JP6362208B2 - Organic dye complex and method for producing the same - Google Patents

Description

  The present invention relates to a novel organic complex comprising a phthalocyanine derivative and a porphyrin derivative. The present invention also relates to a functional material using the composite, and more particularly to a metal oxide semiconductor electrode including the composite and a dye-sensitized solar cell including the electrode.

  Since organic dyes can shift their absorption and emission wavelengths by changing their skeleton, substituents, coordination metals, etc., many designs of structures having desired absorption / emission wavelengths have been studied. Yes.

  Such organic dyes having a desired absorption / emission wavelength are useful in various fields including electronic devices. For example, in the light emitting element field, it is possible to provide light emitting elements having different colors by designing organic dyes. it can.

  In the field of organic dye-sensitized solar cells, organic dyes that can absorb a wider range of wavelengths are preferred so that solar energy can be used more efficiently.

  Conventionally, most of the dyes that have been used in dye-sensitized solar cells are polypyridine Ru-based dyes that exhibit red color (Patent Documents 1 to 4). In recent years, dyes having a skeleton other than polypyridine have been developed, and for example, use of porphyrin dyes (Patent Documents 5 and 6) and phthalocyanine dyes has been attempted (Patent Documents 7 and 8).

  Furthermore, research on dye-sensitized solar cells using a plurality of dyes has also been conducted (see, for example, Non-Patent Document 1). However, in such a method, only a single dye absorption region can be used.

  Furthermore, when combining a plurality of organic dyes, the compatibility between the dyes is also important, and in many cases, the conversion efficiency cannot be improved even with a combination selected based on wavelength characteristics. In particular, there are few dyes that can efficiently use light in the near infrared region, which is preferable for use in dye-sensitized solar cells, and combinations of dyes are limited.

JP 2003-272721 A Japanese Patent Laid-Open No. 2003-212851 JP 2005-47857 A JP 2005-120042 A Japanese Patent Application No. 2012-027274 Japanese Patent Application No. 2012-027276 Japanese Patent No. 4953658 JP 2011-60669 A International Publication No. 2012/014414

Aswani Yella, Michael Grazel, et al. Science, Vol. 334, ppp.629 (2011) Laboratory Chemistry 2nd Edition, Volume 11, Pages 521-552, Maruzen, July 1965

  An object of the present invention is to provide an organic dye complex having a broader absorption wavelength, particularly a broader absorption wavelength in the near infrared region. Furthermore, it aims at utilization to the functional material of this composite_body | complex. More specifically, an electronic device using the composite, more specifically, a metal oxide semiconductor electrode in which the aggregate is adsorbed on an oxide semiconductor, and a dye-sensitized solar cell using the oxide semiconductor electrode The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventor has found that a complex of a phthalocyanine derivative having the structure of the following formula (1) and a porphyrin derivative having the structure of the following formula (2) It has been found that it has a new absorption wavelength different from the sum of the single absorption wavelengths, and has completed the present invention.

(Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or a common substitution of adjacent R ⁿ and R ^{n + 1.} Or may form an unsubstituted aryl or a substituted or unsubstituted heteroaryl,
X ^{1 to} X ⁸ are each independently selected from O, S, and CH ₂ , and n ^{1 to} n ⁸ are each independently 0 or 1,
M ¹ represents any at least one atom or atomic group capable of binding to phthalocyanine)

(In the formula, A, B, C, and D each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, and at least two of the A to D are substituted or unsubstituted aryl or substituted. Or unsubstituted heteroaryl,
M ² represents any at least one atom or atomic group capable of binding to porphyrin)

  The present invention can provide a novel organic dye complex having a broader range of absorption wavelengths that is different from the mere sum of the absorption wavelengths of each constituent molecule alone. Such an organic dye complex can be used as a functional material. For example, by absorbing solar energy in a wider area, the efficiency of a dye-sensitized solar cell using the organic dye complex can be improved.

a is an ultraviolet-visible absorption spectrum when the Russianine derivative A, the porphyrin derivative P1, and the organic dye complex (A + P1) are adsorbed on titanium dioxide. b is an ultraviolet / visible absorption spectrum in an ethanol solution (5 μmol / L) of the phthalocyanine derivative A, the porphyrin derivative P1, and the organic dye complex (A + P1). It is the structure of the dye-sensitized solar cell using the organic dye composite of this invention. It is the ultraviolet-visible absorption spectrum which changed the solution density | concentration of the organic pigment | dye complex (A + P1) ethanol solution of this invention. It is an ultraviolet-visible absorption spectrum of the organic pigment | dye complex (A + P1) of this invention formed by changing the mixing ratio of the phthalocyanine derivative A and porphyrin derivative P1 in ethanol. It is an ultraviolet-visible absorption spectrum in the organic pigment | dye composite_body | complex (A + P1) of this invention, and the ethanol solution of Comparative Examples 1-7. It is the spectral sensitivity of the dye-sensitized solar cell each formed using the organic pigment | dye composite_body | complex (A + P1) of this invention, the phthalocyanine derivative A, and the porphyrin compound P1 each. It is the external appearance of the solar cell produced using the phthalocyanine derivative A of this invention, the porphyrin derivative P1, and these organic pigment | dye composites (A + P1).

  The present invention relates to a novel organic dye complex comprising a phthalocyanine derivative and a porphyrin derivative. The present invention also relates to a functional material using the composite, and more particularly, to an electronic device using the composite, and more particularly to a metal oxide semiconductor electrode including the composite and a dye sensitizer including the electrode. It relates to a solar cell.

  Hereinafter, preferred embodiments of the present invention will be described in detail. The following embodiment is merely an example of the present invention, and those skilled in the art can change the design as appropriate.

Organic dye complex The organic dye complex of the present invention comprises a phthalocyanine derivative having the structure of formula (1) and a porphyrin derivative having the structure of formula (2).

(Phthalocyanine derivatives)
The phthalocyanine derivative of the present invention is a compound having the structure of the following formula (1) and a salt thereof.

In the general formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or adjacent R ⁿ and R ^{n + 1} are One common substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl may be formed. Preferably, four or more of the above R ^{1 to} R ⁸ do not become hydrogen atoms at the same time.

  The aryl constituting the formula (1) includes, but is not limited to, a phenylene ring and a naphthalene ring. The heteroaryl constituting the formula (1) includes a thiophene ring, a pyrrole ring, a furan ring, an imidazole ring, 5-membered rings such as a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring and an isothiazole ring, and a 6-membered ring such as a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring and a 1,2,3-triazine ring are included.

  The aryl or heteroaryl constituting the formula (1) is an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group; a cyano group; Acyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; carbonyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; aryl such as phenoxy group and benzyloxy group Oxy group; Dialkylamino group such as diethylamino group and isopropylamino group; Diaralkylamino group such as dibenzylamino group and diphenethylamino group; Nitro group; α-haloalkyl group such as trifluoromethyl group; Halogen; Hydroxyl group; It may be substituted by a group.

In the general formula (1), X ^{1 to} X ⁸ are each independently selected from O, S, and CH ₂ , and n ^{1 to} n ⁸ are each independently 0 or 1. X ^{1 to} X ⁸ are preferably O. Preferably, at least five of n ^{1 to} n ⁸ are 1.

