary donor AD, exemplary structures are shown below:
the first aspect of the invention provides a porphyrin sensitizer, in particular to a benzodithiophene porphyrin sensitizer; the benzodithiophene porphyrin sensitizer has a D-pi-A structure, wherein D is an electron donor, pi is a bridge, and A is an electron acceptor;
the electron donor contains zinc porphyrin, a main donor and an auxiliary donor, and the zinc porphyrin has the following structure:
the main donor is a benzodithiophene compound selected from benzo [1,2-b:4,5-b ' ] dithiophenes, benzo [1,2-b:5,4-b ' ] dithiophenes, benzo [1,2-b:3,4-b ' ] dithiophenes, benzo [1,2-b:6,5-b ' ] dithiophenes, preferably benzo [1,2-b:4,5-b ' ] dithiophenes and benzo [1,2-b:5,4-b ' ] dithiophenes, more preferably benzo [1,2-b:4,5-b ' ] dithiophenes.
According to embodiments of the present invention, the benzo [1,2-b:4,5-b' ] dithiophenes further contain a modification at the 4, 8-position.
According to an embodiment of the present invention, the benzo [1,2-b:4,5-b' ] dithiophenes further contain a 2-position thiophene substitution or an alkylthiophene substitution, the thiophene substitution or the alkylthiophene substitution having the following structure:
according to the embodiment of the invention, the main donor of the electron donor of the benzo-dithiophene porphyrin sensitizer provided by the invention has the structure shown in the following general formula I-I:
wherein R is a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted straight or branched alkyl group having 6 to 10 carbon atoms, or is hydrogen; for example, R may be a substituted or unsubstituted straight or branched alkyl group having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms; specifically, it may be methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylbutyl, 2-ethylbutyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or the like, and more preferably 2-ethylhexyl, or hydrogen.
R 1 And R is 2 Each of which is a substituted or unsubstituted straight-chain or branched alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkyl-modified thiophene having 1 to 20 carbon atoms, or hydrogen; for example, R 1 And R is 2 Straight or branched alkoxy groups each having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms which may be substituted or unsubstituted; specifically, it may be methylalkoxy, ethylalkoxy, n-propylalkoxy, isopropylalkoxy, n-butylalkoxy, 2-methylbutylalkoxy, 2-ethylbutylalkoxy, n-pentylalkoxy, 2-methylpentylalkoxy, 2-ethylpentylalkoxy, n-hexylalkoxy, 2-methylhexylalkoxy, 2-ethylhexyl alkoxy, n-heptylalkoxy, n-octylalkoxy, n-nonylalkoxy, n-decylalkoxy, n-undecylalkoxy, n-dodecylalkoxy, n-tridecylalkoxy, n-tetradecylalkoxy, n-pentadecylalkoxy, n-hexadecylalkoxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy or n-eicosyloxy, etc., more preferably straight-chain octyloxy, or hydrogen. For example, R 1 And R is 2 Can each be a substituted or unsubstituted straight or branched chain alkyl-modified thiophene of carbon number 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, preferably methylthiophene, ethylthiophene, n-propylthiophene, isopropylthiophene, n-butylthiophene, 2-methylbutylthiophene, 2-ethylbutylthiophene, n-pentylthiene, 2-methylpentylthiophene, 2-ethylpentylthiophene, 2-n-hexylthiophene, more preferably 2-n-hexylthiophene.
According to the embodiment of the invention, the auxiliary donor of the electron donor of the benzo-dithiophene porphyrin sensitizer provided by the invention has the structure shown in the following general formulas I-II:
wherein R is 3 And R is 4 Each is a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted straight or branched alkyl group having 6 to 10 carbon atoms, or is hydrogen; r is R 3 And R is 4 Straight or branched alkyl groups each having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms which may be substituted or unsubstituted; specifically, it may be methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylbutyl, 2-ethylbutyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or the like, more preferably n-octyl, or hydrogen.
According to the embodiment of the invention, the benzo dithiophene porphyrin sensitizer provided by the invention takes a general formula II as pi bridge, and the general formula II has the following structure:
ar is phenyl or phenyl substituted by benzothiadiazole, and has the following structure:
according to the embodiment of the invention, the porphyrin sensitizer provided by the invention, in particular to a benzodithiophene porphyrin sensitizer, which has the structure shown in the following general formula III:
wherein R is a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted straight or branched alkyl group having 6 to 10 carbon atoms, or is hydrogen; for example, R may be a substituted or unsubstituted straight or branched alkyl group having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms; specifically, it may be methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylbutyl, 2-ethylbutyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or the like, and more preferably 2-ethylhexyl, or hydrogen.
R 1 And R is 2 Each of which is a substituted or unsubstituted straight-chain or branched alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkyl-modified thiophene having 1 to 20 carbon atoms, or hydrogen; for example, R 1 And R is 2 Straight or branched alkoxy groups each having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms which may be substituted or unsubstituted; specifically, it may be methylalkoxy, ethylalkoxy, n-propylalkoxy, isopropylalkoxy, n-butylalkoxy, 2-methylbutylalkoxy, 2-ethylbutylalkoxy, n-pentylalkoxy, 2-methylpentylalkoxy, 2-ethylpentylalkoxy, n-hexylalkoxy, 2-methylhexylalkoxy, 2-ethylhexyl alkoxy, n-heptylalkoxy, n-octylalkoxy, n-nonylalkoxy, n-decylalkoxy, n-undecylalkoxy, n-dodecylalkoxy, n-tridecylalkoxy, n-tetradecylalkoxy, n-pentadecylalkoxy, n-hexadecylalkoxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy or n-eicosyloxy and the like, more preferablySelected from linear octyl groups, or hydrogen. For example, R 1 And R is 2 Can each be a substituted or unsubstituted straight or branched chain alkyl-modified thiophene of carbon number 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, preferably methylthiophene, ethylthiophene, n-propylthiophene, isopropylthiophene, n-butylthiophene, 2-methylbutylthiophene, 2-ethylbutylthiophene, n-pentylthiene, 2-methylpentylthiophene, 2-ethylpentylthiophene, 2-n-hexylthiophene, more preferably 2-n-hexylthiophene.
R 3 And R is 4 Each is a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted straight or branched alkyl group having 6 to 10 carbon atoms, or is hydrogen; r is R 3 And R is 4 Straight or branched alkyl groups each having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms which may be substituted or unsubstituted; specifically, it may be methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylbutyl, 2-ethylbutyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or the like, more preferably n-octyl, or hydrogen.
