WO2015177839A1 - Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant - Google Patents

Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant Download PDF

Info

Publication number
WO2015177839A1
WO2015177839A1 PCT/JP2014/063235 JP2014063235W WO2015177839A1 WO 2015177839 A1 WO2015177839 A1 WO 2015177839A1 JP 2014063235 W JP2014063235 W JP 2014063235W WO 2015177839 A1 WO2015177839 A1 WO 2015177839A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
linear
branched alkyl
alkyl group
Prior art date
Application number
PCT/JP2014/063235
Other languages
English (en)
Japanese (ja)
Inventor
井上　要
猛史 越谷
康典 青木
仁志 竿本
岳志 森
功司 町谷
Original Assignee
株式会社日本化学工業所
和歌山県
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日本化学工業所, 和歌山県 filed Critical 株式会社日本化学工業所
Priority to KR1020167033882A priority Critical patent/KR102154732B1/ko
Priority to CN201480079193.2A priority patent/CN106470988B/zh
Priority to PCT/JP2014/063235 priority patent/WO2015177839A1/fr
Publication of WO2015177839A1 publication Critical patent/WO2015177839A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • 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

Definitions

  • the present invention relates to a novel pyrazoline compound, a photoelectric conversion element and a solar cell using the same.
  • Non-Patent Document 1, Patent Document 1 and Patent Document 2 describe a photoelectric conversion electrode and a photoelectric conversion cell using a semiconductor microporous material sensitized with a dye, and a method for producing the same. Materials and manufacturing techniques have been disclosed.
  • the proposed battery is a dye-sensitized photoelectric conversion cell comprising a titanium oxide porous thin layer spectrally sensitized with a ruthenium complex dye, an electrolyte layer mainly composed of iodine, and a counter electrode.
  • the first advantage of this method is that an inexpensive oxide semiconductor such as titanium oxide is used, so that an inexpensive photoelectric conversion element can be provided.
  • the second advantage is that the ruthenium complex dye used is widely absorbed in the visible light range. Therefore, relatively high conversion efficiency can be obtained.
  • ruthenium metal is used as a raw material for the dye.
  • Ruthenium metal exists on the earth only to the same extent as platinum and palladium metal, and has a problem of depleting resources when used in large quantities. Further, the price of the dye becomes expensive, which hinders the mass diffusion of photoelectric conversion cells. For this reason, research on sensitizing dyes based on deruthenium metals has become active in recent years, and dye-sensitized photoelectric conversion cells have become popular in large quantities and become the main source of clean energy sources that do not release carbon dioxide. Therefore, low-cost sensitizing dyes that do not use depleting raw materials have been desired.
  • Patent Document 3 discloses that a pyrazoline compound is used as a light absorber / light shielding agent, but it does not have a carboxyl group or cyanoacrylic acid, and these are used for a photoelectric conversion element. Was not known.
  • An object of the present invention is to develop a high-efficiency sensitizing dye for solar cells that does not use a depleting raw material such as ruthenium, and to provide a photoelectric conversion element and a solar cell using the same.
  • a pyrazoline compound represented by the following general formula (1) As a result of diligent research to solve the major drawbacks of conventionally known sensitizing dyes and solar cells, the present inventor has found that a compound containing a carboxyl group or cyanoacrylic acid at the 3-position end group of pyrazoline meets the purpose. As a result, the present invention was completed. That is, the present invention is characterized by the following points. 1. A pyrazoline compound represented by the following general formula (1).
  • R 1 in the formula is a carboxyl group, cyanoacrylic acid or a structure as shown below.
  • a 1 in the formula has a structure as shown below.
  • a 4 is a hydrogen atom or a structure as shown below, and R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a straight chain having 1 to 8 carbon atoms.
  • a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, a nitro group, a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group Represents a good amino group or cyano group
  • R 7 represents a hydrogen atom, a halogen atom, a hydroxyl group, an acyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched group having 1 to 8 carbon atoms.
  • R 8 and R 9 are each independently A hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a straight chain having 1 to 8 carbon atoms, or Represents a branched alkoxy group, or a phenyl group optionally substituted by a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms
  • X 1 , X 2 and X 3 each independently represents an oxygen atom, a sulfur atom or an imino group which may be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms
  • n is a positive M and l each independently represents an integer of 0 to 2.
  • a 2 in the formula has a structure as shown below.