In the general formula (1), M ¹ represents any at least one atom or atomic group capable of binding to phthalocyanine. M ¹ may be a single central atom or a central atomic group in which the central atom is bonded to another substance.

  In the phthalocyanine derivative of the formula (1) of the present invention, the central atom may be one or two or more. Specific examples of those having two or more central atoms include metal-free phthalocyanine derivatives. In the metal-free phthalocyanine derivative, two hydrogen atoms bonded to nitrogen are each a central atom.

Moreover, the other substance which comprises a central atomic group with a central atom is arbitrary. For example, but not limited thereto, the central atomic group M ¹ bonded to another substance may be an oxide, a hydroxide, or a halide.

Further, M ¹ other than a hydrogen atom may be a typical metal element, a metalloid element, or a transition metal element. When M ¹ is a single central atom other than a hydrogen atom, the central element M ¹ is a group of metal elements composed of zinc, aluminum, magnesium, copper, nickel, cobalt, ruthenium, rhodium, osmium, lead, and tin, or silicon Selected from. Zinc and copper are preferred.

  The phthalocyanine derivative represented by the formula (1) includes, for example, the following compounds A to D and salts thereof. In addition, about the manufacturing method of the phthalocyanine derivative of this invention, it explains in full detail in the Example mentioned later.

(Porphyrin derivative)
The porphyrin derivative of the present invention is a compound having the following formula (2) and a salt thereof.

In the general formula (2), A, B, C, and D each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, and at least two of the A to D are substituted or unsubstituted. A substituted aryl group or a substituted or unsubstituted heteroaryl group.

  Specific examples of the monovalent organic group include, but are not limited to, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group; a phenylethynyl group. Alkynyl group such as cyano group; amino group; acyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; carbonyl group; alkoxycarbonyl having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group Groups; aryloxy groups such as phenoxy group and benzyloxy group; dialkylamino groups such as diethylamino group and isopropylamino group; diaralkylamino groups such as dibenzylamino group and diphenethylamino group; nitro group; trifluoromethyl group and the like Α-haloalkyl group of; hydroxyl group; sulfo group; substituted or unsubstituted Aryl groups such as enylene ring and naphthalene ring; 5-membered rings such as thiophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, and pyridine ring, pyrimidine ring A substituted or unsubstituted heteroaryl group containing a 6-membered ring such as a pyridazine ring, a pyrazine ring, or a 1,2,3-triazine ring. The aryl or heteroaryl constituting the formula (2) may be further substituted with one or more halogens or a monovalent organic group.

In the general formula (2), M ² represents any of the at least one atom or atomic group capable of binding to porphyrin. M ² may be a single central atom or a central atomic group in which the central atom is bonded to another substance.

  In the porphyrin derivative of the formula (2) of the present invention, the number of central atoms may be one, or two or more. Specific examples of those having 2 or more central atoms include metal-free porphyrin derivatives. In the metal-free porphyrin derivative, two hydrogen atoms bonded to nitrogen are each a central atom.

Moreover, the other substance which comprises a central atomic group with a central atom is arbitrary. For example, but not limited thereto, the central atomic group M ² bonded to another substance may be an oxide, a hydroxide, or a halide.

Further, M ² other than a hydrogen atom may be a typical metal element, a metalloid element, or a transition metal element. When M ² is a single central atom other than a hydrogen atom, the central element M ² is a group of metal elements consisting of zinc, aluminum, magnesium, copper, nickel, cobalt, ruthenium, rhodium, osmium, lead, and tin, or silicon Selected from. Zinc, copper, iron, and cobalt are preferable.

  The porphyrin derivative represented by the formula (2) includes, for example, the following compounds P1 to P15 shown in Table 1 and salts thereof. In addition, regarding the manufacturing method of the porphyrin derivative of this invention, it explains in full detail in the Example mentioned later.

(Preparation of organic dye complex)
The organic dye complex of the present invention can be formed by mixing a phthalocyanine derivative having the above formula (1) and a porphyrin derivative having the above formula (2) in a solvent. Specifically, but not limited thereto, (i) by mixing the phthalocyanine derivative solution and the porphyrin derivative solution, (ii) dissolving the other compound in a solution in which one compound is dissolved. Or (iii) The organic dye complex of the present invention may be formed by mixing the phthalocyanine derivative and the porphyrin derivative in a solid state and dissolving in a solvent.

  The organic dye complex of the present invention includes an association product of the phthalocyanine derivative of the above formula (1) and the porphyrin derivative of the above formula (2).

  The aggregate has a new absorption spectrum different from any of the mixed phthalocyanine derivative and porphyrin derivative. FIG. 1a shows an ultraviolet / visible absorption spectrum when (i) phthalocyanine derivative A, (ii) porphyrin derivative P1, and (iii) these organic dye complexes (A + P1) are adsorbed on titanium dioxide. FIG. 1b shows the ultraviolet and visible absorption spectra of these compounds in an ethanol solution (5 μmol / L), respectively.

  The solvent that can be used to form the organic dye complex may be any solvent that dissolves the phthalocyanine derivative and porphyrin derivative to be mixed. Specific examples include, but are not limited to, chain and cyclic saturated aliphatic solvents such as pentane, hexane, octane, nonane, methylcyclohexane, and ethylcyclohexane; toluene, xylene, naphthalene, tetrahydronaphthalene, methylnaphthalene, diphenylmethane, Aromatic solvents such as anisole; Halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, chloronaphthalene; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, benzyl alcohol; Ethylene glycol, glycerin, polyethylene glycol, etc. Aliphatic and polyhydric alcohols; linear and cyclic ketone solvents such as acetone, cyclohexanone, and methyl ethyl ketone; ester solvents such as methyl formate, ethyl acetate, and n-butyl acetate; Halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxaline, methyl cellosolve, ethyl cellosolve, butyl cellosolve Linear and cyclic ether solvents such as dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolinone, 2-butyrolactone, hexamethylphosphoric acid triamide, etc. Polar solvents; nitrogen-containing compounds such as n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine; and mixtures thereof. Preferably, ethanol and chloroform are used.

  As for the working temperature of the mixing step of the phthalocyanine derivative and porphyrin derivative, the lower limit is equal to or higher than the freezing point of the solvent used, and the upper limit is equal to or lower than the boiling point of the solvent used. Specifically, it is preferably 10 ° C. or higher and 200 ° C. or lower.

  The organic pigment | dye complex of this invention is mixed in the density | concentration which the said aggregate forms in at least one part. Specifically, the concentration of the organic dye complex is preferably 1 μmol / L or more, and more preferably 5 μmol / L or more. The formed organic dye complex may be in a solid state by removing the solvent.

  The phthalocyanine derivative of the above formula (1) and the porphyrin derivative of the above formula (2) are mixed at a ratio at least partially forming the above-mentioned aggregate, for example, mixed at a ratio of 1: 9 to 9: 1. it can.

Functional Material The organic dye complex of the present invention can be used as a functional material. More specifically, an electronic device using the composite, more specifically, a metal oxide semiconductor electrode in which the composite is adsorbed on an oxide semiconductor, and a dye-sensitized solar cell using the oxide semiconductor electrode Can be used.