The electron acceptor is carboxyl, cyanoacetic acid, amido hydroxyl, alkoxy silicon base, preferably carboxyl:
according to an embodiment of the present invention, the benzodithiophene porphyrin sensitizer provided by the present invention may be one of the following:
compound 10, having the structure:
compound 12, having the structure:
compound 20, having the structure:
in a second aspect, the present invention provides a method for preparing a benzodithiophene porphyrin sensitizer, and an exemplary method for preparing a general formula III, including the following steps:
(1) Synthesis of intermediate 1:
under the protection of inert gas, dissolving the general formula 1 in an aprotic solvent stable to strong alkali and halogen; adding strong base into the mixture at low temperature (0 to minus 78 ℃), wherein the addition amount is 1 to 10 times of the mole number of the general formula 1; increasing the temperature (the increasing range is 10-20 ℃), and adding an alkane solution of bromine, wherein the bromine is 1-10 times of the 1mol number of the compound; the reaction is monitored by Thin Layer Chromatography (TLC), typically for several hours to days. After the completion of the reaction, the reaction was quenched with saturated aqueous ammonium chloride solution, diluted with n-hexane, and anhydrous MgSO 4 Drying, removing solvent, and performing column chromatography to obtain the compound shown in the general formula 2.
The aprotic solvent is selected from dialkylamides, simple ethers (linear ethers such as diethyl ether, methyl-t-butyl ether), cyclic ethers such as THF and glyme, or mixtures of such solvents, preferably THF; the strong base is selected from sodium methoxide, sodium hydroxide, potassium tert-butoxide, sodium hydride and n-butyllithium, preferably n-butyllithium; the alkane solution is selected from one of normal hexane solution, cyclohexane solution and normal heptane solution, and is preferably normal hexane solution.
The general formula 4 is obtained by Stille coupling reaction of the general formula 2 and the general formula 3 in a solvent and a first palladium catalyst. The addition amount of the palladium catalyst is 0.1 to 0.5 times of the mole number of the general formula 2. The reaction is carried out at the boiling temperature of the solvent, generally (50 to 150 ℃). The reaction is monitored by Thin Layer Chromatography (TLC), typically for several hours to days. After the reaction was completed, the solvent was removed under reduced pressure, and column chromatography was performed to obtain general formula 4.
The aprotic small polar solvent is toluene, xylene, benzene and the like, preferably toluene; the first palladium catalyst is selected from Pd (TFA) 2 、PdCl 2 、Pd 2 (dba) 3 、Pd(PPh 3 ) 2 Cl 2 、PdCl 2 ·dppf、Pd 3 (PPh) 4 、Pd(acac) 2 、Pd(OAc) 2 One of them, preferably Pd 3 (PPh) 4 。
N 2 Under the protection, the general formula 4 is dissolved in an aprotic solvent which is stable to strong alkali and halogen, and strong alkali is added into the mixture at a low temperature (0 to minus 78 ℃), wherein the addition amount of the strong alkali is 1 to 10 times of the number of moles of the compound 1. The temperature was maintained and then tri-n-butyltin chloride was added. After the completion of the reaction, the reaction was quenched with saturated aqueous ammonium chloride solution, anhydrous MgSO 4 Drying and removing the solvent to obtain an intermediate 1.
The aprotic solvent is selected from dialkylamides, simple ethers (linear ethers such as diethyl ether, methyl-t-butyl ether), cyclic ethers such as THF and glyme, or mixtures of such solvents, preferably THF; the strong alkali sodium methoxide, sodium hydroxide, potassium tert-butoxide, sodium hydride and n-butyllithium are preferably n-butyllithium.
(2) Synthesis of intermediate 2:
reference (Science 2011, 334, 629.) methods.
(3) Synthesis of intermediate 3:
obtained by a Stille coupling reaction of intermediate 1 and intermediate 2 in a solvent and a palladium catalyst, see the synthesis of formula 4.
(4) Synthesis of intermediate 4:
N 2 protection, intermediate 3 is dissolved in a benign solvent that does not react with intermediate 3, selected from tetrahydrofuran, dichloromethane, diethyl ether, preferably tetrahydrofuran. Then adding a fluoride reagent to remove the silicon protecting group, wherein the fluoride reagent is selected from tetrabutylammonium fluoride, hydrogen fluoride pyridine salt and triethylamine hydrogen fluoride salt, and preferably tetrabutylammonium fluoride. The reaction is carried out at room temperature and is monitored by Thin Layer Chromatography (TLC), typically for several hours to days. After the reaction was completed, the reaction was quenched with water, and the organic phase was extracted with dichloromethane, anhydrous MgSO 4 Drying, and spin-removing solvent to obtain intermediate 4.
(5) Synthesis of intermediate 5:
intermediate 5 is obtained through a Sonogashira coupling reaction between intermediate 4 and methyl p-bromobenzoate or bromobenzothiadiazole benzoate and a ligand under the conditions of a solvent, a second palladium catalyst and an organic base.
The addition amount of the second palladium catalyst is 0.1 to 0.5 times of the mole number of the intermediate 4. The addition amount of the ligand is 1.2 to 5 times of the mole number of the palladium catalyst. The addition amount of the organic base is 1 to 10 times of the mole number of the intermediate 4. The reaction is carried out at the boiling temperature of the solvent, generally (50 to 150 ℃). The reaction is monitored by Thin Layer Chromatography (TLC), typically for several hours to days. After the reaction was completed, the solvent was removed by spin-drying under reduced pressure, and column chromatography was performed to obtain intermediate 5.
The solvent is one of toluene, tetrahydrofuran, xylene and methyl tertiary butyl ether, preferably tetrahydrofuran; the second palladium catalyst is Pd (TFA) 2 、PdCl 2 、Pd 2 (dba) 3 、Pd(PPh 3 ) 2 Cl 2 、PdCl 2 ·dppf、Pd 3 (PPh) 4 、Pd(acac) 2 、Pd(OAc) 2 One of them, preferably Pd 2 (dba) 3 The method comprises the steps of carrying out a first treatment on the surface of the The organic base is one of triethylamine and diisopropylethylamine, preferably triethylamine; the ligand is dppf, DPEPhos, t-Bu-Xantphos, dcype, (3, 5-DiMePh) 3 P、Cy 3 P、(p-MePh) 3 P、sPhos、(o-MeOPh) 3 P、t-BuXPhos、TFP、AsPh 3 One or more of them, preferably AsPh 3 。
(6) Synthesizing a target benzodithiophene porphyrin sensitizer:
and dissolving the intermediate 5 in a mixed solvent of tetrahydrofuran and methanol, and carrying out hydrolysis and demethylation by using an aqueous solution of NaOH to obtain the target photosensitive dye. The concentration of the NaOH aqueous solution is 1-20%. The volume ratio of the solvent is 1.5-3:1.0-2.0:0.2-0.5. The reaction temperature is 0-40 ℃. The reaction is monitored by Thin Layer Chromatography (TLC), typically for several hours to days. After the completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with water, 1M diluted hydrochloric acid, washed with water again, and anhydrous MgSO 4 Drying, decompressing, spin-removing the solvent, and performing column chromatography to obtain the target benzodithiophene porphyrin sensitizer.
