KR20150132806A - Novel Porphyrin Derivatives, Organic Dye Sensitizers Containing The Same for Highly Efficient Dye-sensitized Solar Cells And Dye-sensitized Solar Cells Containing The Same - Google Patents

Abstract

The present invention relates to novel porphyrin derivatives for an organic electronic device, an organic dye for a dye-sensitized solar cell containing the same, and the dye-sensitized solar cell containing the organic dye. More specifically, as a triple bond or a single bond is introduced between various electron donors and porphyrin and, at the same time, a triple bond or a single bond is introduced between various electron acceptors and the porphyrin, the porphyrin derivatives can be used as a novel organic dye with enhanced long-term stability and energy conversion efficiency for a high efficiency dye-sensitized solar cell. In addition, the high efficiency dye-sensitized solar cell can be manufactured by using the dye containing the porphyrin derivatives of the present invention.

Description

TECHNICAL FIELD The present invention relates to novel porphyrin derivatives, organic dyes for dye-sensitized solar cells containing the same, and dye-sensitized solar cells containing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel porphyrin derivatives, Same}

The present invention relates to a novel porphyrin derivative for organic electronic devices, an organic dye for a dye-sensitized solar cell comprising the porphyrin derivative, and a dye-sensitized solar cell comprising the organic dye. More particularly, A carbon-carbon triple bond or a single bond is introduced between the electron acceptor and the porphyrin and a carbon-carbon triple bond or a single bond is introduced between the various electron acceptors and the porphyrin, and a new high efficiency An organic dye for a dye-sensitized solar cell, and a dye-sensitized solar cell having high efficiency.

Due to environmental and energy problems due to depletion of fossil fuels, environmental pollution, CO ₂ and SO ₂ generation, solar energy is attracting attention as environmentally friendly next generation alternative energy as infinite clean energy. Solar cell is a device that can directly convert sunlight into current (voltage), and research on low cost organic solar cell other than pn junction solar cell using pn junction of existing inorganic semiconductor is actively under way. The advantage of organic solar cells is that they are transparent, thin, lightweight, capable of realizing indoor applications and power windows in addition to low cost, environmentally friendly aspects. Dye-sensitized solar cells (DSSCs) using dye-sensitization have been developed by adsorbing visible light-absorbing dyes in semiconductors having a wide band gap, to be.

DSSC was first developed in 1991 by the adsorption of Ru (Ⅱ) based complexes on a TiO ₂ metal oxide having optically transparent nanoparticle size (15-20 nm) in the Gratzel group in Switzerland. A layer metal oxide, a dye photosensitizer, an electrolyte, and an electrode.

Specifically, a transparent conducting oxide electrode such as a fluorinated tin oxide (FTO) or an indium tin oxide (ITO) used as a substrate of both electrodes and an oxide semiconductor layer (not shown) such as TiO ₂ and ZnO nonoparticulated oxide semi-conductor layer, ruthenium, an electrolyte containing an electrolyte and an oxidation / redox couple, and a metal salt such as platinum acting as a counter electrode .

This solar cell using a ruthenium-based complex as a dye has received attention from academia due to its energy conversion efficiency exceeding 10%, but it has not been commercialized due to a limit of stability which is the biggest problem of a complex dye. In order to overcome these problems, new organic compounds have been studied as dyes. Among them, many studies have been made to use porphyrin compounds, which are well known as photosynthetic substances, as dyes, but their efficiencies were not as high as 1 ~ 3%. The Durrant team at the Imperial University in the UK found that porphyrin dyes are less efficient than ruthenium based complexes because the porphyrin dyes in the excited state are converted to the ground state by dipole dipole attraction between adjacent porphyrin compounds Respectively.

On the other hand, Japanese Patent Application Laid-Open No. 2002-063949 discloses a porphyrin derivative having a photoelectric conversion property, in which a phenyl group is substituted at 5th, 10th, 15th and 20th positions of porphyrin as described below. However, the following porphyrin compounds (R = a hydrogen atom or an acidic substituent) have a disadvantage in that they exhibit low energy conversion efficiency due to recombination of exciton electrons between porphyrin dyes.

Accordingly, there is a growing need for the development of porphyrin derivatives for dye-sensitized solar cells which are superior in long-term stability to conventional ruthenium-based dyes and have a photoelectric conversion rate superior to that of conventional porphyrin-based dyes.

Japanese Laid-Open Publication No. 2002-063949

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a ruthenium-based dye which is easy to synthesize and has excellent photoelectric conversion rate, The present invention provides a porphyrin derivative which overcomes difficulties in application of a device due to a lack of long-term stability and overcomes low efficiency of a solar cell using a conventional porphyrin derivative.

Still another object of the present invention is to provide a dye for a dye-sensitized solar cell and a dye-sensitized solar cell comprising the dye, which are produced using the novel porphyrin derivative according to the present invention.

In order to achieve the above object, the present invention provides a porphyrin derivative represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently (C ₁ -C 20) alkyl;

R ' and R " are each independently hydrogen or (C1-C20) alkoxy;

L ₁ and L ₂ are each independently a single bond or (C 6 -C 20) arylene, and the arylene may be further substituted with (C 1 -C 20) alkyl;

m is an integer of 0 or 1;

A is selected from the following structures;

이고;When n is 0, B is

ego;

when n is 1, B is selected from the following structures;

R ₇ is hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy.

The present invention also provides an organic dye for a dye-sensitized solar cell comprising the porphyrin derivative.

