KR20100128258A - Novel ruthenium-based dye and preparation thereof - Google Patents

Abstract

PURPOSE: A ruthenium-based dye is provided to ensure improved photoelectric conversion efficiency compared with a conventional ruthenium system dye and to strengthen the bondability with oxide semiconductor microparticles. CONSTITUTION: A ruthenium-based dye is represented by chemical formula 1. In chemical formula 1, a1 has at least one ring, wherein the substituent is halogen, amide, cyano, hydroxyl, nitro, C1-20 alkyl, C1-20 alkoxy or acyl; A and B are independently hydrogen or a functional group of chemical formula 1-a.

Description

Novel ruthenium-based dyes and preparation method thereof {NOVEL RUTHENIUM-BASED DYE AND PREPARATION THEREOF}

The present invention relates to a novel ruthenium-based dye used in dye-sensitized solar cells (DSSC) and a method for producing the same.

Since the development of the dye-sensitized nanoparticle titanium oxide solar cell by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of absorbing and generating electron-hole pairs, and a transition metal oxide for transferring generated electrons.

Typical dyes used in dye-sensitized solar cells include the following compounds.

* TBA: tetrabutylammonium cation

However, it is still required to increase the efficiency and durability of the solar cell by increasing the binding force with the oxide semiconductor fine particles, the photoelectric conversion efficiency, the J _sc (short circuit photocurrent density) and the molar extinction coefficient compared to the above dyes. There is a need for research.

Therefore, the present invention exhibits significantly improved photoelectric conversion efficiency than conventional ruthenium-based dyes, enhances the bonding force with oxide semiconductor fine particles, and has excellent J _sc (single-circuit photocurrent density) and molar extinction coefficient to greatly increase the efficiency of solar cells. It is an object to provide a dye which can be improved and a method for producing the same.

In addition, the present invention exhibits a remarkably improved photovoltaic conversion efficiency including the dye, enhanced binding force with oxide semiconductor fine particles, dye-sensitized photoelectric conversion device excellent in J _sc (short circuit photocurrent density) and molar absorption coefficient, and efficiency It is an object to provide a significantly improved dye-sensitized solar cell.

In order to achieve the above object, the present invention provides a ruthenium-based dye represented by the following formula (1):

Where

the a1 ring may have one or more substituents and the substituents may be halogen, amide, cyano, hydroxy, nitro, C _1-20 alkyl, C _1-20 alkoxy or acyl;

이고 (*부분이 결합부분이다), 단 A 및 B 둘 중 적어도 하나는 수소가 아니며;A and B are each independently hydrogen or

(* Moiety is a binding moiety) provided that at least one of both A and B is not hydrogen;

And Ar ₁ and Ar ₂ are each independently a C _6-30 aryl-by-fluorenyl or spy, Ar ₁ and Ar _2, at least one of the two is a by-fluorenyl a spy, the Ar ₁ and Ar ₂ is one or more May be substituted with hydroxy, halogen, nitro, C _1-12 alkyl or C _1-12 alkoxy;

X is phenylene unsubstituted or substituted with one or more hydroxy, halogen, nitro, C _1-12 alkyl or C _1-12 alkoxy;

Y is thiophene substituted or unsubstituted with one or more hydroxy, halogen, nitro, C _1-12 alkyl, C _1-12 alkoxy, or is a connecting line.

In another aspect, the present invention (i) lithium compound of the following formula (2) Li-thiation reaction (lithiation) with n-butyllithium and subsequently reacted with dimethylformamide to prepare a compound of formula (3),

(ii) reacting a compound of formula 3 with formula 4 or formula 4-1 to prepare a compound of formula 5

(Iii) a compound of Formula 5 is represented by Formula 6; Formula 7; And it provides a method for producing a dye represented by the formula (1) comprising sequentially reacting with a compound of formula (8):

[Formula 4-1]

Ar ₁ , Ar ₂ , X and Y in Formula 2-8 are as defined in Formula 1.

In another aspect, the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particle carrying a compound represented by the formula (1).

In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.

The novel ruthenium-based dye of the present invention exhibits significantly improved photoelectric conversion efficiency than conventional dyes, enhances the binding force with titanium dioxide, and improves the efficiency of the solar cell due to excellent J _sc (short circuit photocurrent density) and molar extinction coefficient. It can greatly improve.