In a third aspect, the present invention provides a use of the benzodithiophene porphyrin sensitizer for a solar cell, including the following steps:
(1) Adding the benzodithiophene porphyrin sensitizer into a mixed organic solvent to prepare a photosensitive dye solution with the concentration of 0.1-2.0 mM;
(2) Using fluorine-doped SnO 2 Is transparent conductive glass; will be attached with nano TiO 2 Immersing transparent conductive glass of the film in the solution of the photosensitive dye in the step (1) for dye bath to obtain a photo-anode;
(3) Depositing a Pt catalyst layer on the surface of the other transparent conductive glass to serve as a photocathode; the Pt catalyst layer is prepared by sputtering or coating chloroplatinic acid alcohol solution and sintering in a muffle furnace;
(4) TiO adsorbing the benzo-dithiophene porphyrin sensitizer dye 2 And assembling the thin film layer photo-anode with the photo-cathode deposited with the Pt catalytic layer and the iodine electrolyte to obtain the solar cell.
According to an embodiment of the invention, the testing of DSSCs was performed under a standard solar simulator and corrected to 100 mW-cm by standard silicon solar cells -2 The intensity of the illumination. The current-voltage curve of the cell was measured by the electrochemical workstation (Zennium, germany). The working area of the battery was 0.196cm 2 The photoelectric conversion efficiency was measured to be 2.05 to 6.64%.
In a fourth aspect of the present invention, there is provided a solar cell comprising the above-described benzodithiophene porphyrin sensitizer.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel benzo-dithiophene porphyrin sensitizer taking a sulfur-containing condensed heteroaromatic compound as an electron donor, which can enable an organic solar cell device containing the benzo-dithiophene porphyrin sensitizer to have higher photoelectric conversion efficiency.
Drawings
FIG. 1 is an ultraviolet/visible absorption spectrum of porphyrin dyes synthesized in example 1, example 2 and example 3 in tetrahydrofuran solution.
Fig. 2 is a graph of current versus voltage measured for cells assembled from porphyrin dyes synthesized in example 1, example 2, and example 3.
Detailed Description
Specific implementations of the invention are further described below with reference to the drawings and examples, but the implementation and protection of the invention are not limited thereto. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Interpretation of the terms
Open circuit Voltage (VOC): VOC is the voltage when the external circuit of the solar cell is disconnected or the current is zero, namely the maximum output voltage, and is the value corresponding to the ordinate when the abscissa is 0 in the J-V curve.
Short circuit current (JSC): JSC is the current density on the external circuit when the voltage applied to the solar cell is zero, and is the value corresponding to the abscissa when the ordinate is 0 in the J-V curve.
Fill Factor (FF): FF is the ratio of the maximum power provided by the solar cell under a certain load to the product of VOC and JSC, and represents the capability parameter of the device to provide maximum output power to the outside.
FF＝(Vmax×Jmax)/(VOC×JSC)＝Pmax/(VOC×JSC)
Where Vmax and Jmax are the voltage and current, respectively, of the maximum output power point Pmax.
Photoelectric Conversion Efficiency (PCE): PCE indicates how much of the energy of the incident light can be converted into useful electrical energy, which is the ratio of Pmax (maximum output power) to Pin (incident monochromatic light power).
PCE＝Pmax/Pin＝(VOC×JSC×FF)/Pin
Example 1: compound 10
In this example, R is 2-ethylhexyl, R is synthesized by 1 And R is 2 Is 2-n-hexylthiophene, R 3 And R is 4 Porphyrin photosensitive dye with straight-chain octyl and Ar being benzothiadiazole methyl benzoate has the following structure:
(1) Synthesis of Compound 5
N 2 Protection at-78deg.C, 2.5M n-BuLi in n-hexane (0.58 mL,1.44 mmol) was slowly added dropwise to a tetrahydrofuran solution (10 mL) of Compound 1 (616.9 mg,1.18 mmol), after the addition was complete, stirring was continued at-78deg.C for 90min, and Br was then added 2 (55. Mu.L, 1.07 mmol) solutionThe reaction was added dropwise to 1mL of dry n-hexane, stirred at-60℃for another 90 minutes, and then stirred at room temperature overnight. The reaction was quenched by adding a few drops of saturated aqueous ammonium chloride solution, and the reaction mixture was diluted with 50mL of n-hexane, anhydrous MgSO 4 Drying, spin-off of solvent, column chromatography with dichloromethane/petroleum ether=1:9 afforded compound 2 as a yellow oil.
Compound 2 (342.9 mg,0.57 mmol), compound 3 (335 mg,0.69 mmol) and Pd (PPh) 3 ) 4 (66 mg,0.057 mmol) was added to a dried 100mL two-port reaction flask, 35mL of dry toluene was injected, freeze-degassed 3 times, and heated at reflux overnight. The solvent was removed and column chromatography on petroleum ether/dichloromethane=4:1 afforded compound 4 as a yellow oil.
1 H NMR(400MHz,Chloroform-d)δ7.66–7.61(m,2H),7.45(d,J＝5.7Hz,1H),7.32(dd,J＝3.5,2.0Hz,2H),7.14(d,J＝3.6Hz,1H),6.95(dd,J＝4.8,3.6Hz,2H),6.71(d,J＝3.6Hz,1H).,2.96(td,J＝7.7,5.1Hz,4H),2.77(d,J＝6.7Hz,2H),1.82(pt,J＝7.4,3.7Hz,4H),1.71–1.63(m,1H),1.55–1.45(m,4H),1.43–1.31(m,16H),0.95–0.75(m,12H). 13 C NMR(100MHz,Chloroform-d)δ147.29,147.22,147.17,145.65,138.52,137.35,136.96,136.43,129.34,128.46,127.83,127.75,127.15,126.07,125.25,125.06,124.34,124.29,123.77,123.52,122.94,118.03,41.49,41.41,34.28,34.16,32.38,31.79,31.60,31.56,30.30,30.27,28.95,28.88,28.73,25.54,25.50,23.00,22.62,14.13,10.83.HRMS(MALDI)m/z:[M] + calcd for C 42 H 52 S 5 :716.2668；found,716.2666.