(Metal oxide semiconductor electrode)
The present invention further relates to a metal oxide semiconductor electrode using the organic dye complex. The metal oxide semiconductor electrode of the present invention is obtained by adsorbing the organic dye complex of the present invention described above on the surface of an electrode formed of a metal oxide semiconductor. This metal oxide semiconductor electrode is preferably a porous electrode. Accordingly, the substantial surface area of the electrode can be increased, the amount of photosensitizing dye adsorbed on the electrode can be increased, and the photoelectric conversion efficiency of the solar cell including the metal oxide semiconductor electrode can be increased. Will be able to.

  The metal oxide semiconductor of the present invention includes titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, or strontium titanate, titanium. A compound having a perovskite structure such as calcium oxide, sodium titanate, barium titanate, or potassium niobate can be used.

  Any known method can be used as a method for adsorbing the organic dye complex on the metal oxide semiconductor thin film. For example, a method of immersing a metal oxide semiconductor thin film such as titanium dioxide in the organic dye complex solution of the present invention at a predetermined temperature (dip method, roller method, air knife method, etc.), and the organic dye complex solution is oxidized by metal Examples thereof include a method of applying to a semiconductor layered surface (wire bar method, application method, spin method, spray method, offset printing method, screen printing method, etc.).

(Dye-sensitized solar cell)
The present invention further relates to a dye-sensitized solar cell including the transparent electrode 1, the metal oxide semiconductor electrode 2, the electrolyte 3, and the counter electrode 4 (see FIG. 2).

  The transparent electrode 1 is configured by forming a transparent conductive layer on a transparent substrate (not shown). As the transparent substrate, a general-purpose glass substrate, quartz substrate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, and other transparent plastic substrates can be used. The transparent conductive layer is composed of tin oxide, fluorine-doped tin oxide, ITO, ATO, zinc oxide, aluminum-doped zinc oxide, or a light-transmissive transparent conductive layer in which a coating of tin oxide or fluorine-doped tin oxide is provided on the surface thereof. Can be configured.

As the electrolyte 3, a solid state or a liquid state can be used. Specifically, iodine-based electrolyte, bromine-based electrolyte, selenium-based electrolyte, sulfur-based electrolyte, quinone / hydroquinone-based electrolyte, and cobalt complex-based electrolyte can be used. But are not limited _to, I 2, LiI, dimethylpropyl imidazolium iodide, t- butyl pyridine, 1,2-dimethyl-3-propyl imidazolium iodide, etc., acetonitrile, methoxy acetonitrile, propylene carbonate, ethylene carbonate, A solution or the like dissolved in an electrically inert organic solvent such as 3-methoxypropionyl or propylene carbonate is preferably used.

  Further, for the purpose of reducing volatilization of components in the electrolyte composition, a gelling agent or a polymer crosslinking monomer may be dissolved in the electrolyte composition described above and used as a gel electrolyte. Further, an all-solid-state dye-sensitized solar cell may be formed by dissolving in the polymer using the electrolyte and the plasticizer and volatilizing and removing the plasticizer.

  The counter electrode 4 is composed of, for example, a conductive layer such as platinum, carbon, nickel, chromium, stainless steel, fluorine-doped tin oxide, and ITO formed on a metal substrate such as titanium, Al, and SUS, a glass substrate, or a plastic substrate. Is done. The counter electrode 4 may include a catalyst layer (not shown) such as platinum or carbon, and the platinum may be treated with a sulfur material (see, for example, Patent Document 9).

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
1. Synthesis of phthalocyanine derivative (Synthesis of phthalocyanine derivative A)

Synthesis of compound 1

  Under a nitrogen atmosphere, 4,5-dichlorophthalonitrile (19.0 g, 96.4 mmol), 2,6-dimethylphenol (35.3 g, 289 mmol), potassium carbonate (46.6 g, 337 mmol) in DMF (190 mL). In addition, the mixture was stirred at 100 ° C. for 16 hours. After cooling, it was dispersed in water, and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography. Subsequently, recrystallization was performed using ethyl acetate to obtain Compound 1 (20.6 g, 55.4 mmol, yield 58%, white solid).

Synthesis of compound 2

  Under a nitrogen atmosphere, 4-iodophthalonitrile (11.1 g, 43.7 mmol), 4- (methoxycarbonyl) phenylboronic acid (15.7 g, 87.2 mmol), sodium carbonate (18.5 g, 175 mmol), tetrakis ( Triphenylphosphine) palladium (4.96 g, 4.3 mmol) was added to a mixed solution of DMF (480 mL) and water (155 mL), and the mixture was stirred at 90 ° C. for 2 hours. After cooling, ethyl acetate and water were added and the organic phase was extracted. The extracted organic phase was dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography to obtain compound 2 (7.58 g, 28.9 mmol, 66% yield, white solid).

Synthesis of phthalocyanine derivative A

  Under a nitrogen atmosphere, Compound 1 (34.15 g, 92.7 mmol), Compound 2 (8.11 g, 30.9 mol), and zinc chloride (8.42 g, 61.8 mmol) were added to 1 L of 2-dimethylaminoethanol. Stir at 4 ° C. for 4 hours. After cooling, the mixture was concentrated under reduced pressure, and methanol was added to the residue. The precipitated solid was collected by filtration and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain a methyl ester intermediate.

The intermediate was dissolved in a mixed solution of 600 mL of THF, 100 mL of ethanol and 100 mL of 1 mol / L sodium hydroxide aqueous solution, and heated to reflux for 1 hour. After cooling, the mixture was neutralized with hydrochloric acid, the organic solvent was distilled off under reduced pressure, and the residue was extracted with chloroform. The extracted organic phase was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography. Subsequently, recrystallization was performed using ethyl acetate to obtain Compound A (4.66 g, 3.28 mmol, yield 11%, green solid, TOF-MS m / z 1417 [M + H] ⁺ ).

(Synthesis of phthalocyanine derivative B)

Under a nitrogen atmosphere, Compound 1 (3.00 g, 8.14 mmol) and zinc chloride (2.22 g, 16.3 mmol) were added to 60 mL of 2-dimethylaminoethanol, and the mixture was stirred at 140 ° C. for 4 hours. After cooling, the mixture was concentrated under reduced pressure, methanol was added to the residue, and the precipitated solid was collected by filtration. The obtained crude product was purified by silica gel column chromatography to obtain Compound B (1.06 g, 0.69 mmol, yield 34%, green solid, TOF-MS m / z 1537 [M + H] ⁺ ).

(Synthesis of phthalocyanine derivative C)

  Compound 1 (0.2 g, 0.54 mmol) and copper chloride (0.036 g, 0.27 mmol) were added to 10 mL of 2-dimethylaminoethanol and stirred at 140 ° C. for 2 hours. After cooling, the mixture was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain compound C (0.055 g, 0.035 mmol, yield 26%, green solid).