The present invention also provides a dye-sensitized solar cell comprising the organic dye for the dye-sensitized solar cell.

The solar cell using the organic dye for the high-efficiency dye-sensitized solar cell including the porphyrin derivative of the present invention shows long-term stability even in the external environment, and is a phenyl derivative substituted with an alkoxy, an arylamine derivative substituted with an alkoxy, - Intracellular electron transfer through the carbon triple bonds is strengthened, and the planarity and conjugation of the molecules are increased, so that the absorption of light in the near infrared region becomes possible. Thus, by securing a wide absorption region band from the visible ray to the near- Energy conversion efficiency can be obtained.

1 and 2 are UV absorption and emission spectra of the porphyrin compounds of Examples 1 to 3.
3 is a UV absorption spectrum of the porphyrin compound of Example 4. Fig.
4 is a graph showing the current density of a solar cell using the porphyrin compounds of Examples 1 to 3. FIG.
5 is a graph showing the current conversion efficiency (IPCE) of a solar cell using the porphyrin compounds of Examples 1 to 3. Fig.
6 is a graph showing current conversion efficiency (IPCE) of a solar cell using the porphyrin compound of Example 4. Fig.
7 is a graph showing the current density of a solar cell using the porphyrin compound of Example 4. Fig.

The technical terms and scientific terms used in the present invention can be construed as meaning ordinary meanings understood by those of ordinary skill in the art without departing from the scope of the present invention.

The present invention relates to a porphyrin derivative represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently (C ₁ -C 20) alkyl;

R ' and R " are each independently hydrogen or (C1-C20) alkoxy;

L ₁ and L ₂ are each independently a single bond or (C 6 -C 20) arylene, and the arylene may be further substituted with (C 1 -C 20) alkyl;

m is an integer of 0 or 1;

A is selected from the following structures;

이고;When n is 0, B is

ego;

when n is 1, B is selected from the following structures;

R ₇ is hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy.

The porphyrin-based derivative according to the present invention is intended to overcome the difficulties in application of a device due to lack of long-term stability which is the biggest problem of existing ruthenium-based dyes and to overcome the low efficiency of a solar cell using a conventional porphyrin derivative, The porphyrin derivative according to the present invention has two (C1-C20) alkoxy substituted phenyl groups at positions 5 and 15 of porphyrin and one or two (C1-C20) alkoxy substituents at position 10 of porphyrin And a phenyl-substituted arylamino group is introduced. In some cases, a carbon-carbon triple bond may be formed between the arylamino group and porphyrin.

The solar cell using the novel porphyrin derivative according to the present invention exhibits long-term stability even in the external environment and can be produced by a phenyl derivative substituted with an alkoxy such as an electron donating ability, an arylamine derivative substituted with an alkoxy, It is possible to obtain a high energy conversion efficiency by securing a wide absorption region band from visible light to near infrared light zone by strengthening electron transmission and increasing absorption of near infrared region by increasing planarity and conjugation of molecule .

In one embodiment of the present invention, the porphyrin derivative includes a porphyrin derivative represented by the following general formula (2), (3), (4) or (5)

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , L ₁ , L ₂ , R ₅ , R ₆ , R ', R "and A are the same as defined in Formula 1,

B is selected from the following structures;

R ₇ is hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy.

In one embodiment of the present invention, L ₁ and L ₂ are each independently a single bond or is selected from the following structures:

Wherein R is (C1-C20) alkyl.

In one embodiment of the present invention, the porphyrin-based derivative can be specifically exemplified by the following structure:

The porphyrin derivatives of the present invention can be prepared, for example, by the following Reaction Schemes 1 and 2. Further details are described in Examples 1 to 4 below. However, the production method is not limited to the following Reaction Schemes 1 and 2, but can be synthesized by various methods using known organic reactions.

[Reaction Scheme 1]

[Reaction Scheme 2]

The porphyrin derivative represented by Formula 1 may be useful as a dye for a dye-sensitized solar cell. Accordingly, the present invention provides a dye for a dye-sensitized solar cell comprising the porphyrin derivative of Formula 1.

The present invention also provides a dye-sensitized solar cell comprising the dye for the dye-sensitized solar cell.

In the present invention, the dye-sensitized solar cell may have the following configuration, but not limited thereto:

A first electrode comprising a conductive transparent substrate;

A light absorbing layer formed on one surface of the first electrode;

A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And

Wherein the electrolyte is located in a space between the first electrode and the second electrode.

The materials constituting the solar cell will be described as follows.

The first electrode including the conductive transparent substrate is formed of a transparent electrode formed of at least one material selected from the group consisting of indium tin oxide, fluorine tin oxide, ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ and tin oxide Or a plastic substrate.

The light absorbing layer necessarily contains an organic dye for a dye-sensitized solar cell comprising a porphyrin derivative represented by the general formula (1), and may further comprise semiconductor fine particles, a dye, a compound having hole conduction properties, and the like. The semiconductor fine particles may be formed of a nanoparticle oxide such as titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ), zinc oxide (ZnO) or the like, though not limited thereto. The dye adsorbed on the semiconductor fine particles may be used without limitation as long as it absorbs light in the visible light region, forms a strong chemical bond with the surface of the nano-oxide, and has heat and optical stability. As a representative example, a ruthenium-based organometallic compound can be mentioned. The light absorbing layer may further include a co-adsorbent. The co-adsorbent absorbs light to fill holes formed in dyes that receive electrons, and the holes again become holes, and the holes are filled with the electrolyte again.