Compound 4 (286.8 mg,0.4 mmol) was added to a baked 50mL two-necked flask, N 2 Protection, injecting dried tetrahydrofuran 6mL, slowly dripping 0.25M tetrahydrofuran/n-hexane mixed solution (2.1 mL,0.53 mmol) of n-BuLi at-78 ℃ and stirring for 90min; then, tri-n-butyltin chloride (0.2 mL,0.74 mmol) was slowly added dropwise, the reaction system was warmed to-60℃and stirred for 1h, and then the reaction system was allowed to slowly warm to room temperature. Dropping saturated ammonium chloride aqueous solution to quench reaction, anhydrous MgSO 4 Drying, spin-off the solvent, to give compound 5 as a yellow oil, which was used directly in the next step.
( 2) Synthesis of compound 7 (reference report synthesis: science 2011, 334, 629. )
Compound 6 (600 mg, 0.460 mmol), compound 5 (460 mg, 0.460 mmol) and Pd (PPh) 3 ) 4 (43 mg,0.037 mmol) was added to a previously dried 100mL two-necked flask, 30mL of dried toluene was injected, freeze-deaerated 3 times, and then heated under reflux overnight; the solvent was removed and column chromatography on petroleum ether/dichloromethane=5:1 afforded compound 7 as a green solid.
1 H NMR(400MHz,Chloroform-d)δ9.69(d,J＝4.6Hz,2H),9.12(d,J＝4.7Hz,2H),8.88(d,J＝4.5Hz,2H),8.79(d,J＝4.6Hz,2H),8.36(s,1H),7.77(s,1H),7.65(t,J＝8.4Hz,2H),7.46(t,J＝3.3Hz,2H),7.19(d,J＝3.5Hz,1H),6.97(d,J＝8.5Hz,4H),6.89(d,J＝3.6Hz,1H),6.83(d,J＝3.6Hz,1H),6.73(d,J＝3.6Hz,1H),3.81(tt,J＝6.6,2.5Hz,8H),2.87(q,J＝7.3Hz,2H),2.83–2.73(m,4H),1.89(d,J＝6.2Hz,4H),1.73(p,J＝7.6Hz,2H),1.69–1.55(m,4H),1.43(d,J＝4.8Hz,21H),1.35–1.24(m,16H),1.20(p,J＝3.8Hz,4H),0.92(dqt,J＝8.8,6.7,2.7Hz,20H),0.86–0.81(m,4H),0.79–0.69(m,11H),0.48(d,J＝28.8Hz,32H). 13 C NMR(100MHz,Chloroform-d)δ158.95,151.10,149.97,149.56,148.80,146.08,144.55,136.11,134.29,130.81,130.41,130.27,129.67,128.63,128.29,126.89,126.84,125.07,124.00,123.29,123.19,121.43,120.24,117.40,113.61,104.24,98.49,76.18,67.68,65.29,40.49,33.28,31.39,30.51,30.48,30.44,30.41,30.20,29.24,29.18,28.68,27.89,27.84,27.54,27.50,24.50,24.12,23.36,21.99,21.51,21.43,21.08,18.08,13.14,13.11,13.01,12.93,12.71,10.93,9.83.HRMS(MALDI)m/z:[M] + calcd for C 117 H 154 N 4 O 4 S 5 SiZn:1930.9634；found,1930.9613.
(3) Synthesis of Compound 8
Compound 7 (260 mg,0.134 mmol) was placed in a 50mL two-necked flask, N 2 Protection, injection of 10mL of dry tetrahydrofuran, addition of 0.2mL of 1mol/L tetrahydrofuran solution of tetrabutylammonium fluoride, stirring at room temperature for 30min, addition of water to quench the reaction, extraction of the organic phase (50 mL. Times.3) with dichloromethane, and subsequent anhydrous MgSO 4 Drying, spin-removing solvent, and directly using in the next step without further purification.
(4) Synthesis of Compound 10
The product of the previous step 8, 4- (7-bromobenzo [ c)][1,2,5]Thiadiazole) benzoic acid methyl ester (94 mg,0.268 mmol), palladium catalyst Pd 2 (dba) 3 (25 mg,0.027 mmol) and AsPh 3 (82 mg,0.268 mmol) into a 100mL baked two-necked flask, N 2 Protection, injection of 20mL dry tetrahydrofuran, 4mL freshly distilled triethylamine, freeze-deaeration 3 times, heat reflux for 15h, spin-off solvent, dichloromethane/petroleum ether=2:1 column chromatography to give compound 9.
Compound 9 (230 mg,0.1124 mmol) was placed in a 100mL two-necked flask, and 30mL of tetrahydrofuran, 20mL of methanol, 8mL of a 20% aqueous NaOH solution, N 2 Under protection, the temperature is raised to 40 ℃ and the reaction is stirred, and after TLC detection, the reaction is stopped after about 2.5 h. The reaction was diluted with 100mL of dichloromethane, washed twice with 1M dilute hydrochloric acid twice, once with water, and anhydrous MgSO 4 Drying, spin-drying under reduced pressure, and column chromatography with dichloromethane/methanol=15:1 to give a tan solid as compound 10.
UV-vis(THF):λ max ＝440,457,653nm. 1 H NMR(400MHz,Chloroform-d)δ10.08(d,J＝4.5Hz,2H),9.16(d,J＝4.6Hz,2H),9.02(d,J＝4.6Hz,2H),8.83(d,J＝4.6Hz,2H),8.38(s,1H),8.26(d,J＝7.2Hz,1H),8.12(s,4H),7.90(dd,J＝7.5,3.9Hz,1H),7.77(s,1H),7.70(t,J＝8.4Hz,2H),7.47(t,J＝3.0Hz,2H),7.17(d,J＝3.4Hz,1H),7.01(d,J＝8.5Hz,4H),6.90(d,J＝3.7Hz,1H),6.84(d,J＝3.7Hz,1H),6.71(t,J＝4.1Hz,1H),3.86(ddt,J＝9.8,7.2,3.3Hz,8H),2.88(t,J＝7.7Hz,2H),2.78(dt,J＝15.4,7.2Hz,4H),1.74(p,J＝7.6Hz,2H),1.66(t,J＝7.6Hz,3H),1.44–1.36(m,4H),1.36–1.27(m,12H),1.21(h,J＝3.8Hz,4H),0.99(q,J＝7.0Hz,7H),0.93(td,J＝7.5,7.0,4.5Hz,8H),0.88–0.81(m,4H),0.80–0.68(m,12H),0.55(d,J＝15.3Hz,18H),0.42(t,J＝7.4Hz,23H). 13 C NMR(100MHz,Chloroform-d)δ170.56,159.96,156.14,153.19,152.14,151.30,150.71,149.94,147.17,145.62,145.27,142.32,141.26,138.54,138.44,137.37,137.12,137.01,136.40,135.30,132.42,132.10,131.79,131.46,131.06,130.92,130.44,129.87,129.53,129.20,128.64,127.97,127.92,126.13,125.07,124.36,124.27,123.81,122.49,121.06,118.65,118.43,115.30,112.55,105.35,102.02,98.54,92.12,68.75,49.84,41.53,34.31,32.42,31.57,31.55,31.51,31.47,31.30,30.30,30.24,28.95,28.93,28.92,25.53,25.20,23.05,22.57,22.50,22.18,14.20,14.08,14.01,13.78,10.88.HRMS(MALDI)m/z:[M] + calcd for C 121 H 140 N 6 O 6 S 6 Zn:2028.8445；found,2028.8420.