  • a 5 and A 6 each independently has a structure as shown below, and R 10 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, Straight or branched alkoxy group having 1 to 8 carbon atoms, nitro group, straight or branched alkyl group having 1 to 4 carbon atoms, or straight or branched alkyl group having 1 to 4 carbon atoms Represents an amino group optionally having a phenyl group optionally substituted by a cyano group, a cyano group, an optionally esterified carboxyl group or cyanoacrylic acid, and R 11 and R 12 are each independently a hydrogen atom.
  • X 4 is independently oxygen atom, a sulfur atom or a linear or branched alkyl optionally imino group optionally substituted with a group having 1 to 4 carbon atoms
  • o represents a positive integer.
  • a 3 in the formula has a structure as shown below.
  • R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched structure having 1 to 8 carbon atoms.
  • a phenyl group optionally substituted by an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms Represents an amino group, a cyano group, an optionally esterified carboxyl group or cyanoacrylic acid, and R 16 represents a hydrogen atom, a halogen atom, a hydroxyl group, an acyl group, a linear or branched group having 1 to 8 carbon atoms.
  • R 17 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, or carbon Represents a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group optionally substituted by a linear or branched alkoxy group having 1 to 8 carbon atoms
  • X 5 each independently represents It represents an imino group which may be substituted with an oxygen atom, a sulfur atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and p represents a positive integer.
  • R 1 represents a carboxyl group or cyanoacrylic acid
  • a 1 has the structure shown below
  • a 4 is a hydrogen atom or a structure as shown below
  • a 2 in the formula has the structure as shown below, (In the above, the bond specified by a is bonded to R 1, and the bond specified by b is bonded to the pyrazoline ring.)
  • a 1 is And A 4 is a hydrogen atom or And R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched group having 1 to 4 carbon atoms.
  • X 3 represents an oxygen atom or a sulfur atom
  • n represents 1
  • a 2 is (In the above, the bond specified by a is bonded to R 1, and the bond specified by b is bonded to the pyrazoline ring.)
  • a 5 is And R 10 , R 11 and R 12 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms
  • X 4 each independently represents an oxygen atom or a sulfur atom
  • a 3 is
  • R 13 , R 14 and R 15 are each independently a hydrogen atom, a linear or branched alkoxy group having 1 to 8 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group.
  • R 1 is cyanoacrylic acid or a structure as shown below
  • a 1 has the structure shown below
  • a 4 is a hydrogen atom or a structure as shown below
  • R 3 and R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, carbon Represents a linear or branched alkoxy group having a number of 1 to 8 or a nitro group
  • R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched group having 1 to 8 carbon atoms.
  • a 2 in the formula has a structure as shown below.
  • R 10 each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, a nitro group, or cyano.
  • R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched structure having 1 to 8 carbon atoms. Having a phenyl group optionally substituted by an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms 1.
  • the compound according to 1 above which represents an amino group, a cyano group, or an optionally esterified carboxyl group, and p represents 1 or 2. 5.
  • a photoelectric conversion element comprising a compound represented by the general formula (1). 6).
  • a solar cell comprising a compound represented by the general formula (1).
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 11 and R 12 in the formula are each independently a hydrogen atom, a halogen atom such as chloro or bromo, a hydroxyl group, a methyl group, an isopropyl group or n-hexyl.
  • Alkyl groups such as groups, t-octyl groups, alkoxy groups such as ethoxy groups, t-butoxy groups, isohexyloxy groups, nitro groups, methylamino groups, diethylamino groups, di-n-butylamino groups, diphenylamino groups, etc. Represents an amino group or a cyano group.
  • R 10 , R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom such as bromo / iodo, a hydroxyl group, an alkyl group such as n-propyl group / isobutyl group, a methoxy group / n-hexyloxy / iso Alkoxy groups such as hexyloxy group / n-octyloxy group, amino groups such as nitro group, n-butylamino group / diethylamino group / diphenylamino group, cyano group, carboxyl group, straight chain having 1 to 8 carbon atoms or It represents a carboxyl group esterified with a branched alkyl, for example, a carboxyl group such as methyl carboxylate, t-butylcarboxylic acid, n-octylcarboxylic acid, or cyanoacrylic acid.
  • R 7 represents a hydrogen atom, a halogen atom such as fluoro / bromo, a hydroxyl group, an acyl group such as acetyl group / benzoyl group, an alkyl group such as ethyl group / n-hexyl group, or an alkoxy group such as isopropyloxy group / hexylhexyloxy group
  • R 16 represents a hydrogen atom, a halogen atom such as chloro / iodo, a hydroxyl group, an acyl group such as ethanoyl group / t-butanoyl group, an alkyl group such as methyl group / isoheptyl group, an isopentaoxy group / t-octyloxy group, etc.