The second electrode may be the same as the first electrode, or a conductive layer formed of platinum or the like on the light-transmitting electrode of the first electrode may be used.

Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are provided to explain the present invention more clearly and not to limit the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.

[Preparation Example 1] Preparation of Compound 6

compound 4 Manufacturing

Compound 2 (2.0 g, 5.52 mmol) , the die (1 H - pyrrole-2-yl) methane (di (1 H -pyrrol-2 -yl) methane, compound 1) (0.4 g, 2.76 mmol ) and 4- ( die (1 H - pyrrole-2-yl) methyl) benzonitrile (4- (di (1 H -pyrrol -2-yl) methyl) benzonitrile, compound 3) (0.68 g, 2.76 mmol ) with chloroform (980 mL). Then, BF ₃ OEt ₂ (200 μL, 1.66 mmol) was added rapidly through the syringe and stirred at 24 ° C for 2 hours. Then, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) (1.88 g, 8.28 mmol) was added and stirred for another 12 hours. The solvent was evaporated and the crude product was eluted through a silica gel pad with chloroform. The reaction mixture was purified by flash column chromatography (eluent n -C ₆ H ₁₄ / CH ₃ Cl (volume ratio = 1: 3)) and then recrystallized (ethanol / water = 20/1 by volume) to give a dark brown red solid 4 (0.6 g, 11%).

¹ H-NMR (300 MHz; CDCl ₃ ; TMS)? 10.248 (1 H, s, meso-Ar-H), 9.355 (2H, d, J = 4.8 Hz, Ar- d, J = 4.5 Hz, Ar -H), 8.931 (2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H (d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 -H), 3.918 (8 H, m, -OCH 2), 0.440-0.951 (60 H), -2.76 (2 H, s). FT-IR (KBr) [cm- ¹ ] 2230 (-CN).

compound 5 Manufacturing

Compound 4 (500 mg, 0.46 mmol) was dissolved in CHCl ₃ (150 mL) and NBS (N-bromosuccinimide) (100 mg, 0.56 mmol) was added and the reaction mixture was refluxed for 12 hours, Lt; / RTI > The organic layer was washed several times with brine and dried over anhydrous sodium sulfate. The solvent was evaporated in vacuo and the crude product was purified by column chromatography (eluent: chloroform) to give compound 5 (491 mg, 91%) as a dark purple solid.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2 H, d, J = 4.8 Hz, Ar-H), 8.249 (4 H, m, Ar-H), 7.782 (6 H, m, Ar-H), 3.918 (8 H, m, -OCH 2 ), 0.440-0.951 (60 H), -2.76 (2 H, s). FT-IR (KBr) [cm- ¹ ] 2230 (-CN).

compound 6 Manufacturing

Compound 5 (500 mg, 0.11 mmol) was dissolved in THF (100 mL) and zinc acetate dihydrate (350 mg, 0.54 mmol) was added and refluxed for 12 hours. The solvent was evaporated and the crude product was extracted with CH ₂ Cl ₂ . The organic layer was washed several times with brine, dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated in vacuo to give compound 6 (360 mg, 94%) as a violet solid.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2 H, d, J = 4.8 Hz, Ar-H), 8.249 (4 H, m, Ar-H), 7.782 (6 H, m, Ar-H), 3.918 (8 H, m, -OCH 2 ), 0.440-0.951 (60 H, m -CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN).

[Preparation Example 2] Preparation of Compound 7

(2.5 g, 4.55 mmol) and 2, 4'-bis (hexyloxy) -4'-iodobiphenyl (2.32 g, , 4.78 mmol), Pd (OAc ) 2 (0.05 g, 0.23 mmol), dppf (1,1'-Bis (diphenylphosphino) ferrocene) (0.25 g, 0.45 mmol) and ^{tert -BuO - Na + (1.31 g} , 13.65 mmol) were dissolved in anhydrous toluene (50 mL). The reaction mixture was refluxed overnight. After the reaction, the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed several times with brine. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated in vacuo and purified by silica gel column chromatography (eluent CH ₂ Cl ₂ : n- hexane = 3: 1) to give compound 7 (3.5 g, 81%).

^{1 H-NMR (300 MHz;} (CDCl 3; TMS) δ 7.415-7.452 (4 H, d, J = 8.4 Hz, Ar-H), 7.153-7.231 (6 H, d, J = 8.7 Hz, Ar- H), 6.545-6.612 (4H d, J = 8.7 Hz, Ar-H), 5.546 (H, Br-S, NH), 3.969-4.032 (8 H, t, -OCH 2), 0.857-2.057 (44 _{H, m, -CH 2, -CH} 3). FT-IR (KBr) [cm -1] 3400 (-NH).