Example 2: compound 12
In this example, R is 2-ethylhexyl, R is synthesized by 1 And R is 2 Is 2-n-hexylthiophene, R 3 And R is 4 Porphyrin photosensitive dye with straight-chain octyl and Ar as benzene ring has the following structure:
a method for synthesizing the exemplary porphyrin-based photosensitizing dye, comprising the steps of:
(1) Compound 5, compound 7 and compound 8 were synthesized according to the synthesis method of example 1;
(2) Synthesis of Compound 12:
the product 8 of the above step, methyl p-bromobenzoate (46 mg,0.214 mmol), asPh 3 (26 mg,0.0856 mmol) and Pd 2 (dba) 3 (11.7 mg,0.0129 mmol) into 100mL of dried reaction flask, N 2 Protection, injection of 20mL dry tetrahydrofuran, 4mL freshly distilled triethylamine, and freeze-deaeration for 3 times, then heat reflux for 4h, removal of solvent, column chromatography with dichloromethane/petroleum ether=1:4, finally yields the green solid as compound 11.
Compound 11 (60 mg,0.0313 mmol) was placed in a 100mL two-necked flask, and 10mL of tetrahydrofuran, 50mL of methanol, 2mL of 20% aqueous NaOH solution, N 2 Under protection, the temperature is raised to 40 ℃ and the reaction is stirred, and after TLC detection, the reaction is stopped after about 2.5 h. The reaction was diluted with 50mL of dichloromethane, washed twice with 1M dilute hydrochloric acid twice, once with water, and anhydrous MgSO 4 Drying, spin-drying under reduced pressure, and column chromatography with dichloromethane/methanol=15:1 to give the green solid as compound 12.
1 H NMR(400MHz,Chloroform-d)δ9.73(d,J＝4.6Hz,2H),9.16(d,J＝4.7Hz,2H),8.96(d,J＝4.6Hz,2H),8.82(d,J＝4.7Hz,2H),8.38(s,1H),8.19(d,J＝8.1Hz,2H),8.07(d,J＝7.8Hz,2H),7.78(s,1H),7.69(t,J＝8.4Hz,2H),7.47(t,J＝3.5Hz,2H),7.18(d,J＝3.5Hz,1H),7.00(d,J＝8.5Hz,4H),6.90(d,J＝3.7Hz,1H),6.84(d,J＝3.7Hz,1H),6.73(d,J＝3.5Hz,1H),3.85(p,J＝6.3,4.7Hz,8H),2.88(t,J＝7.7Hz,2H),2.83–2.75(m,4H),1.75(q,J＝7.6Hz,2H),1.68(d,J＝7.6Hz,4H),1.39(ddd,J＝10.6,7.0,3.5Hz,4H),1.36–1.26(m,14H),1.21(h,J＝3.8Hz,6H),0.94(dt,J＝15.0,7.7Hz,14H),0.89–0.82(m,4H),0.74(dd,J＝15.1,7.1Hz,12H),0.60–0.49(m,16H),0.45–0.38(m,21H). 13 C NMR(100MHz,Chloroform-d)δ159.94,151.76,151.28,150.66,150.03,147.17,145.64,145.21,141.26,138.56,138.47,137.39,137.11,136.99,136.40,136.36,135.31,132.23,131.79,131.57,131.32,130.40,130.23,129.89,129.54,127.96,127.91,126.13,125.08,124.36,124.26,123.82,122.50,120.98,118.43,115.24,112.38,105.31,98.47,97.19,94.69,68.71,41.54,34.33,32.44,31.55,31.54,31.49,31.46,31.27,30.29,30.23,28.94,28.90,28.61,28.56,25.55,25.20,23.04,22.55,22.48,22.17,14.18,14.06,13.99,13.77,10.88.UV-Vis(THF):λ max ＝448,574,631nm.HRMS(MALDI)m/z:[M] + calcd for C 115 H 138 N 4 O 6 S 5 Zn:1894.8506；found,1894.8508.
Example 3: compound 20
In this example, R is 2-ethylhexyl, R is synthesized by 1 And R is 2 Is n-octoxy, R 3 And R is 4 Porphyrin photosensitive dye with straight-chain octyl and Ar as benzene ring has the following structure:
(1) Synthesis of Compound 16
N 2 Protection, -78 ℃, 2.5M n-BuLi in n-hexane (0.58 mL,1.44 mmol) was slowly added dropwise to a tetrahydrofuran solution (10 mL) of Compound 13 (528 mg,1.18 mmol), after the dropwise addition was complete, stirring was continued for 90min at-78 ℃, and Br was then added 2 (55. Mu.L, 1.07 mmol) was dissolved in 1mL of dry n-hexane and the reaction solution was added dropwise, and the mixture was stirred at-60℃for another 90 minutes, and then allowed to warm to room temperature and stirred overnight; the reaction was quenched by adding a few drops of saturated aqueous ammonium chloride solution, and the reaction mixture was diluted with 50mL of n-hexane, anhydrous MgSO 4 Drying, then spin-off the solvent, and column chromatography with dichloromethane/petroleum ether=1:9 to give the final yellow oily liquid as compound 14.
Compound 14 (300 mg,0.57 mmol), compound 3 (335 mg,0.69 mmol) and catalyst Pd (PPh) 3 ) 4 (66 mg,0.057 mmol) was added to a baked 100mL two-necked flask, N 2 Protection, 35mL of dry toluene was injected, freeze-deaerated 3 times, and then heated under reflux overnight; the solvent was removed and column chromatography on petroleum ether/dichloromethane=4:1 afforded compound 15.
Compound 15 (256 mg,0.4 mmol) was added to a dried 50mL two-necked flask, N 2 Protection, injecting dried tetrahydrofuran 6mL, slowly dripping 0.25M tetrahydrofuran/n-hexane mixed solution (2.1 mL,0.53 mmol) of n-BuLi at-78 ℃ and stirring for 90min; thenTri-n-butyltin chloride (0.2 mL,0.74 mmol) was slowly added dropwise, the reaction system was warmed to-60℃and stirred for 1h, and then the reaction system was allowed to slowly warm to room temperature; dropping saturated ammonium chloride aqueous solution to quench reaction, anhydrous MgSO 4 Drying, spin-off of solvent, gave a yellow oil which was used directly in the next step without further purification.