The present inventors, when manufacturing a dye-sensitized solar cell by supporting the compound represented by the formula (1) in the oxide semiconductor fine particles, it is strongly bonded to the oxide semiconductor fine particles and excellent in durability, photoelectric conversion efficiency, J _sc (short circuit photocurrent density) and mol It was confirmed that the higher the extinction coefficient than the existing dye-sensitized solar cells exhibited higher efficiency and completed the present invention.

Ruthenium-based dyes of the present invention may preferably be represented by any of the following structures:

In another aspect, the present invention provides a method for producing a dye represented by the formula (1), wherein the dye is (i) Lithium-substituted with the compound of formula (2) with n-butyllithium (lithiation) and continuously with dimethylformamide Reaction to prepare a compound of formula

(ii) reacting a compound of formula 3 with formula 4 or formula 4-1 to prepare a compound of formula 5

(Iii) a compound of Formula 5 is represented by Formula 6; Formula 7; And it can be prepared through the reaction with the compound of formula (8) sequentially.

As a specific example, the compound represented by Chemical Formula 1a may be a dye represented by Chemical Formula 1a. The compound of Chemical Formula 3-1 may be reacted with dimethylformamide after lithium lithiation with n-butyllithium. To prepare a compound of formula 5 by mixing the compound of formula 3-1 with a compound of formula 4 in an organic solvent (e.g. tetrahydrofuran (THF)) in the presence of NaH and reflux, and the compound of formula 5 It can be prepared by reacting with a compound of formula 6 in a solvent (eg dimethylformamide (DMF)) and subsequently with the compound of formula 7 and 8 in sequence.

[Formula 1a]

[Formula 2-1]

[Formula 3-1]

As another example, the compound of Formula 1b

(i) Suzuki coupling reaction of a compound of Formula 2-1 with a compound of Formula 9 to prepare a compound of Formula 10,

(ii) reacting the compound of Formula 10 with n-butyllithium for lithiation and subsequently reacting with dimethylformamide to prepare a compound of Formula 11

(iii) The compound of Formula 11 may be prepared by sequentially reacting the compound of Formula 4, Formula 6, Formula 7, and Formula 8 with the resultant.

[Chemical Formula 1b]

[Formula 2-1]

As another example, the compound of Formula 1c may be (i) lithium-third-reacting the compound of Formula 2-1 with n-butyllithium and subsequently reacting with dimethylformamide to react the compound of Formula 3-1. Manufacturing,

(ii) Compounds of formula 3-1 may be prepared by sequentially reacting with compounds of formulas 4-1, 6, 7, and 8:

[Formula 1c]

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

As another example, the compound of Formula 1d may be prepared by (i) coupling a compound of Formula 2 with a compound of Formula 9 to Suzuki to prepare a compound of Formula 10,

(ii) reacting the compound of Formula 10 with n-butyllithium for lithiation and subsequently reacting with dimethylformamide to prepare a compound of Formula 11

(iii) a compound of formula 11 may be prepared by sequentially reacting with a compound of formulas 4-1, 6, 7, and 8:

≪ RTI ID = 0.0 &

[Formula 2-1]

[Formula 9]

[Formula 10]

[Formula 11]

In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles. The present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by the formula (1) can be applied to the method of manufacturing a dye-sensitized photoelectric conversion device for solar cells using a conventional dye, of course, preferably the present invention The dye-sensitized photoelectric conversion device may be prepared by fabricating a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the dye of the present invention on the thin film.

In this invention, it is preferable that the surface is electroconductive as a board | substrate which provides the thin film of an oxide semiconductor, and what is marketed can also be used. As a specific example, conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony on a surface of glass or a transparent polymer material such as polyethylene terephthalate or polyethersulfone, or a metal thin film such as steel, silver, or gold may be used. The formed thing can be used. In this case, the conductivity is preferably 1000 Ω or less, particularly preferably 100 Ω or less.

As the fine particles of the oxide semiconductor, a metal oxide is preferable. As specific examples, oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, among these, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferred. The oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.

The particle diameter of the fine particles of the oxide semiconductor is preferably 1 to 500 nm, more preferably 1 to 100 nm as the average particle diameter. In addition, the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.

The oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on a substrate by spray spraying, a method of electrically depositing a semiconductor fine particle thin film using a substrate as an electrode, a slurry of semiconductor fine particles or semiconductor fine particles such as a semiconductor alkoxide. After applying the paste containing the fine particles obtained by hydrolyzing the precursor onto the substrate, it can be produced by a method of drying, curing or baking, and a method of applying the paste onto the substrate is preferred. In the case of this method, a slurry can be obtained by disperse | distributing the oxide semiconductor microparticles | fine-particles which are secondary aggregated so that an average primary particle diameter may be 1-200 nm in a dispersion medium by a conventional method.

The dispersion medium for dispersing the slurry can be used without particular limitation so long as it can disperse the semiconductor fine particles, and alcohols such as water and ethanol, ketones such as acetone and acetylacetone, or hydrocarbons such as hexane can be used, and these can be mixed and used. Among them, it is preferable to use water among them in order to reduce the viscosity change of the slurry. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles | fine-particles. Specific examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid and nitric acid, or acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

The substrate coated with the slurry can be fired, and its firing temperature is at least 100 ° C, preferably at least 200 ° C, and the upper limit is generally below the melting point (softening point) of the substrate, and usually the upper limit is 900 ° C, preferably 600. It is below ℃. In the present invention, the firing time is not particularly limited, but is generally within 4 hours.

It is preferable that the thickness of the thin film on a board | substrate in this invention is 1-200 micrometers, Preferably it is 1-50 micrometers. Although some thin layers of oxide semiconductor fine particles are welded when firing, such welding is not particularly troubled for the present invention.

In addition, the oxide semiconductor thin film may be subjected to secondary treatment. For example, the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as an alkoxide, chloride, nitride, or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used. As a chloride, titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

In addition, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, as a specific example by dispersing a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving, or dye The method of immersing the board | substrate with which the said oxide semiconductor thin film was provided in the obtained dispersion liquid is mentioned. The concentration in the solution or dispersion can be appropriately determined by the dye. The deposition time is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours. Specific examples of the solvent that can be used to dissolve the dye include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, t-butanol and the like. The dye concentration of the solution is usually 1 x 10 ^-6 M to 1 M is suitable, preferably 1 x 10 ^-5 M to 1 x 10 ^-1 M. In this way, the photoelectric conversion element of this invention which has oxide semiconductor microparticles | fine-particles on the thin film sensitized with dye can be obtained.

The dye represented by the formula (1) supported by the present invention may be one kind or may be mixed in several kinds. In addition, when mixing, another dye or a metal complex dye can be mixed with the dye of this invention. Examples of the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin, and the like are preferable, and organic dyes used for mixing include metal-free phthalocyanine, porphyrin, cyanine, merocyanine, Methine dyes such as oxonol, triphenylmethane, and acrylic acid dyes as shown in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene-based dyes (MK Nazeeruddin, A). .Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., Vol. 115, p . 6382 (1993). ). In the case of using two or more kinds of dyes, the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved and adsorbed.

In the present invention, when the dye is supported on the thin film of the oxide semiconductor fine particles, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the dyes from bonding. Examples of the inclusion compound include carboxylic acids such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, methyl ester of cholate, and sodium cholate, steroidal compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and calix arene, Polyethylene oxide and the like can be used.

After the dye is supported, the semiconductor electrode surface can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid. As a treatment method, for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.

In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1) In addition, conventional methods for manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and, as a specific example, a photoelectric conversion device electrode (cathode) and a counter electrode supporting the dye represented by Formula 1 on the oxide semiconductor fine particles. (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.

Preferably, one example of a specific method of manufacturing a dye-sensitized solar cell of the present invention is the step of coating a titanium oxide paste on a conductive transparent substrate, baking the substrate coated with a paste to form a titanium oxide thin film, titanium oxide thin film Impregnating the formed substrate into a mixed solution in which the dye represented by Chemical Formula 1 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon. Forming a hole penetrating a glass substrate and a counter electrode, placing a thermoplastic polymer film between the counter electrode and the dye-adsorbed titanium oxide film electrode, and performing a heat compression process to perform the counter electrode and titanium oxide. Bonding a film electrode to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole; Implanting be and can be prepared through the step of sealing the thermoplastic polymer.

Redox electrolytes, hole transport materials, p-type semiconductors, and the like may be in the form of liquids, coagulants (gels and gels), solids, and the like. As liquids, redox electrolytes, dissolved salts, hole transport materials, p-type semiconductors, and the like are dissolved in a solvent, and at room temperature, dissolved salts, etc., in the case of coagulation bodies (gels and gels), these are polymer matrices or low molecular gelling agents. What was contained in etc. can be mentioned, respectively. As the solid, a redox electrolyte, a dissolved salt, a hole transport material, a p-type semiconductor, or the like can be used.