[Example 1] Preparation of Compound 12

compound 10 Manufacturing

Compound 6 (Preparation 1, 500 mg, 0.71mmol), compound 7 (Preparation 2, 0.95 g, 2.83 mmol) , 60% NaH (578 mg, 14.17 mmol), Pd (OAc) 2 (64 mg, 0.28 mmol ) And DPEphos (Bis [(2-diphenylphosphino) phenyl] ether (305 mg, 0.57 mmol) were dissolved in anhydrous THF (50 mL) and refluxed for 24 hours. The solvent was evaporated and extracted several times with CH ₂ Cl ₂ and brine. The organic layer was dried over anhydrous sodium sulfate, filtered and the filtrate was evaporated under vacuum. And then purified by flash column chromatography using chloroform as eluent to give compound 10 (170 mg, 25%) as a dark green oil.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 = 8.4 Hz, Ar-H), 7.153-7.231 (6 H, d, J = 8.7 Hz, Ar-H), 6.545-6.612 (4H d, J = 8.7 Hz, Ar-H), 3.850-3.972 _{H, m, -OCH 2),} 0.440-0.951 (104 H, m, CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN).

compound 11 Manufacturing

Compound 10 (130 mg, 0.14 mmol) was added to anhydrous CH ₂ Cl ₂ (25 mL) and then a solution of DIBAL-H (Diisobutylaluminium hydride, 1 M in hexanes, 0.27 mL, 0.27 mmol) was added dropwise at 0 ° C. under a nitrogen atmosphere - < / RTI > drop-wise. The reaction mixture was stirred at room temperature for 4 hours, then quenched with aqueous NH ₄ Cl (200 mL) and further stirred for 2 hours. After the aqueous layer was removed, the organic layer was washed with brine and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography (eluent CHCl ₃ ) gave compound 11 (100 mg, 77%) as a dark green oil.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 10.325 (1H, s, -CHO), 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 (2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J (2H, m, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H) J = 8.7 Hz, Ar-H), 6.545-6.612 (4H, d, J = 8.7 Hz, Ar-H), 7.153-7.231 Ar-H), 3.850-3.972 (16 H, m, -OCH 2), 0.440-0.951 (104 H, m, CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 1750 (-CO). MS (MALDI-TOF): m / z found: 1862.93 (M ⁺ ), calc .: 1860.93.

compound 12 Manufacturing

Compound 11 (100 mg, 0.10 mmol), several drops of piperidine and cyanoacetic acid (36 mg, 0.36 mmol) were dissolved in CHCl ₃ (50 mL) and refluxed for 1 day. The reaction mixture was cooled to room temperature and extracted with CH ₂ Cl ₂ . The organic layer was washed several times with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give compound 12 (80 mg, 75%) as a dark green oil.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 10.325 (1H, s, -CHO), 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 (2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J (2H, m, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H) J = 8.7 Hz, Ar-H), 6.545-6.612 (4H, d, J = 8.7 Hz, Ar-H), 7.153-7.231 Ar-H), 3.850-3.972 (16 H, m, -OCH 2), 0.440-0.951 (104 H, m, CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN). MS (MALDI-TOF): m / z found: 1929.97 (M ⁺ ), calc .: 1928.01.

[Example 2] Preparation of Compound 15

Compound 8 was prepared as described in J. Mater. Chem. A, 2013, 1, 9848.

compound 13 Manufacturing

Compound 13 was obtained in the same manner as in the preparation of Compound 10 of Example 1.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 ), 7.43 (2 H, d , J = 8.1HzAr-H), 7.31 (2 H, d, J = 8.4 Hz, Ar-H), 7.17 (2 H, d, J = 8.1 Hz, Ar-H) , 6.63 (4 H, m, Ar-H), 3.918 (16 H, m, -OCH 2), 0.440-0.951 (104 H, m-CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN).

compound 14 Manufacturing

Compound 14 was obtained in the same manner as in the preparation of Compound 11 of Example 1.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 ), 7.43 (2 H, d , J = 8.1 Hz, Ar-H), 7.31 (2 H, d, J = 8.4 Hz, Ar-H), 7.17 (2H, d, J = 8.1 Hz, Ar-H ), 6.63 (4 H, m , Ar-H), 3.918 (16 H, m, -OCH 2), 0.440-0.951 (104 H, m-CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 1750 (-CO). MS (MALDI-TOF): m / z found: 2095.25 (M ⁺ ), calc .: 2093.22.

compound 15 Manufacturing

Compound 15 was obtained in the same manner as in the preparation of Compound 12 of Example 1.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 ), 7.43 (2 H, d , J = 8.1 Hz, Ar-H), 7.31 (2 H, d, J = 8.4 Hz, Ar-H), 7.17 (2 H, d, J = 8.1 Hz, Ar- H), 6.63 (4 H, m, Ar-H), 3.918 (16 H, m, -OCH 2), 0.440-0.951 (104 H, m-CH 2, -CH 3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN). MS (MALDI-TOF): m / z found: 2162.29.25 (M ⁺ ), calc .: 2160.23.

[Example 3] Preparation of Compound 18

compound 16 Manufacturing

Compound 16 was obtained in the same manner as in the preparation of Compound 10 of Example 1.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 = 9 Hz, Ar-H) , 6.822-6.792 (4 H, d, J = 9 Hz, Ar-H), 3.918 (12 H, m, -OCH 2), 0.440-0.951 (82 H, m-CH _2, -CH _3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN). MS (MALDI-TOF): m / z found: 1494.40 (M ⁺ ), calc .: 1693.85.

compound 17 Manufacturing

Compound 17 was obtained in the same manner as in the preparation of Compound 11 of Example 1.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 = 9 Hz, Ar-H) , 6.822-6.792 (4 H, d, J = 9 Hz, Ar-H), 3.918 (12 H, m, -OCH 2), 0.440-0.951 (82 H, m-CH _2, -CH _3). FT-IR (KBr) [cm- ¹ ] 1750 (-CO). MS (MALDI-TOF): m / z found: 1510.42 (M ⁺ ), calc .: 1508.82.

compound 18 Manufacturing

Compound 18 was obtained in the same manner as in the preparation of Compound 12 of Example 1.