1 H NMR(400MHz,Chloroform-d)δ7.48–7.40(m,2H),7.34(dd,J＝9.2,5.5Hz,1H),7.13(d,J＝3.5Hz,1H),6.71(d,J＝3.6Hz,1H),4.26(td,J＝6.6,3.8Hz,4H),2.76(d,J＝6.8Hz,2H),1.88(dqd,J＝10.4,6.7,3.8Hz,4H),1.58(dt,J＝15.2,6.9Hz,5H),1.43–1.28(m,24H),0.98–0.78(m,12H). 13 C NMR(100MHz,Chloroform-d)δ145.57,144.26,144.11,137.19,135.09,132.33,131.71,130.58,128.85,126.08,125.76,125.04,120.45,115.02,73.95,73.90,41.51,34.29,32.42,31.88,30.56,29.46,29.36,29.33,28.91,26.12,26.10,25.55,23.03,22.72,14.15,10.86.HRMS(MALDI)m/z:[M] + calcd for C 38 H 56 O 2 S 3 :640.3437；found,640.3441.
(2) Synthesis of Compound 17
Compound 6 (70 mg,0.0539 mmol), compound 16 (100 mg,0.11 mmol) and palladium catalyst Pd (PPh) 3 ) 4 (9.96 mg,0.0086 mmol) was added to a baked 100mL two-necked flask, N 2 Under protection, 25mL of dry toluene was injected, freeze-deaerated 3 times, and then heated under reflux overnight; the solvent was removed and column chromatography on petroleum ether/dichloromethane=5:1 afforded compound 17 as a green oil.
1 H NMR(400MHz,Chloroform-d)δ9.73(d,J＝4.6Hz,2H),9.16(d,J＝4.7Hz,2H),8.93(d,J＝4.6Hz,2H),8.84(d,J＝4.7Hz,2H),8.18(s,1H),7.67(t,J＝8.4Hz,2H),7.59(s,1H),7.22(d,J＝3.5Hz,1H),6.98(d,J＝8.5Hz,4H),6.77(d,J＝3.5Hz,1H),4.44(td,J＝6.6,2.6Hz,4H),3.82(t,J＝6.5Hz,8H),2.81(d,J＝6.7Hz,2H),1.92(dt,J＝18.0,7.5Hz,4H),1.44(d,J＝5.0Hz,21H),1.36(q,J＝5.7Hz,12H),1.30–1.23(m,16H),1.20–1.16(m,4H),0.94(h,J＝6.0,5.3Hz,16H),0.81–0.66(m,16H),0.51(dt,J＝13.4,7.1Hz,14H),0.44–0.36(m,24H). 13 C NMR(100MHz,CDCl 3 )δ158.90,151.16,150.06,149.67,148.99,144.48,143.13,142.88,141.97,136.12,134.23,131.43,131.25,131.00,130.61,130.48,130.45,129.83,128.76,128.14,125.30,125.08,123.99,120.02,114.35,113.88,110.47,108.85,104.28,98.90,95.53,73.07,72.85,67.68,40.49,33.27,31.38,30.90,30.78,30.74,30.18,29.60,28.68,28.43,28.34,28.25,28.17,27.88,27.49,25.10,25.00,24.50,24.13,22.01,21.67,21.59,21.54,21.07,18.07,13.15,13.10,13.02,12.99,12.69,10.90,9.84.HRMS(MALDI)m/z:[M] + calcd for C 113 H 158 N 4 O 6 S 3 SiZn:1855.0399；found,1855.0376.
(3) Synthesis of Compound 18
Compound 17 (73 mg,0.0393 mmol) was placed in a 50mL two-port reaction flask, N 2 Protection, 10mL of dry tetrahydrofuran was injected, 0.2mL of 1M tetrabutylammonium fluoride in tetrahydrofuran was injected, stirred at room temperature for 30min, quenched with water, and the organic phase (50 mL. Times.3) was extracted with dichloromethane, anhydrous MgSO 4 Drying, spin-removing solvent, and directly using in the next step without further purification.
(4) Synthesis of Compound 20
The product 18 of the above step, methyl p-bromobenzoate (43 mg,0.2 mmol) and Pd as a catalyst 2 (dba) 3 (11 mg,0.0118 mmol) and AsPh 3 (24 mg,0.0786 mmol) into a 100 mL-dried two-port reaction flask, N 2 Under protection, 15mL of dry tetrahydrofuran and 3mL of triethylamine are injected, freeze-deaeration is carried out for 3 times, heating reflux is carried out for 4 hours, the solvent is removed by rotary evaporation under reduced pressure, and dichloromethane/methanol=30:1 column chromatography is carried out, thus obtaining green solid which is taken as a compoundAnd (3) an object 19.
Compound 19 (60 mg,0.0337 mmol) was placed in a 100mL two-necked flask, 10mL tetrahydrofuran, 50mL methanol, 2mL of 20% aqueous NaOH solution, N 2 Under protection, the temperature is raised to 40 ℃ and the reaction is stirred, and after TLC detection, the reaction is stopped after about 2.5 h. The reaction was diluted with 50mL of dichloromethane, washed twice with 1M dilute hydrochloric acid twice, once with water, and anhydrous MgSO 4 Drying, spin-drying under reduced pressure, and column chromatography with dichloromethane/methanol=15:1 to give the green solid as compound 20.
1 H NMR(400MHz,Chloroform-d)δ9.73(s,2H),9.15(d,J＝4.7Hz,2H),8.97(d,J＝14.9Hz,2H),8.91–8.74(m,2H),8.20(d,J＝19.6Hz,3H),8.13–7.94(m,2H),7.68(t,J＝8.6Hz,2H),7.58(s,1H),7.22(s,1H),6.99(d,J＝8.5Hz,4H),6.77(s,1H),4.44(d,J＝6.8Hz,4H),3.84(s,8H),2.81(d,J＝6.8Hz,2H),1.90(dq,J＝15.1,7.6Hz,4H),1.55(dd,J＝19.5,11.6Hz,5H),1.49–1.11(m,28H),1.10–0.84(m,16H),0.77(t,J＝9.1Hz,16H),0.57–0.32(m,36H). 13 C NMR(100MHz,Chloroform-d)δ157.78,149.61,149.16,149.11,148.55,148.38,147.89,143.39,142.02,141.76,140.83,140.78,135.03,133.10,130.33,130.29,130.23,130.14,130.05,129.88,129.50,129.47,129.43,129.40,129.10,129.04,128.99,128.60,128.54,128.48,128.35,128.28,128.20,128.15,128.11,128.06,127.80,127.74,127.67,127.04,123.98,122.89,118.86,113.24,113.00,103.11,71.98,71.74,66.52,39.38,32.16,30.27,29.67,29.64,29.17,28.49,27.57,27.32,27.27,27.14,27.07,26.77,26.54,26.50,26.45,23.99,23.89,23.39,23.06,20.90,20.48,20.44,20.08,20.06,12.05,11.92,11.90,11.64,8.73.UV-Vis(THF):λ max ＝448,574,631nm.HRMS(MALDI)m/z:[M] + calcd for C 111 H 142 N 4 O 8 S 3 Zn:1818.9276；found,1818.9272.