Examples of the hole transport material include an amine derivative, a conductive polymer such as polyacetylene, polyaniline, and polythiophene, and an object using a discotech liquid crystal phase such as triphenylene-based compound. Moreover, CuI, CuSCN, etc. can be used as a p-type semiconductor. It is preferable that the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.

As the redox electrolyte used in the solar cell of the present invention, a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen redox-based electrolytes are preferable. As a halogen molecule in the halogen redox electrolyte composed of halogen compound-halogen molecules, an iodine molecule is preferable. As a halogen compound having a halogen ion as a large ion, halogenated metal salts such as LiI, NaI, KI, CaI ₂ , MgI ₂ and CuI, or organic ammonium salts of halogens such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine, Or I ₂ can be used.

In addition, when the redox electrolyte is configured in the form of a solution containing the same, an electrochemically inert one may be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable. The solvents may be used alone or in combination. In the case of a gel positive electrolyte, one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight.

In the solar cell of the present invention, a counter electrode (anode) is disposed in a photoelectric conversion element (cathode) on which a dye is carried on an oxide semiconductor fine particle on a substrate so as to face it, and a solution containing a redox electrolyte is filled therebetween. Can be obtained.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Synthesis of Dyes

All reactions were run in an argon atmosphere and the solvent was distilled off with a suitable reagent purchased from Sigma-Adrich. ¹ H NMR spectra were measured on a Varian Mercury 300 spectrometer. Absorbance spectra were measured with a Perkin-Elmer Lambda 2S UV-visible spectrometer.

Example 1 Synthesis of 2-bromo-9-fluorenone

2-bromofluorene (19.6 g, 80 mmol), pyridine (200 ml), 25% tetramethylammonium hydroxide (2 ml) were added and stirred for 12 hours while bubbling air at room temperature. Sulfuric acid was added thereto, followed by filtration and recrystallization with ethanol to give a yellow solid 2-bromo-9-fluorenone (17.8 g, 85.1%).

Example 2 Synthesis of 4,4'-di-tert-butylbiphenyl

Biphenyl (30. g, 200 mmol), anhydrous iron chloride (160 mg) and methylene chloride (200 ml) were mixed and stirred at room temperature. Tert-butyl chloride (46.4 ml, 432 mmol) was slowly added thereto, followed by stirring for 12 hours. After the completion of the reaction, the mixture was extracted three times with hexane (200 ml), dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. 4,4'-di-tert-butylbiphenyl (42 g, 97.2%) was obtained without further purification.

Example 3 Synthesis of 2-bromo-4,4'-di-tert-butylbiphenyl

4,4'-di-tert-butylbiphenyl (7.98 g, 30 mmol), anhydrous iron chloride (20 mg) and chloroform (30 ml) were mixed and stirred while maintaining 0 ° C. Then, bromine (4.8 g, 30 mmol) dissolved in 20 ml of chloroform was slowly added, followed by stirring for 12 hours. After completion of the reaction, sodium carbonate was added until the orange color disappeared, extracted three times with hexane (100 ml), dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. 2-Bromo-4,4'-di-tert-butylbiphenyl containing impurity was obtained.

Example 4 Synthesis of 2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene

2-bromo-4,4'-di-tert-butylbiphenyl (6.12 g, 10 mmol) containing impurities was dissolved in tetrahydrofuran (100 ml) and then maintained at -78 ° C. N-butyllithium (12 ml, 15 mmol) was slowly added thereto, followed by stirring for 1 hour. 2-bromofluorene (2.6 g, 10 mmol) was dissolved in tetrahydrofuran (40 ml) and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. The mixture was dissolved in acetic acid (30 ml) and stirred, and a drop of concentrated hydrochloric acid was added and refluxed for one hour. After cooling to room temperature, the precipitate is filtered and washed with water to give 2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene and 4,4'-di-tert A mixture of -butylbiphenyl was obtained. The mixture was separated by a mobile phase of n-hexane in a silica gel packed column to give 2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene (2.74 g , 54%).