^{1 H-NMR (300 MHz;} CDCl 3; TMS) δ 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 ( 2 H, d, J = 4.8 Hz, Ar-H), 8.821 (2 H, d, J = 4.8 Hz, Ar-H), 8.442 (2 H, d, J = 4.8 Hz, Ar-H), 8.307 (2H, d, J = 4.8 Hz, Ar-H), 8.249 (4H, m, Ar-H), 7.782 = 9 Hz, Ar-H) , 6.822-6.792 (4 H, d, J = 9 Hz, Ar-H), 3.918 (12 H, m, -OCH 2), 0.440-0.951 (82 H, m-CH _2, -CH _3). FT-IR (KBr) [cm- ¹ ] 2230 (-CN). MS (MALDI-TOF): m / z found: 1577.46 (M ⁺ ), calc .: 1575.85.

[Example 4] Preparation of Compound 23

Compound 19 and compound 21 were prepared according to the references NATURE CHEMISTRY, 2014, 6, 242.

compound 20 Manufacturing

(0.18 g, 0.34 mmol), Compound 19 (0.5 g, 0.71 mmol) and Compound 8 (1.8 g, 2.48 mmol) in 60% NaH (0.43 g, 10.62 mmol), Pd (OAc) ₂ (0.03 g, 27 mmol), DPEphos ) In a 250 mL Schlenk flask equipped with a condenser and dried under vacuum. When drying was completed, anhydrous THF (50 mL) was added under nitrogen reflux, and the mixture was refluxed and stirred at 80 DEG C for 24 hours. When the reaction was completed, the temperature was lowered to room temperature, extracted with CH ₂ Cl ₂ , and washed several times with distilled water. The organic layer was dried over anhydrous MgSO ₄ , the solvent was removed under reduced pressure, and the product was separated by column chromatography (eluent CHCl ₃ ) to obtain 20 (20%).

^{1 H NMR (300 MHz, CDCl} 3): δ 9.59 (d, J = 4.4 Hz, 2H), 9.11 (d, J = 4.4Hz, 2H), 8.80 (d, J = 4.8Hz), 2H), 8.65 (m, 6H), 6.96 (d, J = 8.4 Hz, 2H), 7.20 (d, J = J = 6.6 Hz, 4H), 6.44 (d, J = 2.2 Hz, 1H), 6.42 (d, J = 2.2 Hz, 1H), 3.91 4H), 3.82 (t, J = 6.6Hz, 4H), 3.82 (t, J = 6.6Hz, 8H), 1.80-1.65 (m, 8H), 4.48-1.33 (m, 8H), 1.32-1.20 (m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 (m, 16H), 0.60-0.38

compound 22 Manufacturing

Compound 20 (222 mg, 0.1475 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1 M in THF, 0.35 mL, 0.320 mmol) were added to a round flask containing THF (20 mL) and stirred for 30 minutes. After stirring, the mixture was extracted with distilled water and CH ₂ Cl ₂ , and the organic layer was dried with sodium sulfate. AsPH on evaporating the organic solvent of the dried organic layer resulting solid _{3 (80mg, 0.280mmol), Pd} 2 (dba) 3 (25mg, 0.030mmol), compound 21 (100mg, 0.280mmol), THF (20mL) and Et ₃ N (3 mL) was added and the mixture was refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give compound 22 (200 mg, 70%).

^{1 H NMR (300 MHz, CDCl} 3): δ 9.80 (d, J = 4.4 Hz, 2H), 9.24 (d, J = 4.4Hz, 2H), 8.80 (d, J = 4.8Hz), 2H), 8.65 (d, J = 8.8 Hz, 2H), 8.46 (t, J = 8.4 Hz, 2H), 8.46 (d, J = 6.6 Hz, 4H), 6.44 (d, J = 2.2 Hz, J = 6.6 Hz, 4H), 3.82 (t, J = 6.6 Hz, 8H), 1.80-1.65 (m, 8H) 16H), 0.60-0.38 (m, 16H), 0.55 (t, J = 7.3 Hz, 12H)

compound 23 ≪ / RTI &

Compound 22 (150 mg, 0.090 mmol), sodium hydroxide (20% w / w in water, 8 mL) and THF / MeOH (21 mL: 3 mL (7: 3)) were placed in a round flask, When the compound 22 disappeared with TLC, the reaction was terminated and neutralized to pH 7 with 1M HCl. It was then extracted with CH ₂ Cl ₂ and distilled water, the organic layer was dried over sodium sulfate and filtered. The filtrate was evaporated in vacuo and the resulting solid was purified by silica column chromatography (eluent dichloromethane: methanol (10: 1)) to afford 23 .

^{1 H NMR (300 MHz, CDCl} 3): δ 9.80 (d, J = 4.4 Hz, 2H), 9.24 (d, J = 4.4Hz, 2H), 8.80 (d, J = 4.8Hz), 2H), 8.65 (d, J = 8.8 Hz, 2H), 8.46 (t, J = 8.4 Hz, 2H), 8.46 (d, J = 6.6 Hz, 4H), 6.44 (d, J = 2.2 Hz, J = 6.6 Hz, 4H), 3.82 (t, J = 6.6 Hz, 8H), 1.80-1.65 (m, 8H) 16H), 0.60-0.38 (m, 16H), 0.55 (t, J = 7.3 Hz, 12H)

[Example 5] Preparation of Compound 29

Compound 27 was prepared according to the reference NATURE CHEMISTRY, 2014, 6, 242, and Compound 24 was prepared according to New J. Chem, 2015, 39, 3736-3746.

compound 25 Manufacturing

Compound 19 (146 mg, 0.13 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1 M in THF, 0.34 mL, 0.340 mmol) were added to a round flask containing THF (20 mL) and stirred for 30 min. After stirring, the mixture was extracted with distilled water and CH ₂ Cl ₂ , and the organic layer was dried with sodium sulfate. The evaporation of the organic solvent of the dried organic layer resulting solid _{AsPH 3 (78mg, 0.260mmol),} Pd 2 (dba) 3 (23mg, 0.030mmol), compound 24 (146mg, 0.260mmol), THF (40mL) and Et ₃ N (3 mL) was added and the mixture was refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give compound 25 (150 mg, 74%).