Example 4
The porphyrin photosensitive dyes prepared in example 1, example 2 and example 3 were subjected to uv-vis absorption spectrum test, and the uv-vis absorption spectrum is shown in fig. 1.
Wherein, relevant parameters and instruments of the ultraviolet-visible absorption spectrum test are as follows.
Solvent: tetrahydrofuran;
concentration: 2X 10 -5 M；
Temperature: room temperature;
instrument: shimadzu UV-2450 ultraviolet visible spectrophotometer.
As can be seen from FIG. 1, the three porphyrin dyes prepared in example 1, example 2 and example 3 all have typical absorption peaks of porphyrin compounds in the range of 400 to 500nm and 550 to 700 nm: soret and Q bands. The dye prepared in example 2 and example 3 has an absorption spectrum slightly different from that of the near ultraviolet region only in the range of 300 to 400nm, and the absorption spectra of the visible region and the near infrared region are almost overlapped. The different substituents on the donor do not have much influence on the absorption spectra of the two dyes. The introduction of benzothiadiazole then produces a significant disturbance of the absorption spectrum of the dye prepared in example 3, the Soret band of which has a weak absorption intensity and a split, the shoulder at 457nm appearing on the right side of the maximum absorption wavelength (440 nm). In addition, the absorption spectrum of the dye prepared in example 3 is remarkably widened in the absorption band of 450-550 nm, the molar extinction coefficient of the Q band is increased, and the red shift of 22nm occurs.
Example 5
The three porphyrin dyes with dithienobenzene as an electron donor prepared in the examples 1,2 and 3 are applied to the preparation of dye sensitized solar cells, and the three porphyrin dyes comprise the following steps:
(1) Cleaning conductive glass
Fluorine doped SnO 2 Transparent conductive glass was purchased from martial arts solar technologies Inc. (2.2 mm thick, 14 Ω/aq,90% transmittance, 20cm x 15 cm).
Cutting conductive glass into small pieces of 2cm×1.5cm, placing in aqueous solution of detergent, ultrasonic treating for 30min, and ultrasonic treating with distilled water, acetone, and ethanol for 30min. Finally, the conductive glass is immersed in absolute ethyl alcohol for standby.
(2) Preparation of counter electrode
Configuration of 20mM H 2 PtCl 6 Then two drops of the solution are dripped on the surface of clean small pieces of conductive glass, and the solution is placed on a spin coater for spin (2000 r/min) for 10s, so that the chloroplatinic acid solution is uniformly dispersed on the surface of the conductive glass. Placing the conductive glass coated with chloroplatinic acid in a muffle furnace, and programming to heat: heating to 400 ℃ at a speed of 20 ℃/min, preserving heat for 20min, cooling to room temperature, taking out, and placing in a dryer for standby.
(3) Preparation of photoanode
The photo anode adopts commercial TiO 2 The slurry (seven-color light, average particle size of transmission layer 20nm; average particle size of scattering layer 200 nm) was prepared by screen printing technique. The thickness of the transport layer is about 10 μm; the thickness of the scattering layer is about 10 μm. The sintering temperature rising process in the muffle furnace is as follows: heating to 125 deg.c from room temperature at 10 deg.c/min and maintaining for 5min; heating to 250deg.C, and maintaining for 5min; heating to 325 ℃, and preserving heat for 5min; heating to 375 deg.C, and maintaining for 5min; heating to 450 ℃, and preserving heat for 15min; finally, the temperature is raised to 500 ℃ and the temperature is kept for 15min. And naturally cooling, taking out, and placing in a dryer for standby. Then at 40mM TiCl 4 The aqueous solution was hydrolyzed at 70 ℃ for 30min, and the electrode was again placed in a muffle furnace for sintering: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat for 40min. The procedure was then terminated and after cooling to room temperature, taken out for use.
(4) Battery assembly and testing
The dye is dyed by using a mixed solvent of tetrahydrofuran and ethanol (volume ratio: tetrahydrofuran: ethanol=1:4), the dye bath time is 12h, and the concentration is 0.2mM. And (3) dropwise adding a drop of electrolyte solution on the photo-anode adsorbed with the photosensitive dye, and assembling the photo-anode and the counter electrode into the DSSCs with a sandwich structure. The effective area of DSSCs is 0.196cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Iodine electrolyte formulation: will be 0.03M I 2 0.05M LiI,0.6M PMII,0.1M guanidine thiocyanate and 0.5M 4-tert-butylpyridine were dissolved in a mixed solvent of acetonitrile and valeronitrile (v/v=85/15).
The test of DSSCs was performed under a standard solar simulator and corrected to 100mW cm by a standard silicon solar cell -2 The intensity of the illumination. J of batteryThe V curve is measured by an electrochemical workstation (Zennium, germany). The monochromatic photoelectric conversion efficiency (IPCE) of the cell was measured by a workstation (QTest Station 2000IPCE Measurement System,CROWNTECH,USA).
The measured current-voltage graph is shown in fig. 2, and the data are summarized in table 1.
Table 1: the solar cell provided by the invention has the performance
Dye V oc [mV] J sc [mA cm -2 ] FF[％] PCE[％]
Based on example 1 688 15.81 61.0 6.64
Based on example 2 707 14.96 60.9 6.44
Based on example 3 580 4.95 71.0 2.05
The above examples are only preferred embodiments of the present invention, and are merely for illustrating the present invention, not for limiting the present invention, and those skilled in the art should not be able to make any changes, substitutions, modifications and the like without departing from the spirit of the present invention.

Claims (13)

1. The benzodithiophene porphyrin sensitizer is characterized by having a D-pi-A structure, wherein D is an electron donor, pi is a bridge, and A is an electron acceptor;
the electron donor consists of zinc porphyrin, a main donor and an auxiliary donor, and the zinc porphyrin has the following structure:
the main donor is a benzodithiophene compound, and the benzodithiophene compound is benzo [1,2-b:4,5-b' ] dithiophene;
the auxiliary donor has the structure shown in the following general formulas I-II:
wherein R is 3 And R is 4 Is unsubstituted straight-chain or branched alkyl with 1-20 carbon atoms, or is hydrogen;
the pi bridge has a structure of the following general formula II:
wherein Ar is phenyl or benzothiadiazole substituted phenyl, having the structure:
the electron acceptor is carboxyl
2. The benzodithiophene porphyrin sensitizer according to claim 1, wherein the main donor is benzo [1,2-b:4,5-b' ] dithiophene further comprising a modification at the 4, 8-position.