(Synthesis of phthalocyanine derivative D)
Synthesis of compound 3

  Under a nitrogen atmosphere, 4,5-dichlorophthalonitrile (2.0 g, 10.2 mmol), 2,6-diisopropylphenol (4.6 g, 25.8 mmol), potassium carbonate (3.8 g, 27 0.5 mmol) was added to DMF (40 mL), and the mixture was stirred at 80 to 100 ° C. for 12 hours. After cooling, it was dispersed in 800 mL of water, and the precipitated solid was collected by filtration. This was dissolved in ethyl acetate and washed with water. The organic layer was dried over sodium sulfate and then concentrated under reduced pressure to obtain a crude product. This was slurry washed with methanol to obtain Compound 3 (2.8 g, 5.8 mmol, 57% yield, light green solid).

Synthesis of phthalocyanine derivative D

Under a nitrogen atmosphere, compound 3 (2.00 g, 4.16 mmol) and zinc chloride (1.13 g, 8.32 mmol) were added to 40 mL of 2-dimethylaminoethanol, and the mixture was stirred at 140 ° C. for 4 hours. After cooling, the mixture was concentrated under reduced pressure, methanol was added to the residue, and the precipitated solid was collected by filtration. The obtained crude product was purified by silica gel column chromatography to obtain compound D (0.64 g, 0.32 mmol, yield 31%, green solid, TOF-MS m / z 1986 [M + H] ⁺ ).

2. Synthesis of porphyrin derivative (synthesis of porphyrin derivative P1)
Synthesis of 4- (5-hexylthiophen-2-yl) benzaldehyde

  To the reaction vessel, 4-bromobenzaldehyde (9.17 g), 2- (5-hexylthiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (14.00 g) , Tripotassium phosphate (11.00 g), toluene (150 mL) and dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium (II) (0.20 g) were added and stirred and heated to 70 ° C. did. After completion of the reaction, the reaction solution was passed through celite, and the filtrate was concentrated. This was developed and separated on a silica gel column (chloroform) to obtain a product (4- (5-hexylthiophen-2-yl) benzaldehyde, 7.79 g).

Synthesis of 5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin

  In a reaction vessel, pyrrole (0.92 g), 4- (5-hexylthiophen-2-yl) benzaldehyde (2.79 g), methyl terephthalaldehyde (0.56 g), chloroform (130 mL) and ethanol (0.5 ml) ) And cooled to about 10 ° C. Thereto, boron trifluoride (0.47 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.32 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/2), and the product (5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) was obtained. ) Phenyl] porphyrin, 0.34 g).

Synthesis of 5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex

  5- (4-Methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin (0.33 g) was dissolved in chloroform (16.5 mL). Thereto, zinc acetate dihydrate (0.62 g) dissolved in methanol (6 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc) (II) complex, 0.33 g) was obtained.

Synthesis of 5- (4-carboxylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex (porphyrin derivative P1)

5- (4-Methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex (0.31 g) in THF (30 mL) and water (7 mL). Thereto was added 48% sodium hydroxide (0.70 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The purple precipitate was recovered and the purple product (5- (4-carboxylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex, 0.28 g) was obtained.
¹ H-NMR (δ _{H /} ppm, THF, 400 MHz) 0.96 (t, 9H), 1.50-1.40 (m, 18H), 1.81 (quin, 6H), 2.95 (t , 6H), 6.92 (d, 3H), 7.51 (d, 3H), 8.00 (d, 6H), 8.20 (d, 6H), 8.31 (d, 2H), 8 .43 (d, 2H), 8.84-8.96 (m, 8H)
(Synthesis of porphyrin derivative P2)
Synthesis of 2-formyl-5-hexylthiophene

  A reaction vessel containing 2-hexylthiophene (20.0 g) and dehydrated tetrahydrofuran (100 mL) was cooled to −10 ° C., and n-butyllithium (90 mL) was added dropwise thereto. After 2 hours, DMF (18 mL) was slowly added dropwise. After stirring this solution at 10 ° C. for 1 hour, a saturated aqueous ammonium chloride solution was added dropwise, and the mixture was extracted with hexane. The organic phase was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The oily substance obtained by distilling off the solvent was developed and separated by a silica gel column (chloroform / heptane = 1/1) to obtain the product (2-formyl-5-hexylthiophene, 22.8 g).

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin

  To a reaction vessel, pyrrole (2.73 g), 2-formyl-5-hexylthiophene (6.0 g), methyl terephthalaldehyde (1.67 g), chloroform (1500 mL) and ethanol (6 mL) were added, and about 10 ° C. Cooled to. Thereto was added boron trifluoride (1.45 g) dropwise, and the mixture was stirred for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.94 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/1), and the product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin, 1.43 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex

  5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (1.35 g) was dissolved in chloroform (160 mL). Thereto was added dropwise zinc acetate dihydrate (3.77 g) dissolved in methanol (38 mL). After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 1.53 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin zinc (II) complex (porphyrin derivative P2)

5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (1.40 g) dissolved in THF (210 mL) and water (70 mL) I let you. Thereto was added 48% sodium hydroxide (7.0 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin zinc (II) complex, 1.27 g) was obtained.
¹ H-NMR (δ _H / ppm, CDCl ₃ , 400 MHz) 0.98 (t, 9H), 1.45 (m, 12H), 1.61 (quin, 6H), 1.96 (quin, 6H) , 3.14 (t, 6H), 7.17 (d, 3H), 7.71 (d, 3H), 8.35 (d, 2H), 8.53 (d, 2H), 8.89 ( d, 2H), 9.23 (d, 2H), 9.24 (s, 4H)

(Synthesis of porphyrin derivative P3)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin

  To a reaction vessel, pyrrole (2.73 g), 2-formyl-5-hexylthiophene (6.0 g), methyl terephthalaldehyde (1.67 g), chloroform (1500 mL) and ethanol (6 mL) were added, and about 10 ° C. Cooled to. Thereto was added boron trifluoride (1.45 g) dropwise, and the mixture was stirred for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.94 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/1), and the product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin, 1.43 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin copper (II) complex

  5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (0.53 g) was dissolved in chloroform (100 mL). Thereto, copper acetate (0.50 g) dissolved in methanol (40 mL) was added dropwise. After confirming the completion of the reaction by TLC, the solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform / hexane = 1/1), and a purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin was obtained. Copper (II) complex, 0.42 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin copper (II) complex (porphyrin derivative P3)

  5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin copper (II) complex (0.42 g) dissolved in THF (100 mL) and water (10 mL) I let you. Thereto was added 48% sodium hydroxide (1.50 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin copper (II) complex, 0.40 g) was obtained.

(Synthesis of porphyrin derivative P4)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin cobalt (II) complex

  5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (0.53 g) was dissolved in chloroform (100 mL). Thereto was added dropwise cobalt acetate tetrahydrate (0.70 g) dissolved in methanol (70 mL). After confirming the completion of the reaction by TLC, the solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform / hexane = 1/2), and a purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin was obtained. Cobalt (II) complex, 0.50 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin cobalt (II) complex (porphyrin derivative P4)

5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin cobalt (II) complex (0.50 g) dissolved in THF (150 mL) and water (15 mL) I let you. Thereto was added 48% sodium hydroxide (2.00 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin cobalt (II) complex, 0.29 g).