^{1 H NMR (300 MHz, CDCl} 3): δ 9.679 (d, J = 4.5 Hz, 2H), 9.592 (d, J = 4.5Hz, 2H), 8.867 (d, J = 4.5Hz, 2H), 8.847 ( J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.688 (d, J = 6.6 Hz, 4H), 3.992 (t, J = 6.6 Hz, 4H), 3.854 = 6.6 Hz, 4H), 1.80-1.65 (m, 8H), 4.48-1.33 (m, 8H), 1.32-1.20 (m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 ), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 26 Manufacturing

Compound 25 (67 mg, 0.04 mmol), CuI (1 mg, 0.001 mmol) and Pd (PPh ₃ ) ₂ Cl ₂ (3 mg, 0.001 mmol) are placed in a Schlenk flask. Vacuum pressure for one hour, then add 40 ml of Dry Toluene. Then, Et ₃ N (64 mg, 0.63 mmol) was added thereto, and TIPS (Triisopropylsilylacetylene) (20 ml, 0.08 mmol) was added thereto and refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give 26 (54 mg, 76%).

^{1 H NMR (300 MHz, CDCl} 3): δ 9.669 (d, J = 4.4 Hz, 2H), 9.646 (d, J = 4.4Hz, 2H), 8.854 (d, J = 4.8Hz), 2H), 8.839 (t, J = 8.6 Hz, 2H), 7.170 (d, 4H), 7.068 (d, J = 8.4 Hz, 2H), 7.70 J = 6.6 Hz, 4H), 6.996 (t, J = 6.6 Hz, 4H), 6.996 ), 1.826-1.65 (m, 8H), 4.48-1.33 (m, 8H), 1.32-1.20 (m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 (m, 16 H) 0.55 (t, J = 7.3 Hz, 12 H)

compound 28 Manufacturing

Compound 26 (60 mg, 0.04 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1 M in THF, 0.35 mL, 0.320 mmol) were placed in a round flask containing THF (20 mL) and stirred for 30 min. After stirring, the mixture was extracted with distilled water and CH ₂ Cl ₂ , and the organic layer was dried with sodium sulfate. The evaporation of the organic solvent of the dried organic layer resulting solid _{AsPH 3 (24mg, 0.080mmol),} Pd 2 (dba) 3 (7mg, 0.010mmol), compound 27 (31mg, 0.080mmol), THF (20mL) and Et ₃ N (0.68 mL) was added and the mixture was refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give compound 28 (45 mg, 64%).

^{1 H NMR (300 MHz, CDCl} 3): δ 10.013 (d, J = 4.4 Hz, 2H), 9.667 (d, J = 4.4Hz, 2H), 8.952 (d, J = 4.8Hz), 2H), 8.852 (d, J = 4.8 Hz, 2H), 8.298 (t, J = 8.4 Hz, 2H), 8.172 (d, J = 8.4 Hz, 2H), 7.957 (d, J = 8.6 Hz, 1H), 7.791-7.606 (d, J = 8.4 Hz, 2H), 7.022 (d, J = 6.6 Hz, 4H), 6.909 J = 6.6 Hz, 4H), 3.877 (t, J = 6.6 Hz, 8H), 1.811-1.65 (m, 8H), 4.48 (M, 16H), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 29 Manufacturing

Compound 28 (45 mg, 0.020 mmol), sodium hydroxide (20% w / w in water, 8 mL) and THF / MeOH (21 mL: 3 mL (7: 3)) were placed in a round flask, When the compound 28 had disappeared with TLC, the reaction was terminated and neutralized to pH 7 with 1M HCl. It was then extracted with CH ₂ Cl ₂ and distilled water, the organic layer was dried over sodium sulfate and filtered. The filtrate was evaporated in vacuo and the resulting solid was purified by silica column chromatography (eluent dichloromethane: methanol (10: 1)) to afford 29 .

^{1 H NMR (300 MHz, CDCl} 3): δ 10.002 (d, J = 4.4 Hz, 2H), 9.659 (d, J = 4.4Hz, 2H), 8.941 (d, J = 4.8Hz), 2H), 8.848 (d, J = 8.4 Hz, 2H), 8.290 (t, J = 8.4 Hz, 2H), 8.164 (d, J = 8.4 Hz, 2H), 7.014 (d, J = 6.6 Hz, 4H), 6.909 , 4H), 3.982 (t, J = 6.6 Hz, 4H), 3.861 (t, J = 6.6 Hz, 8H), 1.824-1.65 (m, 8H), 4.48-1.33 (m, 8H), 1.32-1.20 J = 7.3 Hz, 12H), 1.01-0.80 (m, 28H), 0.77-0.60 (m, 16H), 0.60-0.38