Example 5 2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -2-yl)- Synthesis of N-phenyl-9,9'-spirobi [fluorene] -2-amine

2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene (2.74 g, 6.93 mmol), aniline (0.26 g, 2.77 mmol), t-butoxy 50 mL of toluene was added to sodium (0.67 g, 6.93 mmol, 2.5 eq), Pd ₂ (ba) ₃ 0.04 g (0.12 mmol), and P (t-Bu) ₃ (0.03 g, 0.12 mmol) for 10 hours under nitrogen atmosphere. Under reflux. After cooling the reaction solution to room temperature, 30 mL of distilled water was added and stirred. The toluene layer was then extracted, dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure. The reaction mixture was developed with normal hexane and purified by column chromatography to give 2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia [ 1.57 g (60%) of fluorene] -2-yl) -N-phenyl-9,9'-spirobi [fluorene] -2-amine was obtained.

Example 6 N- (4-bromophenyl) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia Synthesis of [Fluoren] -2-yl) -9,9'-spirobi [fluorene] -2-amine

2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -2-yl) -N in 50 mL of DMF -Phenyl-9,9'-spirobi [fluorene] -2-amine (1.57 g, 1.66 mmol) was added and stirred. 0.3 g (1.66 mmol) of NBS was added to the reaction solution, followed by stirring at 50 ° C. for 2 hours, followed by pouring 100 mL of distilled water and stirring. The solid formed was filtered, dissolved in THF, dried over anhydrous magnesium sulfate, and the solvent THF was removed under reduced pressure to obtain a reaction mixture of liquid, which formed a solid in the reaction mixture over time. 50 mL of ethanol was added thereto, stirred, and the impurities were washed, filtered and dried to obtain N- (4-bromophenyl) -2 ', 7'-di-tert-butyl-N- (2', 7'- 0.60 g (35%) of di-tert-butyl-9,9'-spirobi [fluorene] -2-yl) -9,9'-spirobi [fluorene] -2-amine was obtained.

Example 7 2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl)- Synthesis of N- (4- (3-hexylthiophen-2-yl) phenyl) -9,9'-spirobi [fluorene] -2-amine ("compound of formula 10")

N- (4-bromophenyl) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia [fluorene]- 2-yl) -9,9'-spirobi [fluorene] -2-amine ("Compound of formula 2", 0.58 g, 0.56 mmol), 4-hexylthiophen-5-yl boronic acid ("Formula 9 ", 0.12 g, 0.56 mmol) tetrakis- (triphenylphosphine) palladium (0) (0.012 g, 0.011 mmol) and 2 M aqueous potassium carbonate solution were added and refluxed under nitrogen gas for 12 hours, followed by stirring. . After stirring, the organic layer was extracted with methylene chloride and water, distilled under reduced pressure, and purified by column (eluent-MC: Hx = 1: 4), 2 ', 7'-di-tert-butyl-N- ( 2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) -N- (4- (3-hexylthiophen-2-yl) phenyl) -9 0.54 g (75%) of, 9'-spirobi [fluorene] -2-amine was obtained.

Example 8 5- (4-((2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) (2', 7'-di- Synthesis of tert-butyl-9,9'-spirobi [fluorene] -7-yl) amino) phenyl) -4-hexylthiophen-2-carbaaldehyde (“Compound 11”)

2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) -N- (4- In anhydrous ethanol solution of (3-hexylthiophen-2-yl) phenyl) -9,9'-spirobi [fluorene] -2-amine ("compound of formula 10", 0.54 g, 0.42 mmol), n- BuLi (0.35 ml, 1.6 M solution in hexane) was added under argon. After 3 h, DMF (0.05 g, 0.7 mmol) was added thereto at 0 ° C. under argon and washed with 5% KOH. The reaction solution was dried over magnesium sulfate, the solvent was removed, and the obtained solid was subjected to silica gel chromatography (eluent-MC: Hx = 1: 1) to give 5- (4-((2 ', 7'-di-tert-butyl-). 9,9'-spirobi [fluorene] -3-yl) (2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -7-yl) amino) phenyl 0.41 g (75%) of 4-hexylthiophene-2-carbaaldehyde ("Compound of formula 11") was obtained.

Example 9 4-((2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) (2', 7'-di-tert-butyl Synthesis of -9,9'-Spirobi [fluorene] -7-yl) amino) benzaldehyde ("Compound of Formula 3")

In Example 8, the compound of Formula 3 was synthesized using the compound of Formula 2 (0.43 g, 0.42 mmol) instead of the compound of Formula 10.