3. The benzodithiophene porphyrin-based sensitizer according to claim 2, wherein the main donor of the electron donor of the benzodithiophene porphyrin-based sensitizer has the following general formula i-i:
wherein R is unsubstituted straight-chain or branched-chain alkyl with 1-20 carbon atoms or hydrogen; r is R 1 And R is 2 Is unsubstituted straight-chain or branched alkoxy with 1-20 carbon atoms, unsubstituted straight-chain or branched alkyl-modified thiophene with 1-20 carbon atoms, or hydrogen.
4. The benzodithiophene porphyrin-based sensitizer according to claim 1, wherein the benzodithiophene porphyrin-based sensitizer has a structure of D-pi-a, wherein D is an electron donor, pi is a bridge, and a is an electron acceptor; the electron acceptor is carboxyl; the benzodithiophene porphyrin sensitizer has a structure shown in the following general formula III:
wherein R is unsubstituted straight-chain or branched-chain alkyl with 1-20 carbon atoms or hydrogen;
R 1 and R is 2 Is unsubstituted straight-chain or branched-chain alkoxy with 1-20 carbon atoms, or unsubstituted straight-chain or branched-chain alkyl-modified thiophene with 1-20 carbon atoms, or hydrogen;
R 3 and R is 4 Is an unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, or is hydrogen.
5. The benzodithiophene porphyrin-like sensitizer according to claim 3, wherein R is 2-ethylhexyl group, R in the structure of the general formula i-i of the main donor 1 And R is 2 2-n-hexylthiophene, having the following structure:
r in the structure of the auxiliary donor general formula I-II 3 And R is 4 Is a linear octyl group having the following structure:
the pi bridge has a structure of the following general formula II:
wherein Ar is phenyl or benzothiadiazole substituted phenyl, having the structure:
6. the benzodithiophene porphyrin-like sensitizer according to claim 3, wherein said agent isR is 2-ethylhexyl radical in the general formula I-I of the main donor, R 1 And R is 2 Is n-octoxy and has the following structure:
r in the structure of the auxiliary donor general formula I-II 3 And R is 4 Is a linear octyl group having the following structure:
the pi bridge has a structure of the following general formula II:
wherein Ar is phenyl or benzothiadiazole substituted phenyl, having the structure:
7. the benzodithiophene porphyrin sensitizer is characterized in that the benzodithiophene porphyrin sensitizer is a compound 10 and has the following structure:
8. the benzodithiophene porphyrin sensitizer is characterized in that the benzodithiophene porphyrin sensitizer is a compound 12 and has the following structure:
9. the benzodithiophene porphyrin sensitizer is characterized in that the benzodithiophene porphyrin sensitizer is a compound 20 and has the following structure:
10. a process for preparing a benzodithiophene porphyrin-like sensitizer according to claim 4 of the general formula III, characterized in that it comprises the following steps:
synthesis of intermediate 3: the intermediate 1 and the intermediate 2 are subjected to Stille coupling reaction in an aprotic small-polarity solvent and a palladium catalyst to obtain the catalyst; the aprotic small polar solvent is toluene; the palladium catalyst is Pd (PPh) 4 ；
Synthesis of intermediate 4: dissolving the intermediate 3 in a benign solvent which does not react with the intermediate 3 at room temperature, adding a fluoride reagent to remove a silicon protecting group, quenching the reaction after the reaction is finished, and extracting, drying and spin-drying to obtain the compound; the benign solvent is tetrahydrofuran; the fluoride reagent is tetrabutylammonium fluoride;
synthesis of intermediate 5: intermediate 4 and methyl p-bromobenzoate or brominated methyl benzothiadiazole benzoate undergo a Sonogashira coupling reaction with a ligand under the conditions of a solvent, a palladium catalyst and an organic base to obtain the intermediate; the solvent is tetrahydrofuran; the palladium catalyst Pd 2 (dba) 3 The method comprises the steps of carrying out a first treatment on the surface of the The organic base is triethylamine; the ligand is AsPh 3 ；
Synthesizing a target benzodithiophene porphyrin sensitizer: dissolving the intermediate 5 in a mixed solvent of tetrahydrofuran and methanol, and carrying out hydrolysis and demethylation by using an aqueous solution of NaOH to obtain the product.
11. Use of a benzodithiophene porphyrin-like sensitizer according to one of claims 1 to 9 for the manufacture of sensitized solar cells.
12. The use according to claim 11, characterized in that it comprises the following steps:
(1) Adding the benzodithiophene porphyrin sensitizer into a mixed organic solvent to prepare a photosensitive dye solution with the concentration of 0.1-2.0 mM;
(2) Using fluorine-doped SnO 2 Is transparent conductive glass; will be attached with nano TiO 2 Immersing transparent conductive glass of the film in the solution of the photosensitive dye in the step (1) for dye bath to obtain a photo-anode;
(3) Depositing a Pt catalyst layer on the surface of the other transparent conductive glass to serve as a photocathode; the Pt catalyst layer is prepared by sputtering or coating chloroplatinic acid alcohol solution and sintering in a muffle furnace;
TiO to which dye of benzodithiophene porphyrin sensitizer is adsorbed 2 And assembling the thin film layer photo-anode with the photo-cathode deposited with the Pt catalytic layer and the iodine electrolyte to obtain the solar cell.
13. A solar cell comprising a benzodithiophene porphyrin sensitizer according to any one of claims 1 to 9.
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Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Dichromophoric zinc porphyrins: Filling the absorption gap between the soret and Q bands;Zhao, Long et al;The Journal of Physical Chemistry C;第119卷(第10期);5350-5363 *
Enhanced light-harvesting of benzodithiophene conjugated porphyrin electron donors in organic solar cells;Zhou, Xuan et al;Journal of Materials Chemistry C: Materials for Optical and Electronic Devices;第7卷(第2期);380-386 *
Panchromatic terthiophenyl-benzodithiophene conjugated porphyrin donor for efficient organic solar cells;Tang, Wei et al;Journal of Materials Chemistry C: Materials for Optical and Electronic Devices;第10卷(第3期);1077-1083 *
Synthesis and characterization of novel D-A porphyrin-containing copolymers for polymer solar cells;Deng, Lijun et al;Materials Science & Engineering, B: Advanced Functional Solid-State Materials;第177卷(第18期);1641-1648 *

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