[Example 6] Preparation of Compound 34

Compound 30 was prepared according to ChemSus Chem, Volume 4, Issue 5, pages 591-594, May 23,

compound 31 Manufacturing

Compound 19 (100 mg, 0.09 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1 M in THF, 0.35 mL, 0.320 mmol) were added to a round flask containing THF (40 mL) and stirred for 30 min. After stirring, the mixture was extracted with distilled water and CH ₂ Cl ₂ , and the organic layer was dried with sodium sulfate. The evaporation of the organic solvent of the dried organic layer resulting solid _{AsPH 3 (54mg, 0.180mmol),} Pd 2 (dba) 3 (16mg, 0.20mmol), compound 30 (162mg, 0.180mmol), THF (40mL) and Et ₃ N (0.18 mL) was added and the mixture was refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give compound 31 (81 mg, 48%).

^{1 H NMR (300 MHz, CDCl} 3): δ 9.698 (d, J = 4.5 Hz, 2H), 9.599 (d, J = 4.5Hz, 2H), 8.883 (d, J = 4.5Hz, 2H), 8.854 ( J = 8.4 Hz, 2H), 7.867 (d, J = 8.4 Hz, 2H), 7.691 (t, J = 8.4 Hz, 2H), 7.553 (d, J = 8.4 Hz, 4H), 7.327-7.7245 J = 6.4 Hz, 4H), 4.022 (t, J = 6.6 Hz, 8H), 3.858 (t, J = 6.6 Hz, 16H), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H), 1.32-1.20 (m, 16H), 1.01-0.80

compound 32 Manufacturing

Compound 31 (70 mg, 0.04 mmol), CuI (1 mg, 0.001 mmol) and Pd (PPh ₃ ) ₂ Cl ₂ (3 mg, 0.001 mmol) are placed in a Schlenk flask. Vacuum pressure for one hour, then add 40 ml of Dry Toluene. Add Et ₃ N (90 ml, 0.66 mmol), add TIPS (Triisopropylsilylacetylene) (30 ml, 0.13 mmol) and reflux for 12 hours. The solvent was then evaporated and purified by column chromatography to give 32 (27 mg, 37%).

^{1 H NMR (300 MHz, CDCl} 3): δ 9.686 (d, J = 4.4 Hz, 2H), 9.648 (d, J = 4.4Hz, 2H), 8.860 (d, J = 4.8Hz, 4H), 7.872 ( (d, J = 8.4 Hz, 2H), 7.703 (t, J = 8.6 Hz, 2H), 7.533 (d, 4H), 7.327-7.245 (T, J = 6.6 Hz, 8H), 3.966 (t, J = 6.6 Hz, 8H), 1.826-1.65 (m, 8H) 16H), 0.60-0.38 (m, 16H), 0.55 (t, J = 7.3 Hz, 12H)

compound 33 Manufacturing

Compound 32 (80 mg, 0.04 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1 M in THF, 0.04 mL, 0.040 mmol) were placed in a round flask containing THF (20 mL) and stirred for 30 min. After stirring, the mixture was extracted with distilled water and CH ₂ Cl ₂ , and the organic layer was dried with sodium sulfate. The evaporation of the organic solvent of the dried organic layer resulting solid _{AsPH 3 (26mg, 0.090mmol),} Pd 2 (dba) 3 (8mg, 0.010mmol), compound 27 (33mg, 0.090mmol), THF (35mL) and Et ₃ N (0.75 mL) was added and the mixture was refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give 33 (10 mg, 40%).

^{1 H NMR (300 MHz, CDCl} 3): δ 10.021 (d, J = 4.4 Hz, 2H), 9.689 (d, J = 4.4Hz, 2H), 8.960 (d, J = 4.8Hz), 2H), 8.869 (d, J = 8.4 Hz, 2H), 8.294 (t, J = 8.4 Hz, 2H), 8.157 , 2H), 7.735 (d, J = 8.4 Hz, 4H), 7.538 (d, J = 8.4 Hz, 2H), 7.026 ), 4.426 (t, J = 6.6 Hz, 2H), 4.025 (t, J = 6.6 Hz, 8H), 3.884 (t, J = 6.6 Hz, 8H), 1.836-1.65 (m, 8H), 1.32-1.20 (m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 (m, 16H), 0.60-0.38 12H)

compound 34 Manufacturing

Compound 33 (10 mg, 0.001 mmol), sodium hydroxide (20% w / w in water, 8 mL) and THF / MeOH (21 mL: 3 mL (7: 3)) were placed in a round flask, When the compound 33 disappeared with TLC, the reaction was terminated and neutralized to PH7 with 1M HCl. It was then extracted with CH ₂ Cl ₂ and distilled water, the organic layer was dried over sodium sulfate and filtered. The filtrate was evaporated in vacuo and the resulting solid was purified by silica column chromatography (eluent dichloromethane: methanol (10: 1)) to afford 34 .