(Synthesis of porphyrin derivative P5)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin (porphyrin derivative P5)

5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (0.15 g) was dissolved in THF (50 mL) and water (10 mL). Thereto was added 48% sodium hydroxide (1.50 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin, 0.10 g).
¹ H-NMR (δ _H / ppm, CDCl ₃ , 400 MHz) 0.98 (t, 9H), 1.40-1.50 (m, 12H), 1.60 (quin, 6H), 1.96 ( quin, 6H), 3.14 (t, 6H), 7.17 (d, 3H), 7.71 (d, 3H), 8.35 (d, 2H), 8.54 (d, 2H), 8.78-9.14 (m, 8H)

(Synthesis of porphyrin derivative P6)
Synthesis of 5-formylthiophene-2-carboxylic acid methyl ester

  To the reaction vessel, 5-formylthiophene-2-carboxylic acid (0.50 g), 4-dimethylaminopyridine (0.11 g), methanol (0.87 g) and chloroform (12 mL) were added and cooled to 5 ° C. 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.74 g) was added thereto. After stirring at room temperature for 1 hour, 3 mol / L hydrochloric acid (8 mL) was added. The reaction solution was extracted with chloroform, and the organic layer was washed with saturated brine. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain a crude product. This was purified by a silica gel column (chloroform) to obtain a yellow product (5-formylthiophene-2-carboxylic acid methyl ester, 0.45 g).

Synthesis of 5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin

  In a reaction vessel, pyrrole (1.26 g), 2-formyl-5-hexylthiophene (2.77 g), 5-formylthiophene-2-carboxylic acid methyl ester (0.80 g), chloroform (700 mL) and ethanol (3 mL ) And cooled to about 10 ° C. Thereto, boron trifluoride (0.67 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.20 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/2 → 5/1), and the product (5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexyl) was separated. Thiophen-2-yl) porphyrin, 1.43 g) was obtained.

Synthesis of 5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc (II) complex

  5- (5-Methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin (0.50 g) was dissolved in chloroform (60 mL). There, the zinc acetate dihydrate (1.39g) dissolved in methanol (14mL) was dripped. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc ( II) Complex, 0.42 g) was obtained.

Synthesis of 5- (5-carboxylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc (II) complex (porphyrin derivative P6)

5- (5-Methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc (II) complex (0.41 g) in THF (60 mL) and water ( 20 mL). Thereto was added 48% sodium hydroxide (2.00 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. Extracted with chloroform and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1) to give a purple product (5- (5-carboxylthiophen-2-yl) -10,15,20-tri ( 5-hexylthiophen-2-yl) porphyrin zinc (II) complex, 0.40 g) was obtained.
¹ H-NMR (δ _H / ppm, CDCl ₃ , 400 MHz) 0.98 (t, 9H), 1.41-1.47 (m, 12H), 1.60 (quin, 6H), 1.96 ( quin, 6H), 3.14 (t, 6H), 7.17 (d, 3H), 7.70 (d, 3H), 7.94 (d, 2H), 8.26 (d, 2H), 9.12 (d, 2H), 9.23 (s, 4H), 9.26 (d, 2H)

(Synthesis of porphyrin derivative P7)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4'-methoxycarbonyl) biphenyl) porphyrin

  In a reaction vessel, pyrrole (1.07 g), 2-formyl-5-hexylthiophene (2.35 g), 4′-formylbiphenyl-4-carboxylic acid methyl ester (0.96 g), chloroform (120 mL) and ethanol ( 3 mL) was added and cooled to about 10 ° C. To this, boron trifluoride (0.57 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.80 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin, 0 .40 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4'-methoxycarbonyl) biphenyl) porphyrin zinc (II) complex

  5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin (0.40 g) was dissolved in chloroform (100 mL). Thereto was added dropwise zinc acetate dihydrate (0.60 g) dissolved in methanol (40 ml). After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin zinc (II) complex, 0.40 g) was obtained.

Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-carboxyl) biphenyl) porphyrin zinc (II) complex (porphyrin derivative P7)

5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin zinc (II) complex (0.40 g) in THF (70 mL) and water (30 mL). Thereto was added 48% sodium hydroxide (3.00 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / ethyl acetate = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-carboxyl) biphenyl) porphyrin zinc (II) complex, 0.37 g) was obtained.
¹ H-NMR (δ _H / ppm, CDCl ₃ , 400 MHz) 0.96-1.00 (m, 9H), 1.44-1.46 (m, 12H), 1.60 (quin, 6H), 1.96 (quin, 6H), 3.14 (t, 6H), 7.17 (d, 3H), 7.70 (d, 3H), 8.04 (d, 4H), 8.33 (d , 4H), 8.98-9.25 (m, 8H)

(Synthesis of porphyrin derivative P8)
Synthesis of 2- (4-hexylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

  To the reaction vessel, 1-bromo-4-hexylbenzene (10.00 g), bis (pinacolato) diborane (12.60 g), potassium acetate (12.13 g) and DMF (200 mL) were added and stirred. Bis (triphenylphosphine) palladium (II) dichloride (0.61 g) was added thereto and heated to 80 ° C. After heating and stirring overnight, chloroform and water were added to separate and wash. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (hexane → hexane / chloroform = 1/2) to give the product (2- (4-hexylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane. 9.30 g).

Synthesis of 5- (4-hexylphenyl) thiophene-2-carbaldehyde

  2- (4-Hexylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.10 g), 5-bromothiophene-2-carbaldehyde (4.07 g) in a reaction vessel A 10% aqueous sodium carbonate solution (55 mL) and dioxane (60 mL) were added and stirred. Tetrakistriphenylphosphine palladium (598 mg) was added thereto and heated to 80 ° C. After heating and stirring overnight, chloroform and water were added to separate and wash. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified by a silica gel column (hexane / chloroform = 4/1 → chloroform) to obtain a product (5- (4-hexylphenyl) thiophene-2-carbaldehyde, 4.70 g).

Synthesis of 5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin

  Pyrrole (1.58 g), 5- (4-hexylphenyl) thiophene-2-carbaldehyde (4.80 g), methyl terephthalaldehyde (0.97 g) were dissolved in chloroform (180 mL) and ethanol (3 mL), Cooled to about 10 ° C. Thereto was added boron trifluoride (0.83 g) dropwise, and the mixture was stirred as it was for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (4.10 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin, 0 .50 g) was obtained.

Synthesis of 5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex

  5,10,15-Tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin (0.50 g) was dissolved in chloroform (120 mL). There, the zinc acetate dihydrate (0.70g) dissolved in methanol (60 mL) was dripped. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (hexane / chloroform = 2/1), and the purple product (5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4- Methoxycarbonylphenyl) porphyrin zinc (II) complex, 0.40 g) was obtained.