Example 10 Synthesis of 4-bromomethyl-4'-methyl-2,2'-bipyridine

This compound utilizes the synthesis method of the existing literature ( Inorg. Chem. 1991, 30 , 2942). 1 H NMR (CDCl ₃ ): 8.65 (d, JH-H = 4.5 Hz, 1H), 8.54 (d, JH-H = 4.5 Hz, 1H), 8.43 (s, 1H), 8.24 (s, 1H), 7.34 (d, JH-H = 4.5 Hz, 1H), 7.17 (d, JH-H = 4.5 Hz, 1H), 4.47 (s, 2H), 2.45 (s, 3H).

Example 11 Synthesis of 4,4'-bisbromomethyl-2,2'-bipyridine

This compound used the synthesis method of the existing literature ( Inorg. Chem. 1991, 30 , 2942). 1 H NMR (CDCl ₃ ): 8.67 (d, JH-H = 4.5 Hz, 2H), 8.43 (s, 2H), 7.36 (d, JH-H = 4.5 Hz, 2H), 4.48 (s, 4H).

Example 12 Synthesis of 4-diethylphosphonomethyl-4'-methyl-2,2'-bipyridine ("Compound of Formula 4")

A mixed solution of the compound of Example 10 (2 g, 7.60 mmol) and excess triethylphosphite (5 mL, 0.29 mol) was stirred under 80 ° C. conditions for 6 hours. Thereafter, after cooling to room temperature, excess triethylphosphite was removed under vacuum conditions. The oily residue was column chromatographed to give the title compound as pale yellow. 1 H NMR (CDCl ₃ ): 8.60 (d, JH-H = 4.5 Hz, 1H), 8.52 (d, JH-H = 4.5 Hz, 1H), 8.32 (s, 1H), 8.22 (s, 1H), 7.31 (d, JH-H = 5.4 Hz, 1H), 7.12 (d, JH-H = 5.4 Hz, 1H), 4.06 (dq, 3 JH-P = 7.2 Hz, 4H), 3.22 (d, 2 JH-P = 21.3 Hz, 2H), 2.43 (s, 3 H), 1.26 (t, 3 JH-H = 7.2 Hz, 6H).

[ Example  13] 4,4'- Vis ( Diethylphosphonomethyl ) -2,2'- Of bipyridine (a compound of Formula 4-1)  synthesis

In Example 12, the compound of Example 11 was used instead of the compound of Example 10. 1 H NMR (CDCl ₃ ): 8.60 (d, JH-H = 5.1 Hz, 2H), 8.33 (s, 2H), 7.32 (d, JH-H = 5.1 Hz, 2H), 4.07 (dq, 3 JH-P = 11.4 Hz, 3 JH- H = 7.2 Hz, 8H), 3.23 (d, 2 JH-P = 22.2 Hz, 4H), 1.27 (t, 3 JH-H = 7.2 Hz, 12H).

Example 14 (E) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia [fluorene] -3 -Yl) -N- (4- (2- (4'-methyl-2,2'-bipyridin-4-yl) vinyl) phenyl) -9,9'-spirobiby [fluorene] -2- Synthesis of Amine ("Compound of Formula 5")

Potassium t -butoxide (0.16 g, 1.41 mmol) was added dropwise to a THF solution (30 mL) in which a compound of Formula 3 (1.37 g, 1.41 mmol) and a compound of Formula 4 (0.45 g, 1.41 mmol) were dissolved. Stirred for 10 h. Thereafter, 10 mL of water was added dropwise, only THF was dried in vacuo, extracted with dichloromethane, and recrystallized with dichloromethane / hexane to obtain the title compound.

Example 15 (E) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3 -Yl) -N- (4- (3-hexyl-5- (2- (4'-methyl-2,2'-bipyridin-4-yl) vinyl) thiophen-2-yl) phenyl) -9 Synthesis of 9'-Spyrobi [fluorene] -2-amine (“Compound 12”)

The compound of Formula 12 was obtained by using the compound of Formula 11 (1.49 g, 1.41 mmol) instead of the compound of Formula 3 in [Example 14].

[Formula 12]

Example 16 Synthesis of Compound of Formula 5-1

In Example 14, the compound of Formula 4-1 was obtained by using the compound of Formula 4-1 (0.65 g, 1.41 mmol) and potassium t-butoxide (0.32 g, 1.41 mmol) instead of the compound of Formula 4.

[Formula 5-1]

Example 17 Synthesis of Compound of Formula 12-1

In Example 14, the compound of Formula 11 (1.49 g, 1.41 mmol) instead of the compound of Formula 3, the compound of Formula 4-1 (0.65 g, 1.41 mmol) instead of the compound of Formula 4, and potassium t-butoxide Side (0.32 g, 1.41 mmol) was used to give the compound of Formula 12-1.

[Formula 12-1]

Example 18 Synthesis of Compound of Formula 1a

Dissolve the compound of formula 5 (0.45 g, 0.40 mmol) and dichloro ( p -cymene) ruthenium (II) dimer ("compound of formula 6", 0.12 g, 0.20 mmol) in DMF and the solution at 80 ° C. Stir for hours. 4,4'-dicarboxylic acid-2,2'-bipyridine ("Compound of formula 7", 0.097 g, 0.40 mmol) was added dropwise and stirred at 160 ° C. for 4 hours. In this solution, ammonium cyocyanate (“Compound 9”, 0.91, 11.96 mmol) was added thereto, stirred at 130 ° C. for 4 hours, and then dried under vacuum, water (200 mL) was added, and the compound was precipitated. The precipitate was filtered using filter paper and dried in air. This precipitate was dissolved by dropwise addition of 1.2 mmol of tetrabutylammonium hydroxide dissolved in methanol, and the dissolved solution was separated by column chromatography with methanol using Sephadex LH-20. The separated dye solution was added with a dilute nitric acid solution to obtain a dye precipitate, and then separated by a filter paper to obtain the title compound as a dark purple powder.

[Formula 1a]

MS: m / z 1602 [M < + >]. Anal. Calcd for C ₉₉ H ₈₅ N ₇ O ₄ RuS ₂ : C, 74.22; H, 5. 35; N, 6. 12; 0, 3.99; Ru, 6.31; S, 4.00. Found: C, 74.07; H, 5. 34; N, 6.11; 0, 3.98; Ru, 6.30; S, 3.99.

Example 19 Synthesis of Compound of Formula 1b

In Example 18, the title compound was obtained using the compound of Formula 12 (0.52 g, 0.40 mmol) instead of the compound of Formula 5.

[Chemical Formula 1b]

MS: m / z 1767 [M < + >]. Anal. Calcd for C ₁₀₉ H ₉₉ N ₇ O ₄ RuS ₃ : C, 74.04; H, 5. 64; N, 5.54; 0, 3.62; Ru, 5.72; S, 5.44. Found: C, 73.89; H, 5.63; N, 5.53; 0, 3.61; Ru, 5.71; S, 5.43.

Example 20 Synthesis of Compound of Formula 1c

In Example 18, the title compound was obtained using the compound of Formula 5-1 (0.84 g, 0.40 mmol) instead of the compound of Formula 5.

[Formula 1c]

MS: m / z 2558 [M < + >]. Anal. Calcd for C ₁₇₂ H ₁₅₀ N ₈ O ₄ RuS ₂ : C, 80.75; H, 5.91; N, 4.38; 0, 2.50; Ru, 3.95; S, 2.51. Found: C, 80.59; H, 5. 90; N, 4.37; 0, 2.49; Ru, 3.95; S, 2.50.

Example 21 Synthesis of Compound of Formula 1d

In Example 18, the title compound was obtained using the compound of Formula 12-1 (0.97 g, 0.40 mmol) instead of the compound of Formula 5.

≪ RTI ID = 0.0 &

MS: m / z 2891 [M < + >]. Anal. Calcd for C ₁₉₂ H ₁₇₈ N ₈ O ₄ RuS ₄ : C, 79.77; H, 6. 21; N, 3.88; 0, 2.21; Ru, 3.50; S, 4.44. Found: C, 79.61; H, 6. 20; N, 3.87; 0, 2.20; Ru, 3.49; S, 4.43.

Experiment: Preparation and Measurement of Dye-Sensitized Solar Cell

In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured using a 12 μm TiO ₂ transparent layer. A TiO ₂ paste (Solaronix, 13 nm paste) was screen printed to produce an 8 μm thick TiO ₂ transparent layer. This TiO ₂ film was treated with 40 mM TiCl ₄ solution and dried at 500 ° C. for 30 minutes. After the treated film was cooled to 60 ° C., each of the dye compounds 1a, 1b, 1c and 1d prepared in the Examples of the present invention was impregnated with the dimethylformamide solution. As reference, an ethanol solution of N3 was used. A sealed sandwich cell was assembled by heating a hot melt film (Surlyn 1702, 25 μm thick) as a spacer between the dye-adsorbed TiO ₂ electrode and the platinum-electrode. As the electrolyte solution, a solution of 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI ₂ , 0.025 M GSCn and 0.28 M tert -butylpyridine was dissolved in acetonitrile.