^{1 H NMR (300 MHz, CDCl} 3): δ 10.015 (d, J = 4.4 Hz, 2H), 9.686 (d, J = 4.4Hz, 2H), 8.957 (d, J = 4.8Hz, 2H), 8.866 ( (d, J = 8.4 Hz, 2H), 8.292 (d, J = 8.4 Hz, 2H), 8.186 2H), 7.735 (t, J = 8.4 Hz, 2H), 7.535 (d, J = 8.4 Hz, 4H), 7.322-7.248 J = 6.6 Hz, 8H), 3.884 (t, J = 6.6 Hz, 8H), 2.791 (t, J = 6.3 Hz, 4H), 6.577-6.563 (m, 6H), 2.375-2.325 (m, 8H), 4.48-1.33 (m, 8H), 1.32-1.20 (m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 0.38 (m, 16 H) 0.55 (t, J = 7.3 Hz, 12 H)

Evaluation of spectroscopic characteristics

The UV absorption spectra of the porphyrin-based dye compounds 12 , 15 , 18 and 23 obtained in Examples 1 to 4 are shown in FIGS. The UV emission spectra of the porphyrin-based dye compounds 12 , 15 and 18 obtained in Examples 1 to 3 are shown in Fig.

[Examples 5 to 8 and Comparative Examples 1 to 3] Preparation and characterization of dye-sensitized solar cell

A dye-sensitized solar cell using a porphyrin compound was fabricated as follows.

 A dispersion of titanium oxide particles having an average particle size of 13 nm in particle diameter was applied on a conductive film made of ITO of the first electrode to a surface area of 0.25 cm 2 by a doctor blade method and subjected to a heat treatment and firing process at 450 캜 for 30 minutes, A porous film having a thickness of 탆 was prepared.

Then, the resultant was kept at 80 ° C., and the porphyrin compound obtained in each of Examples 1 to 4 was immersed in a 0.3 mM dye dispersion in ethanol, and the dye adsorption treatment was performed for 12 hours or more.

Thereafter, the dye-adsorbed porous membrane was washed with ethanol and dried at room temperature to prepare a first electrode having a light absorbing layer.

Separately, the second electrode was formed by depositing a second conductive film made of Pt on a first conductive film made of ITO by sputtering, and using a drill having a diameter of 0.75 mm for injecting an electrolyte, a fine hole was formed.

Thereafter, the support made of a thermoplastic polymer film having a thickness of 60 μm was sandwiched between the first and second electrodes having the porous film formed thereon at 80 ° C. for 16 seconds to bond the two electrodes. Then, the electrolyte was injected through the micropores formed in the second electrode, and the micropores were sealed using a cover glass and a thermoplastic polymer film to prepare a dye-sensitized solar cell. The electrolyte used herein was 1-methyl-3-propylimidazolium iodide, 0.1M lithium iodide, 0.05M iodine, 0.5M 4-tert-butylpyridine And then dissolved in 3-methoxypropionitrile.

The voltage-current density and the current conversion efficiency (IPCE) of the battery were measured and are shown in FIGS. 4, 5, and 6, respectively, and are shown in Table 1.

Porphyrin derivative J _sc [mA cm ^-2 ] V _oc [mV] FF (%) 侶 (%) Example 5 Compound 12
(Example 1) 13.34 723 72.3 6.97 Example 6 Compound 15
(Example 2) 13.91 707 75.2 7.40 Example 7 Compound 18
(Example 3) 14.26 722 74.7 7.69 Example 8 Compound 23
(Example 4) 17.6 913 75.0 12.1

From the results shown in Table 1, it can be seen that the dye-sensitized solar cells of Examples 5 to 8 have two (C1-C20) alkoxy substituted phenyl groups at positions 5 and 15 of porphyrin, It has been found that the use of the porphyrin derivatives of Examples 1 to 4 in which an arylamino group substituted with phenyl substituted with one or two (C1-C20) alkoxy is used as a dye has excellent light conversion efficiency. In particular, in the case of Example 8, in addition to the phenyl group substituted with two (C1-C20) alkoxy substituted at positions 5 and 15 of porphyrin, one or two (C1-C20) Compound 23 having a carbon-carbon triple bond between a phenyl-substituted arylamino group and porphyrin was used as a dye, and thus exhibited excellent photoconversion efficiency.

The battery produced by using the porphyrin compound according to the present invention is a battery which is based on a porphyrin dye having high stability against light and heat, and has an alkoxy-substituted phenyl derivative having strong electron-donating ability, an alkoxy substituted arylamine derivative, It has been found that the dye-sensitized solar cell can be driven with high efficiency.

Claims (7)

A porphyrin derivative represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently (C ₁ -C 20) alkyl;
R ' and R " are each independently hydrogen or (C1-C20) alkoxy;
L ₁ and L ₂ are each independently a single bond or (C 6 -C 20) arylene, and the arylene may be further substituted with (C 1 -C 20) alkyl;
m is an integer of 0 or 1;
A is selected from the following structures;

When n is 0, B is

ego;
when n is 1, B is selected from the following structures;

R ₇ is hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy. The method according to claim 1,
A porphyrin derivative represented by the following general formula (2), (3), (4) or (5)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , L ₁ , L ₂ , R ₅ , R ₆ , R ', R "and A are as defined in claim 1,
B is selected from the following structures;

R ₇ is hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy. 3. The method of claim 2,
Wherein L ₁ and L ₂ are each independently a single bond or a porphyrin derivative selected from the following structures:

Wherein R is (C1-C20) alkyl. 3. The method of claim 2,
A porphyrin derivative selected from the following structures:

A dye for a dye-sensitized solar cell comprising a porphyrin derivative according to any one of claims 1 to 4. A dye-sensitized solar cell comprising the dye for a dye-sensitized solar cell of claim 5. The method according to claim 6,
The dye-sensitized solar cell
A first electrode comprising a conductive transparent substrate;
A light absorbing layer formed on one surface of the first electrode;
A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And
And an electrolyte located in a space between the first electrode and the second electrode.

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