  • R 8 , R 9 and R 17 are each independently a hydrogen atom, an alkyl group such as a methyl group or t-butyl group, an alkoxy group such as an isobutoxy group or t-octyloxy group, a phenyl group, a 4-methylphenyl group, or the like
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represents an oxygen atom, a sulfur atom, or an imino group which may be substituted with an alkyl group such as a methyl group or an isopropyl group.
  • n, o and p are each independently a positive integer, preferably 0 to 4, and m and l are each independently an integer of 0 to 2.
  • the pyrazoline compound of the general formula (1) can be synthesized as follows. Aryl (or heteroaryl) ethanone having A 2 represented by general formula (1) and aryl (or heteroaryl) carbaldehyde having an equivalent amount of A 3 are reacted in ethanol at room temperature by adding an aqueous sodium hydroxide solution. . After completion of the reaction, water is added and the precipitated solid is filtered to obtain the desired product. When no solid precipitates, the chalcone represented by the following general formula (3) can be obtained by performing ethyl acetate / water extraction and then purifying by silica gel chromatography.
  • aryl (or heteroaryl) hydrazine (or hydrazine hydrochloride) represented by the following general formula (2) are reacted under reflux in ethanol. After the reaction, recrystallization is performed as it is, or ethyl acetate / water extraction is performed, followed by purification by silica gel chromatography to obtain a pyrazoline represented by the following general formula (1). Also, the prepared pyrazoline is dissolved in N, N-dimethylformamide, and Vilsmeier reagent prepared with phosphoryl chloride and N, N-dimethylformamide is added dropwise at 0 ° C., and the temperature is slowly raised to 70 ° C. to react.
  • the pyrazoline compound of the present invention can be synthesized by the following method. That is, a compound represented by the following general formula (2) and an equivalent amount of a compound represented by the following general formula (4) are reacted by refluxing in ethanol and recrystallized as it is after the reaction, or ethyl acetate / water After extraction, purification is performed by silica gel chromatography to synthesize a compound represented by the following general formula (5).
  • the compound represented by the general formula (5) is converted into a compound represented by the following general formula (6) and a palladium catalyst (for example, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium).
  • a palladium catalyst for example, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium.
  • the compound represented by the general formula (7) is treated with cyanoacetic acid or 2- (4-oxo-2-thioxothiazolidine-3-yl) in an organic solvent (for example, acetonitrile, chloroform, DMF, toluene, etc.) in the presence of piperidine.
  • an organic solvent for example, acetonitrile, chloroform, DMF, toluene, etc.
  • the pyrazoline compound of the present invention represented by the following general formula (8) or the following general formula (9) can be obtained.
  • X in the general formulas (2) and (4) to (9) represents Cl, Br, I or OSO 2 CF 3
  • r represents 1 or 2
  • a 1 , A 3 and A 5 represent the general formula ( It represents the same meaning as in 1).
  • the pyrazoline compound of the present invention can be synthesized by the following method. That is, the compound represented by the following general formula (10) and an equivalent amount of the compound represented by the following general formula (11) are reacted by refluxing in ethanol and recrystallized as it is after the reaction, or ethyl acetate / water After the extraction, purification is performed by silica gel chromatography to synthesize a compound represented by the following general formula (12). Next, the compound represented by the general formula (12) is dissolved in N, N-dimethylformamide, and a Vilsmeier reagent prepared with phosphoryl chloride and N, N-dimethylformamide is added dropwise at 0 ° C., and slowly heated to 70 ° C.
  • the compound represented by the general formula (13) is converted into a compound represented by the following general formula (14) and a palladium catalyst (for example, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium ( II) dichloride, etc.) and a base (for example, potassium carbonate, cesium carbonate, sodium hydroxide, etc.) and in the presence of an organic solvent (for example, tetrahydrofuran, toluene, benzene, etc.), the reaction is conducted under reflux.
  • a palladium catalyst for example, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium ( II) dichloride, etc.
  • a base for example, potassium carbonate, cesium carbonate, sodium hydroxide, etc.
  • an organic solvent for example, tetrahydrofuran, toluene, benzene
  • the compound represented by the general formula (15) is converted to cyanoacetic acid or 2- (4-oxo-2-thioxothiazolidine-3-yl) in an organic solvent (for example, acetonitrile, chloroform, DMF, toluene, etc.) in the presence of piperidine.
  • an organic solvent for example, acetonitrile, chloroform, DMF, toluene, etc.
  • X in the general formulas (10) to (17) represents Cl, Br, I or SO 2 CF 3
  • a 6 has a structure as shown below.