N3 used as a reference compound is a ruthenium-based catalyst used in conventional dye-sensitized solar cells and has a structure as follows.

[Dye N3]

The photoelectrochemical properties of the solar cell were measured and shown in Table 1 below.

dyes J _sc (mA / cm ² ) V _oc (V) FF η (%) Comparative Example (N3) 9.80 0.63 0.66 4.1 Compound 1a 9.90 0.63 0.66 4.1 Compound 1b 10.8 0.63 0.68 4.6 Compound 1c 10.3 0.63 0.67 4.3 Compound 1d 11.7 0.63 0.66 4.8

In Table 1, J _sc is a short-circuit photocurrent density, V _oc is an open circuit photovoltage, FF is a fill factor, as shown in Table 1 Likewise, it can be confirmed that the dye of the present invention can be effectively used as a dye of a dye-sensitized solar cell, and it can be confirmed that it is also excellent in performance.

Claims (9)

Ruthenium-based dyes represented by Formula 1 below:
[Formula 1]

Where
the a1 ring may have one or more substituents and the substituents may be halogen, amide, cyano, hydroxy, nitro, C _1-20 alkyl, C _1-20 alkoxy or acyl;
A and B are each independently hydrogen or

(* Moiety is a binding moiety) provided that at least one of both A and B is not hydrogen;
And Ar ₁ and Ar ₂ are each independently a C _6-30 aryl-by-fluorenyl or spy, Ar ₁ and Ar _2, at least one of the two is a by-fluorenyl a spy, the Ar ₁ and Ar ₂ is one or more May be substituted with hydroxy, halogen, nitro, C _1-12 alkyl or C _1-12 alkoxy;
X is phenylene unsubstituted or substituted with one or more hydroxy, halogen, nitro, C _1-12 alkyl or C _1-12 alkoxy;
Y is thiophene substituted or unsubstituted with one or more hydroxy, halogen, nitro, C _1-12 alkyl or C _1-12 alkoxy, or is a connecting line. The method of claim 1,
A ruthenium-based dye, wherein the dye is represented by one of the following structures:

(i) preparing a compound represented by the following Chemical Formula 3 by lithiation of the compound represented by the following Chemical Formula 2 with n-butyllithium and subsequently reacted with dimethylformamide;
(ii) reacting a compound of formula 3 with formula 4 or formula 4-1 to prepare a compound of formula 5
(Iii) a compound of Formula 5 is represented by Formula 6; Formula 7; And it provides a method for producing a dye represented by the formula (1) comprising sequentially reacting with a compound of formula (8):
(2)

(3)

[Chemical Formula 4]

[Formula 4-1]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Chemical Formula 8]

Ar ₁ , Ar ₂ , X and Y in Chemical Formula 2-8 are as defined in Chemical Formula 1 of claim 1. A dye-sensitized photoelectric conversion device comprising oxide semiconductor fine particles carrying the ruthenium-based dye of claim 1. The method of claim 4, wherein
A dye-sensitized photoelectric conversion device characterized in that a ruthenium-based dye is supported on the oxide semiconductor fine particles in the presence of an inclusion compound. The method of claim 4, wherein
Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide as an essential component. The method of claim 4, wherein
Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles have an average particle diameter of 1 to 500 nm. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device of claim 4 as an electrode. The method of claim 8,
Wherein the dye-sensitized solar cell, coating a titanium oxide paste on a conductive transparent substrate, baking the paste-coated substrate to form a titanium oxide thin film, the dye represented by the formula (1) is dissolved in a substrate formed with a titanium oxide thin film Impregnating the mixed solution to form a titanium oxide film electrode on which dye is adsorbed, providing a second glass substrate having a counter electrode formed thereon, a hole penetrating the second glass substrate and the counter electrode. Forming a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode to which the dye is adsorbed, and performing a heat compression process to bond the counter electrode and the titanium oxide film electrode to each other; Injecting an electrolyte into the thermoplastic polymer film between the pole and the titanium oxide film electrode, and the thermoplastic polymer The dye-sensitized solar cell, characterized in that is produced through the step of sealing.