Synthesis of (porphyrin derivative P8) of 5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex

5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (0.40 g) in THF (50 mL) and water (30 mL). 48% sodium hydroxide (3 mL) was added thereto, and the mixture was heated at about 68 ° C. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. Extraction was performed with chloroform, and the organic phase was washed with water. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (chloroform → chloroform / ethyl acetate = 4/1) to give a purple product (5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex, 0.30 g) was obtained.
¹ H-NMR (δ _H / ppm, CDCl ₃ , 400 MHz) 0.92 (t, 9H), 1.30-1.42 (m, 18H), 1.69 (quin, 6H), 2.69 ( t, 6H), 7.31 (d, 6H), 7.67 (d, 3H), 7.79 (d, 6H), 7.87 (d, 3H), 8.36 (d, 2H), 8.52 (d, 2H), 8.91-9.34 (m, 8H)

(Synthesis of porphyrin derivative P9)
Synthesis of 9- (2-thiophene) -3,6-di-t-butylcarbazole

  In a reaction vessel, 3,6-di-t-butylcarbazole (12.46 g), copper (8.23 g), potassium carbonate (8.15 g), 2-bromothiophene (8.73 g) and nitrobenzene (100 mL) were added. In addition, the mixture was stirred at 160 ° C. for 1 day. Chloroform was added to the reaction solution and allowed to pass through Celite. The filtrate was concentrated and separated and purified on a silica gel column (chloroform / hexane = 1/2) to give the product (9- (2-thiophene) -3,6-di-t-butylcarbazole, 6.75 g). Obtained.

Synthesis of 9-[(2-formyl) thiophen-5-yl] -3,6-di-tert-butylcarbazole

  9- (2-thiophene) -3,6-di-t-butylcarbazole (6.75 g) was dissolved in dehydrated THF (50 mL) and cooled to 0 ° C. N-Butyllithium (13 mL) was slowly added dropwise thereto. After 30 minutes, DMF (1.6 mL) was added. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column (hexane / ethyl acetate = 20/1 → 10/1 → 8/1) to give a yellow product (9-[(2-formyl) thiophen-5-yl]- 3,6-di-t-butylcarbazole (5.65 g) was obtained.

Synthesis of 5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin

  In a reaction vessel, pyrrole (0.62 g), methyl terephthalaldehyde (0.38 g), 9-[(2-formyl) thiophen-5-yl] -3,6-di-t-butylcarbazole (2.70 g) ), Chloroform (150 mL) and ethanol (2 mL) were added and cooled to about 10 ° C. To this, boron trifluoride (0.36 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.70 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] was obtained. -20- (4-methoxycarbonylphenyl) porphyrin, 0.98 g).

5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) Complex synthesis

  5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin (0.98 g ) Was dissolved in chloroform (100 mL). Thereto, zinc acetate dihydrate (0.70 g) dissolved in methanol (40 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] was isolated. ] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 1.00 g) was obtained.

5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex Synthesis of (porphyrin derivative P9)

5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) The complex (1.00 g) was dissolved in THF (150 mL) and water (15 mL). Thereto was added 48% sodium hydroxide (1.5 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The purple precipitate was recovered and the purple product (5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-Carboxyphenyl) porphyrin zinc (II) complex, 0.70 g) was obtained.
¹ H-NMR (δ _H / ppm, CDCl ₃ , 400 MHz) 1.53 (s, 54H), 7.63 (dd, 3H), 7.67 (t, 6H), 7.88 (t, 6H) , 8.01 (dd, 3H), 8.22 (s, 6H), 8.41 (d, 2H), 8.59 (d, 2H), 9.02 (d, 2H), 9.42 ( d, 2H), 9.48 (s, 4H)

(Synthesis of porphyrin derivative P10)
Synthesis of 5-bromo-5'-formyl-2,2'-bithiophene

  5-Formyl-2,2′-bithiophene (5.00 g) was dissolved in DMF (6 mL) and cooled to 0 ° C. N-bromosuccinimide (4.80 g) was added thereto. After completion of the reaction, water was added and the solution was separated and washed. The organic phase was dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a crude product. This was washed with THF and ethyl acetate to give the product (5-bromo-5′-formyl-2,2′-bithiophene, 6.00 g).

Synthesis of 5- (5- (4-hexylphenyl) thiophen-2-yl) thiophene-2-carbaldehyde

  To the reaction vessel, 5-bromo-5′-formyl-2,2′-bithiophene (5.52 g), 2- (4-hexylphenyl) -4,4,5,5-tetramethyl-1,3,2 -Dioxaborolane (6.23 g), 10% aqueous sodium carbonate solution (65 mL), dioxane (60 mL) and xylene (20 mL) were added and stirred. Tetrakistriphenylphosphine palladium (0.66 g) was added thereto and heated to 80 ° C. After stirring with heating for 4 hours, chloroform and water were added to separate and wash. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (hexane / chloroform = 1/1 → chloroform) to give the product (5- (5- (4-hexylphenyl) thiophen-2-yl) thiophene-2-carbaldehyde, 5.40 g. )

Synthesis of 5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin

  Pyrrol (1.38 g), 5- (5- (4-hexylphenyl) thiophen-2-yl) thiophene-2-carbaldehyde (5.40 g), methyl terephthalaldehyde (0.85 g) in chloroform (150 mL) And ethanol (2 mL) and cooled to about 10 ° C. Thereto was added boron trifluoride (0.73 g) dropwise, and the mixture was stirred as it was for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.40 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- ( 4-methoxycarbonylphenyl) porphyrin, 0.40 g) was obtained.

Synthesis of 5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex

  5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin (0.40 g) in chloroform ( 80 mL). Thereto, zinc acetate dihydrate (0.45 g) dissolved in methanol (20 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (hexane / chloroform = 1/2 → chloroform), and the purple product (5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophene was obtained. -2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 0.20 g).

5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex (porphyrin derivative P10 )

5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (0. 20 g) was dissolved in THF (50 mL) and water (30 mL). Thereto was added 48% sodium hydroxide (3 mL), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. Extraction was performed with chloroform, and the organic phase was washed with water. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (chloroform → chloroform / ethyl acetate = 4/1) to give a purple product (5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] Thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex, 0.15 g) was obtained.
¹ H-NMR (δ _{H /} ppm, THF, 400 MHz) 0.92 (t, 9H), 1.30-1.40 (m, 18H), 1.67 (quin, 6H), 2.65 (t , 6H), 7.25 (d, 6H), 7.41 (t, 3H), 7.45 (t, 3H), 7.64 (d, 6H), 7.70 (t, 3H), 7 .86 (t, 3H), 8.31 (d, 2H), 8.45 (d, 2H), 8.86 (d, 2H), 9.25 (d, 2H), 9.27 (s, 4H)

(Synthesis of porphyrin derivative P11)
Synthesis of 5,10,15,20-tetrakis (4-methoxycarbonylphenyl) -21H, 23H-porphyrin

  To the reaction vessel, pyrrole (1.48 g), methyl terephthalaldehyde (3.60 g), chloroform (600 mL) and ethanol (9 mL) were added. Thereto was added boron trifluoride (0.94 g) dropwise, and the mixture was stirred for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.74 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated on a silica gel column to obtain a product (5,10,15,20-tetrakis (4-methoxycarbonylphenyl) -21H, 23H-porphyrin, 0.45 g).