  • a 7 has the structure shown below, s represents a positive integer (where s is less than n), t represents an integer of 0 to 2 (where t is less than m or l), A 2 , A 3 , A 4 , R 2 , R 3 , R 4 , X 1 , l, m, and n represent the same meaning as in general formula (1).
  • the pyrazoline compound of the present invention can be synthesized by the following method. That is, a compound represented by the following general formula (2) and an equivalent amount of the compound represented by the following general formula (18) are reacted by refluxing in ethanol and recrystallized as it is after the reaction, or ethyl acetate / water After extraction, the compound represented by the following general formula (19) is synthesized by purification by silica gel chromatography. Next, the compound represented by the general formula (19) is converted into a compound represented by the following general formula (20) and a palladium catalyst (for example, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium.
  • a palladium catalyst for example, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium.
  • the compound represented by the general formula (21) is converted to cyanoacetic acid or 2- (4-oxo-2-thioxothiazolidine-3-yl) in an organic solvent (for example, acetonitrile, chloroform, DMF, toluene, etc.) in the presence of piperidine.
  • an organic solvent for example, acetonitrile, chloroform, DMF, toluene, etc.
  • X in the general formulas (2) and (18) to (23) represents Cl, Br, I or SO 2 CF 3
  • a 8 has a structure as shown below.
  • a 10 has the structure shown below
  • a 9 has the structure shown below
  • u represents a positive integer (where u is less than o)
  • a 1 , A 3 , A 5 , A 6 , R 10 , R 11 , R 12 , X 4 and o are represented by the general formula (1) It represents the same meaning as the thing.
  • the photoelectric conversion element of the present invention is composed of a semiconductor electrode, an electrolyte, and a counter electrode in which a dye represented by the general formula (1) is adsorbed on a conductive support. Electrons are generated by irradiating light, and current response Is shown.
  • a solar battery is a battery used by irradiating light to this photoelectric conversion element and connecting it to an external circuit.
  • the conductive support used in the present invention is a conductive support such as metal, or a conductive metal (platinum, gold, silver, copper, aluminum, etc.) or metal oxide (indium) on a glass or plastic surface.
  • a conductive metal platinum, gold, silver, copper, aluminum, etc.
  • metal oxide indium
  • the conductive support preferably has transparency, and more preferably transmits light of 80% or more.
  • the conductive support may be dipped in the same metal alkoxide or chloride as the semiconductor electrode, followed by drying or heat treatment.
  • a single semiconductor such as silicon or germanium can be used, but it is more preferable to use a porous metal oxide such as titanium, zinc, tin, zirconium, niobium, magnesium, aluminum, or strontium. . These metal oxides may be single crystal or polycrystal. In the case of fine particles, the particle diameter is preferably 1 nm to 1 ⁇ m, and a mixture of different particle diameters may be used.
  • the preparation method of the coating liquid containing semiconductor fine particles is shown below, it is not limited to this.
  • the semiconductor fine powder having the particle size can be obtained by heating and pressurizing the precursor alkoxide after hydrolysis using an acid or base catalyst.
  • the coating liquid is preferably uniformly dispersed with semiconductor fine particles and a resin used as a binder.
  • the dispersion include water, alcohols such as methanol and ethanol, acetone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, and hexane. , Cyclohexane, diethyl ether, dioxane, tetrahydrofuran and the like are used alone or in combination.
  • a surfactant, a polyhydric alcohol such as polyethylene glycol for viscosity adjustment, or a monoterpene alcohol such as terpineol may be used.
  • Examples of the method for producing a semiconductor thin film include a doctor blade method, a screen printing method, a squeegee method, a spin coating method, and a spray method.
  • the film thickness obtained is preferably 1-30 ⁇ m.
  • the semiconductor thin film may be a single layer or a multilayer. In the case of multiple layers, layers having different particle diameters or different types may be laminated.
  • the coated semiconductor thin film When the coated semiconductor thin film is subjected to a heat treatment, the fine particles are bonded to each other to improve the flow of electrons, and the adhesion to the conductive support and the strength of the film are also improved.
  • the heat treatment is preferably performed at 100 ° C. or higher and 450 to 600 ° C. in air or in an oxygen atmosphere.
  • the obtained thin film may be further immersed in the same metal alkoxide or chloride as that of the semiconductor electrode and dried or heat-treated in the same manner as described above.
  • Examples of the method of adsorbing the dye represented by the general formula (1) on the semiconductor thin film include a method of immersing a semiconductor electrode in a dye solution and a method of applying a dye solution.
  • a dispersion may be used.
  • Solvents for dissolving the dye in the present invention include alcohol solvents such as methanol, ethanol, isopropanol and t-butanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether, dioxane and tetrahydrofuran, acetonitrile, Nitrile solvents such as pionitrile, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, chlorobenzene, o-dichlorobenzene, n- Hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene and xylene can be used, and these may be used alone or in combination.
  • alcohol solvents such as methanol, ethanol, isopropanol and
  • the immersion temperature of the dye is from the freezing point to the boiling point of the commonly used dye solution, and the immersion time is preferably 1 to 50 hours.
  • the concentration of the dye solution is usually 0.01 mM to 0.1 M, preferably 0.1 to 0.5 mM.
  • a co-adsorbent may be used in order to prevent the association between the dyes during the immersion of the dyes. Examples of the co-adsorbent include cholic acid derivatives such as cholic acid, deoxycholic acid, and chenodeoxycholic acid.
  • the concentration of the coadsorbent is preferably 5 to 20 mM.
  • the surface of the semiconductor electrode after immersion in the dye may be treated with a solution containing an amine compound such as 4-t-butylpyridine.
  • the electrolyte used in the present invention includes halogen ions such as I ⁇ / I 3 ⁇ and Br ⁇ / Br 2 , metal ions such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion, and cobalt complex, Sulfur ions such as alkylthiol-alkyl disulfides, quinone ions and the like can be mentioned.
  • halogen ions such as I ⁇ / I 3 ⁇ and Br ⁇ / Br 2
  • metal ions such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion, and cobalt complex
  • Sulfur ions such as alkylthiol-alkyl disulfides, quinone ions and the like can be mentioned.
  • halogen ion a combination with a halogen compound is preferable.
  • Metal iodide such as lithium iodide, sodium iodide and potassium iodide, quaternary ammonium salt of iodine such as tetraalkylammonium iodide and imidazolium iodide
  • Metal bromides such as lithium bromide, sodium bromide and potassium bromide, and quaternary ammonium salts of bromine such as tetraalkyl bromide and pyridinium bromide can be used.
  • the concentration of these electrolytes is preferably 0.05M to 1.0M.
  • Solvents for dissolving the electrolyte shown above are nitrile solvents such as acetonitrile and propionitrile, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as ethylene glycol, propylene glycol and diethylene glycol, 1-methyl- Examples thereof include ionic liquids such as 3-propylimidazolium iodide and 1-methyl-3-hexylimidazolium iodide.
  • a solid hole transport material such as solid copper iodide or copper thiocyanide or a conductive polymer such as polypyrrole, polythiophene, or polyethylenedioxythiophene may be used as the charge transfer layer.
  • the above-mentioned conductive support itself may be used, but those coated with a thin film of platinum, gold, rhodium, carbon, polypyrrole, polyethylenedioxythiophene or the like are more preferable.
  • These thin films can be produced by a method of heat-treating a metal chloride such as platinum chloride, a vapor deposition method, a sputtering method, a CVD method, or a spin coating method.
  • a spacer is provided between the semiconductor electrode and the counter electrode to prevent contact.
  • the spacer is preferably a polymer film such as polyethylene or polypropylene, and the film thickness is usually 20 to 60 ⁇ m.
  • reaction solution was cooled, and the precipitate was separated by filtration, washed and recrystallized to obtain 0.16 g of a pyrazoline compound.
  • 0.1 g of this pyrazoline compound was dissolved in 1 ml of DMF, a Vilsmeier reagent was added, the temperature was slowly raised to 70 ° C., and then the reaction was terminated after confirming that the raw materials had disappeared.
  • the reaction solution was poured into an aqueous sodium acetate solution, stirred, aged and hydrolyzed, and the precipitate was filtered, washed and recrystallized to obtain 0.05 g of a formyl product.
  • pyrazoline compound 0.647 g, 4-ethynylbenzaldehyde 0.150 g, bis (triphenylphosphine) palladium (II) dichloride 0.0311 g, copper iodide (I) 0.0169 g in nitrogen in 5.0 ml of tetrahydrofuran in the presence of 5.0 ml of triethylamine Refluxed overnight under atmosphere.
  • pyrazoline compound 0.150 g, 5-formyl-2-thiopheneboronic acid 0.0877 g, bis (triphenylphosphine) palladium (II) dichloride 0.0130 g, cesium carbonate 0.151 g in ethanol 1.0 ml, tetrahydrofuran 3.0 ml in a nitrogen atmosphere Reflux overnight.
  • 0.38 g of this pyrazoline compound was dissolved in 5 ml of DMF, a Vilsmeier reagent was added, the temperature was slowly raised to room temperature, and then the reaction was terminated after confirming that the raw materials had disappeared.
  • the reaction solution was extracted by adding an aqueous sodium hydroxide solution and ethyl acetate, and the residue was recrystallized to obtain 0.14 g of a formyl form.
  • Formyl form 0.13 g, acetonitrile 5 ml, cyanoacetic acid 0.058 g and piperidine 0.058 g were weighed and stirred at reflux for 6 hours.