5,10,15,20-Tetrakis (4-methoxycarbonylphenyl) -21H, 23H-porphyrin (0.40 g) was dissolved in chloroform (50 mL). Thereto, zinc acetate dihydrate (1.24 g) dissolved in methanol (12 ml) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column to obtain a purple product (5,10,15,20-tetrakis (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 0.38 g).
Synthesis of 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin zinc (II) complex (porphyrin derivative P11)

  5,10,15,20-Tetrakis (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (0.35 g) was dissolved in THF (35 mL) and water (8 mL). Thereto was added 48% sodium hydroxide (0.8 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, 3% formic acid water was added to the residue to make it weakly acidic. The precipitate was recovered and developed and separated on a silica gel column to obtain a purple product (5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin zinc (II) complex, 0.29 g).

(Synthesis of porphyrin derivative P12)
Synthesis of 5,10,15,20-tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin

  To the reaction vessel, p-methoxyphenyldipyromethane (1.00 g), p-anisaldehyde (0.54 g) and dichloromethane (200 mL) were added. Trifluoroacetic acid (0.80g) was dripped there and it stirred for 1 hour. N, N-diisopropylethylamine (0.90 g) was added and stirred for 1 hour. To this solution, p-chloranil (1.48 g) was added and further stirred for 2 hours. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column to obtain a product (5,10,15,20-tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin, 0.13 g).

Synthesis of 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin zinc (II) complex (porphyrin derivative P12)

  5,10,15,20-Tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin (0.12 g) was dissolved in chloroform (30 mL). Thereto, zinc acetate dihydrate (0.55 g) dissolved in methanol (10 mL) was added dropwise. After confirming the completion of the reaction by TLC, the solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column to obtain a purple product (5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin zinc (II) complex, 0.08 g).

(Synthesis of porphyrin derivative P15)
Synthesis of 5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynyl-21H, 23H-porphyrin

  To the reaction vessel, pyrrole (0.66 g), methyl terephthalaldehyde (1.21 g), phenylpropargylaldehyde (0.32 g), chloroform (500 mL) and ethanol (7 mL) were added. Thereto was added boron trifluoride (0.42 g) dropwise, and the mixture was stirred as it was for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.67 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column to obtain a product (5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynyl-21H, 23H-porphyrin, 0.16 g).

Synthesis of 5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynylporphyrin zinc (II) complex

  5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynyl-21H, 23H-porphyrin (0.13 g) was dissolved in chloroform (20 mL). Thereto, zinc acetate dihydrate (0.42 g) dissolved in methanol (5 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column to obtain a purple product (5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynylporphyrin zinc (II) complex, 0.11 g).

Synthesis of 5,10,15-tri (4-carboxyphenyl) -20-phenylethynylporphyrin zinc (II) complex (porphyrin derivative P15)

  5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynylporphyrin zinc (II) complex (0.10 g) was dissolved in THF (12 mL) and water (4 mL). Thereto was added 48% sodium hydroxide (0.40 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected and developed and separated on a silica gel column to obtain a purple product (5,10,15-tri (4-carboxyphenyl) -20-phenylethynylporphyrin zinc (II) complex, 0.06 g). .

(Porphyrin derivatives P13 and P14)
As 5,10,15,20-tetraphenyl-21H, 23H-porphyrin (porphyrin derivative P13, CAS number: 917-23-7), one commercially available from Wako Pure Chemical Industries, Ltd. was used. Further, tetrakis (4-carboxyphenyl) porphyrin (porphyrin derivative P14, CAS number: 14609-54-2) used was commercially available from Tokyo Chemical Industry Co., Ltd.

3. Comparative compounds As comparative examples, a phthalocyanine zinc complex (Comparative compound Pc-a, CAS number: 13420-04-8, manufactured by Tokyo Chemical Industry Co., Ltd.) and 21H, 23H-porphyrin (Comparative compound Por-a, CAS number: 101) -60-0, manufactured by Funakoshi Co., Ltd.).

4). Synthesis of Organic Dye Complex The ethanol solution of the obtained phthalocyanine derivative A and the ethanol solution of porphyrin derivative P1 were mixed at 25 ° C. so as to have the mixing ratio and concentration of A and P1 set in the following examples.

5. Evaluation of organic dye complexes (measurement of ultraviolet and visible absorption spectra)
(A) Ultraviolet / visible absorption spectrum measurement in a state of being adsorbed on titanium dioxide On a glass substrate (fluorine-doped tin oxide film-forming glass, 35 mm × 33 mm), a titanium dioxide paste (catalyst conversion, PST-21NR) is applied. Then, it was printed in a square shape (1 cm × 1 cm, film thickness 0.8 μm) by screen printing, dried, and fired at 500 ° C. The formed titanium dioxide film was subjected to ethanol solution (0.1 mmol / L) of phthalocyanine derivative A, porphyrin derivative P1 ethanol solution (0.1 mmol / L), and organic dye complex (A + P1) ethanol solution (0.1 mmol / L). L) for 12 hours at 25 ° C., respectively. After immersion, the substrate was washed with ethanol, dried, and the ultraviolet / visible absorption spectrum was measured. The results are shown in FIG.
(B) Ultraviolet / visible absorption spectrum measurement in ethanol A 5 μmol / L ethanol solution of each of phthalocyanine derivative A, porphyrin derivative P1 and organic dye complex A + P1 was prepared, and an ultraviolet / visible absorption spectrum was measured. The results are shown in FIG.

  In both FIG. 1 (a) and FIG. 1 (b), a long wavelength shift of the absorption spectrum was observed.

(Measurement of association constant of organic dye complex)
According to the Rose-Drago method (see Non-Patent Document 2), the association constant of the organic dye complex (A + P1) in an ethanol solution was measured. The results are shown in Table 2.

  As shown in Table 2, it was found that the organic dye complex (A + P1) formed an association having a very large association constant.

(Measurement of ultraviolet and visible absorption spectrum when the concentration of organic dye complex is changed)
4. Solution concentration of the organic dye complex (A + P1) is 1.25 μmol / L, 2.5 μmol / L, It changed to micromol / L, 10 micromol / L, 20 micromol / L, and 30 micromol / L, and the ultraviolet and visible absorption spectrum of each solution was measured. The results are shown in FIG.

  As shown in FIG. 3, it was found that the organic dye complex (A + P1) partially formed an aggregate even at an extremely low concentration of 1.25 μmol / L.

(Measurement of ultraviolet and visible absorption spectra when the mixing ratio of phthalocyanine derivative and porphyrin derivative is changed)
In the synthesis of the organic dye complex (A + P1), the mixture was adjusted by changing the mixing ratio of the phthalocyanine derivative A and the porphyrin derivative P1, and the ultraviolet / visible absorption spectrum of the obtained solution was measured. The results are shown in FIG.

  As shown in FIG. 4, it was found that the organic dye complex (A + P1) of the present invention partly formed an aggregate in the mixing ratio range of 1: 9 to 9: 1.

(Formation of various organic dye complexes)
Similar to the organic dye complex (A + P1), the phthalocyanine derivatives A to D or the comparative compound Pc-a and the porphyrin derivatives P1 to P15 or the comparative compound Por-a are mixed at a ratio of 1: 1 to obtain the organic dye complex. A 5 μmol / L ethanol solution of the body or organic dye mixture was prepared. The results are shown in Table 3 and FIG. The presence or absence of the formation of the aggregate in the solution is determined based on the absorption spectrum of the wavelength when the phthalocyanine derivative and the porphyrin derivative are mixed at 1: 1, based on the maximum absorption spectrum of the phthalocyanine derivative used alone. When the absorption wavelength was 90% or less and a new absorption wavelength was observed on the longer wavelength side, it was determined that an aggregate was formed.

  As is apparent from Table 3 and FIG. 5, in Comparative Examples 5 to 7, the respective absorption spectra of the phthalocyanine derivative and porphyrin derivative merely overlapped, and the absorption spectrum of the aggregate was not observed.

(Preparation of dye-sensitized solar cell)
(1) Dye-sensitized solar cells using the organic dye complex (A + P1: Example 1) prepared in the above synthesis example, and the phthalocyanine derivative A alone and the porphyrin derivative P1 alone were prepared by the following procedure.

i. On a glass substrate (fluorine-doped tin oxide film-formed glass, 35 mm × 33 mm),
Titanium dioxide paste (catalyst conversion, PST-21NR) is printed in a square shape (1 cm × 1 cm, film thickness 8 μm) by screen printing, dried, and then further titanium dioxide paste (catalyst conversion, PST-400C). ) Was screen printed to a film thickness of 4 μm. This was baked at 500 ° C. to form a power generation layer.

  ii. The electrode on which the power generation layer was formed was prepared by using an ethanol solution of phthalocyanine derivative A (0.1 mmol / L), a porphyrin derivative P1 ethanol solution (0.1 mmol / L), and an organic dye complex (A + P1) ethanol solution (0. 1 mmol / L) at 25 ° C. for 12 hours. After immersion, the substrate was washed with ethanol and dried to obtain an anode electrode.

  iii. Adhesive is applied around the power generation layer of the anode electrode, and the anode electrode and a platinum-coated titanium plate (cathode electrode) treated with thioacetamide having a separately prepared electrolyte injection hole are bonded with the adhesive. The electrodes were bonded so that both electrodes were arranged in parallel at a constant interval of about 50 μm.

  iv. Next, an electrolytic solution was injected from the electrolytic solution injection port. Here, the electrolyte includes iodine (0.1 molM / L), lithium iodide (0.1 mol / L), 1-propyl-3-methylimidazolium iodide (0.8 mol / L), and N- A solution in which methylbenzimidazole (0.5 mol / L) was added to 3-methoxypropionitrile so as to have the concentration described in parentheses was used.

  v. The electrolyte injection hole was sealed with an adhesive, and solder for terminal removal was applied onto the anode electrode to complete the experimental cell.

(Measurement of spectral sensitivity)
The spectral sensitivity of the produced solar battery cell was measured with a spectral sensitivity measuring device (CEP-2000 manufactured by Spectrometer Co., Ltd.). The results are shown in FIG. Moreover, the external appearance of these photovoltaic cells is shown in FIG.

(performance test)
The performance of the dye-sensitized solar cell obtained as described above was evaluated.

After creating the cell, the cell was placed in a dryer (DK810, manufactured by Yamato Scientific Co., Ltd.) having an internal temperature of 85 ° C. After 24 hours, the cell was taken out and cooled to room temperature, and then the conversion efficiency of the cell was measured under irradiation conditions of AM 1.5, 1 SUN (100 mW / cm ² ). The results are shown in Table 4.

The photoelectric conversion efficiency was calculated by the following formula.
Photoelectric conversion efficiency (%) =
100 × [(Short-circuit current density × Open circuit voltage × Curve factor) / (Irradiated solar energy)]

  As shown in Table 4 above, the dye-sensitized solar cell produced using the organic dye composite of the present invention as a photosensitizing dye showed high photoelectric conversion efficiency. This is because, as is apparent from FIG. 6, the organic dye complex of the present invention has an absorption wavelength that extends to the longer wavelength side, which is different from the mere sum of the absorption wavelengths of the phthalocyanine derivative and porphyrin derivative. It is considered that a wider range of light can be absorbed and the photoelectric conversion efficiency is improved.

DESCRIPTION OF SYMBOLS 1 Transparent electrode 2 Metal oxide semiconductor electrode 3 Electrolyte 4 Counter electrode

Claims (7)

The following general formula (1)
(In the formula, R ^{1 to} R ⁸ are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and the substituted aryl or the substituent of the substituted heteroaryl has a carbon number. Selected from 1 to 3 alkyl groups, carboxy groups or halogens , and 4 or more of the above R ^{1 to} R ⁸ are not simultaneously hydrogen atoms,
X ^{1 to} X ⁸ are O, n ^{1 to} n ⁸ are each independently 0 or 1,
M ¹ represents any at least one atom or atomic group capable of binding to phthalocyanine)
A phthalocyanine derivative represented by
The following general formula (2)
(In the formula, A, B, C and D each independently represent a monovalent organic group, and at least two of the A to D are substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. Yes,
M ² represents any at least one atom or atomic group capable of binding to porphyrin)
A porphyrin derivative represented by the formula: or a complex thereof. ^2. The composite according to claim 1, wherein M ¹ and M ² are each independently selected from a hydrogen atom, a typical metal element, a metalloid element, or a transition metal element.   The complex according to claim 1, wherein at least three of the A to D are substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. The following general formula (1)
(In the formula, R ^{1 to} R ⁸ are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and the substituted aryl or the substituted heteroaryl has a carbon number of 1; Selected from ˜3 alkyl groups, carboxy groups or halogens , and four or more of the above R ^{1 to} R ⁸ are not hydrogen atoms at the same time,
X ^{1 to} X ⁸ are O, n ^{1 to} n ⁸ are each independently 0 or 1,
M ¹ represents any at least one atom or atomic group capable of binding to phthalocyanine)
A phthalocyanine derivative represented by
The following general formula (2)
(In the formula, A, B, C and D each independently represent a monovalent organic group, and at least two of the A to D are substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. Yes,
M ² represents any at least one atom or atomic group capable of binding to porphyrin)
A method for producing a complex comprising mixing a porphyrin derivative represented by the formula (I) or a salt thereof in a liquid medium. The following general formula (1)
(In the formula, R ^{1 to} R ⁸ are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and the substituted aryl or the substituted heteroaryl has a carbon number of 1; Selected from ˜3 alkyl groups, carboxy groups or halogens , and four or more of the above R ^{1 to} R ⁸ are not hydrogen atoms at the same time,
X ^{1 to} X ⁸ are O, n ^{1 to} n ⁸ are each independently 0 or 1,
M ¹ represents any at least one atom or atomic group capable of binding to phthalocyanine)
A phthalocyanine derivative represented by
The following general formula (2)
(In the formula, A, B, C and D each independently represent a monovalent organic group, and at least two of the A to D are substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. Yes,
M ² represents any at least one atom or atomic group capable of binding to porphyrin)
The photosensitizing dye for solar cells containing the composite_body | complex with the porphyrin derivative represented by these, or its salt.   6. An oxide semiconductor electrode, wherein the photosensitizing dye according to claim 5 is adsorbed on an oxide semiconductor.   A dye-sensitized solar cell comprising the oxide semiconductor electrode, transparent electrode, electrolyte and counter electrode of claim 6.