  • the reaction solution was extracted with ethyl acetate / water and recrystallized with ethanol / ethyl acetate to obtain 0.10 g of the desired product having a ⁇ max of 536 nm.
  • Formyl body 0.130 g, cyanoacetic acid 0.0500 g, and piperidine 63.9 ⁇ l were refluxed in acetonitrile 2 ml and toluene 2 ml under a nitrogen atmosphere for 6 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate / water and recrystallized with methanol / tetrahydrofuran to obtain 0.130 g of the desired product.
  • Formyl form 0.100 g, cyanoacetic acid 0.0380 g, and piperidine 48.6 ⁇ l were refluxed in acetonitrile 2 ml and toluene 2 ml under a nitrogen atmosphere for 6 hours. After completion of the reaction, the mixture was extracted with ethyl acetate / water and recrystallized with methanol / tetrahydrofuran to obtain 0.050 g of the desired product.
  • reaction mixture was extracted with ethyl acetate / water and recrystallized to obtain 0.23 g of formyl form.
  • Formyl form 0.130 g, cyanoacetic acid 0.0444 g, and piperidine 56.7 ⁇ l were refluxed in 2 ml of acetonitrile and 1 ml of chloroform under a nitrogen atmosphere for 6 hours.
  • the reaction mixture was extracted with ethyl acetate / water and recrystallized with methanol / tetrahydrofuran to obtain 0.124 g of the desired product.
  • Formyl form 0.0500 g, cyanoacetic acid 0.0211 g, and piperidine 27.0 ⁇ l were refluxed in 1 ml of acetonitrile and 0.5 ml of chloroform under a nitrogen atmosphere for 3 hours. After completion of the reaction, the mixture was extracted with ethyl acetate / water and recrystallized with methanol / tetrahydrofuran to obtain 0.043 g of the desired product.
  • the precipitated solid was recovered by cooling and washed with an aqueous sodium hydroxide solution and ethanol to obtain 0.443 g of a pyrazoline body.
  • 0.420 g of this pyrazoline compound was dissolved in 5 ml of DMF, a Vilsmeier reagent was added at 0 ° C., the temperature was slowly raised to 100 ° C., and then the reaction was terminated after confirming that the raw materials had disappeared.
  • the reaction solution was extracted by adding an aqueous sodium hydroxide solution and ethyl acetate, and the residue was recrystallized to obtain 0.080 g of a formyl form.
  • the reaction mixture was extracted with ethyl acetate / water and recrystallized to obtain 0.210 g of formyl form.
  • Formyl form 0.130 g, cyanoacetic acid 0.0500 g, and piperidine 63.9 ⁇ l were refluxed overnight in 2 ml acetonitrile and 2 ml chloroform under a nitrogen atmosphere.
  • the mixture was extracted with ethyl acetate / water and recrystallized with ethyl acetate / hexane to obtain 0.120 g of the desired product.
  • the conductive support (FTO) substrate was washed with alkali and UV-ozone, then immersed in 40 mM titanium tetrachloride aqueous solution and heated at 70 ° C for 30 minutes.
  • Titanium oxide (Dyesol, 18NR-T) was printed on a FTO substrate with a film thickness of 4 to 6 ⁇ m by screen printing, dried at 120 ° C., and baked at 500 ° C.
  • the fired titanium oxide electrode was again immersed in 40 mM titanium tetrachloride aqueous solution and heated at 70 ° C. for 30 minutes.
  • a solar simulator Pseudo-sunlight was irradiated with (Minaga Electric Co., Ltd., XES-40S1, AM1.5G, 100mW / cm 2 ), and the current-voltage characteristics were measured using a source meter (Keithley Instruments, Model 2400) .
  • the photoelectric conversion element was produced using the compound synthesize
  • the element using the dye according to the present invention has confirmed the current response due to light irradiation and can be used as a photoelectric conversion element. Moreover, power generation can be confirmed in the dye-sensitized solar cell element, and the short-circuit current is compared with the case where a pyrazoline dye having an adsorbing group such as cyanoacrylic acid or carboxylic acid is used at the 1-position as in Comparative Example 1 or Comparative Example 2. The conversion efficiency shows a high value.
  • the photoelectric conversion device and solar cell using the pyrazoline compound represented by the general formula (1) of the present invention high conversion efficiency, and low cost, the compound is extremely useful industrially.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne : un composé de pyrazoline représenté par la formule générale (1) (dans laquelle les symboles sont tels que définis dans la description) ; et un élément de conversion photoélectrique et une cellule solaire, utilisant chacun ce composé de pyrazoline. L'élément de conversion photoélectrique et la cellule solaire, utilisant chacun un composé de pyrazoline représenté par la formule générale (1), sont caractérisés en ce qu'ils ont un rendement de conversion élevé et en ce qu'ils sont produits à faible coût.
PCT/JP2014/063235 2014-05-19 2014-05-19 Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant WO2015177839A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020167033882A KR102154732B1 (ko) 2014-05-19 2014-05-19 신규한 피라졸린 화합물 및 이것을 사용한 광전 변환 소자
CN201480079193.2A CN106470988B (zh) 2014-05-19 2014-05-19 新颖的吡唑啉化合物、使用其的光电转换元件及太阳电池
PCT/JP2014/063235 WO2015177839A1 (fr) 2014-05-19 2014-05-19 Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/063235 WO2015177839A1 (fr) 2014-05-19 2014-05-19 Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant

Publications (1)

Publication Number Publication Date
WO2015177839A1 true WO2015177839A1 (fr) 2015-11-26

Family

ID=54553537

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/063235 WO2015177839A1 (fr) 2014-05-19 2014-05-19 Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant

Country Status (3)

Country Link
KR (1) KR102154732B1 (fr)
CN (1) CN106470988B (fr)
WO (1) WO2015177839A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112876460A (zh) * 2021-02-05 2021-06-01 山西大学 7-二乙胺基-3-乙酰基香豆素衍生物及其合成方法和应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115504971B (zh) * 2022-11-09 2023-03-28 世华合创生物技术开发(山东)有限公司 一种洛替拉纳的合成方法
CN118221667A (zh) * 2024-05-21 2024-06-21 安徽大学 一种含有苯并噻唑结构的有机蓝色荧光材料及其在光伏胶膜制备中的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006241086A (ja) * 2005-03-04 2006-09-14 Nippon Kagaku Kogyosho:Kk 新規な光線吸収材料
JP2008234901A (ja) * 2007-03-19 2008-10-02 Konica Minolta Business Technologies Inc 光電変換素子及び太陽電池

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190950A (en) 1977-06-01 1980-03-04 The United States Of America As Represented By The Department Of Energy Dye-sensitized solar cells
GB9217811D0 (en) 1992-08-21 1992-10-07 Graetzel Michael Organic compounds
WO2008146405A1 (fr) * 2007-06-01 2008-12-04 Nippon Chemical Works Co., Ltd. Substance fluorescente
CN101910136B (zh) * 2008-01-25 2012-08-15 株式会社日本化学工业所 具有乙炔基的荧光剂
JP2011144229A (ja) 2010-01-13 2011-07-28 Sumitomo Bakelite Co Ltd シアネート樹脂組成物、プリプレグ、積層板、プリント配線板、及び半導体装置
WO2012125884A1 (fr) * 2011-03-17 2012-09-20 Southern Research Institute Dérivés de célécoxib, leur utilisation et leur préparation
AR088351A1 (es) * 2011-10-31 2014-05-28 Lilly Co Eli Analogos de pirazol sustituidos
KR101592628B1 (ko) * 2012-09-20 2016-02-11 주식회사 엘지화학 이미다졸 유도체 및 이를 이용한 유기 전자 소자

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006241086A (ja) * 2005-03-04 2006-09-14 Nippon Kagaku Kogyosho:Kk 新規な光線吸収材料
JP2008234901A (ja) * 2007-03-19 2008-10-02 Konica Minolta Business Technologies Inc 光電変換素子及び太陽電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHRISTOPH J. FAHRNI ET AL.: "Tuning the Photoinduced Electron- Transfer Thermodynamics in 1,3,5-Triaryl-2- pyrazoline Fluorophores: X-ray Structures, Photophysical Characterization, Computational Analysis, and in Vivo Evaluation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 125, no. 13, pages 3799 - 3812, XP055238201, ISSN: 0002-7863 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112876460A (zh) * 2021-02-05 2021-06-01 山西大学 7-二乙胺基-3-乙酰基香豆素衍生物及其合成方法和应用
CN112876460B (zh) * 2021-02-05 2022-05-31 山西大学 7-二乙胺基-3-乙酰基香豆素衍生物及其合成方法和应用

Also Published As

Publication number Publication date
KR20170003622A (ko) 2017-01-09
KR102154732B1 (ko) 2020-09-10
CN106470988A (zh) 2017-03-01
CN106470988B (zh) 2019-03-01

Similar Documents

Publication Publication Date Title
He et al. New Bithiazole‐Based Sensitizers for Efficient and Stable Dye‐Sensitized Solar Cells
Gupta et al. Carbazole based A-π-D-π-A dyes with double electron acceptor for dye-sensitized solar cell
JP5466943B2 (ja) パイ電子共役系を拡張した色素増感型太陽電池用増感色素
KR100969675B1 (ko) 신규한 엔-아릴카바졸 잔기-함유 유기염료 및 이의제조방법
JP5138371B2 (ja) 色素増感光電変換素子
Lim et al. Enhancing the performance of organic dye-sensitized solar cells via a slight structure modification
KR101320999B1 (ko) 신규한 유기염료 및 이의 제조방법
JP5306354B2 (ja) 色素増感型光電変換素子
JP6278504B2 (ja) 新規化合物及びそれを用いた光電変換素子
Abdellah et al. Influence of carbonyl group on photocurrent density of novel fluorene based D-π-A photosensitizers: Synthesis, photophysical and photovoltaic studies
Jo et al. A comparison of the electronic and photovoltaic properties of novel twin-anchoring organic dyes containing varying lengths of π-bridges in dye-sensitized solar cells
JP2010265458A (ja) 有機色素および光電変換装置
JP2014043401A (ja) 金属錯体、およびそれを用いた色素増感太陽電池
WO2015177839A1 (fr) Nouveau composé de pyrazoline et élément de conversion photoélectrique l'utilisant
Tamilavan et al. Synthesis of triphenylamine-based thiophene-(N-aryl) pyrrole-thiophene dyes for dye-sensitized solar cell applications
JP2003282165A (ja) 色素増感光電変換素子
JP5794589B2 (ja) 色素増感太陽電池及び増感色素
Lee et al. Synthesis of Organic Dyes with Linkers Between 9, 9-Dimethylfluorenyl Terminal and α-Cyanoacrylic Acid Anchor, Effect of the Linkers on UV-Vis Absorption Spectra, and Photovoltaic Properties in Dye-Sensitized Solar Cells.
JP2007112987A (ja) 化合物、光電変換素子及び光電気化学電池
KR100969676B1 (ko) 신규한 줄로리딘계 염료 및 이의 제조방법
Tamilavan et al. Structural optimization of thiophene-(N-aryl) pyrrole-thiophene-based metal-free organic sensitizer for the enhanced dye-sensitized solar cell performance
JP5515188B2 (ja) 新規なピラゾリン化合物及びそれを用いた光電変換素子
JP6440296B2 (ja) 色素増感太陽電池用増感剤としてのトリフェニルアミン結合型ジベンゾピロメテン系色素
JPWO2013147145A1 (ja) 色素増感光電変換素子
KR20090083863A (ko) 신규한 유기 염료 및 이의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14892238

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167033882

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14892238

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP