KR101271534B1 - Porphyrins conjugated polymers and method for preparing thereof - Google Patents

Abstract

The present invention relates to a porphyrin-based conjugated polymer derivative capable of increasing energy conversion efficiency by utilizing solar light up to an infrared region, and a preparation method thereof. More specifically, the present invention relates to a porphyrin-based conjugated polymer that can be used as a dye of a solar cell, and a method of manufacturing the same.
The porphyrin-based conjugated polymer according to the present invention can be used as a dye having a low band gap in a solar cell and thus can utilize the sun's light to the infrared region, thereby increasing the energy conversion efficiency of the solar cell.

Description

Porphyrin-based conjugated polymers for solar cells and preparation method thereof

The present invention relates to a porphyrin-based conjugated polymer capable of increasing energy conversion efficiency by utilizing solar light up to an infrared region, and a manufacturing method thereof. More specifically, the present invention relates to a porphyrin-based conjugated polymer that can be used as a dye of a solar cell, and a method of manufacturing the same.

Nature's photosynthesis system is a very sophisticated nanometer-sized biological plant. Photosynthesis systems produce chemical energy from the sun that is indispensable to all living things on Earth. The core of this biofactory can be explained by the stepwise movement of energy and electrons generated from light between the antenna complex (condensing and energy transfer) and the reaction center (electron transfer).

Quantum yields obtained from such multi-step energy / electron transfer in natural biofactories are close to 100. Attempts to artificially synthesize photosynthetic systems having such high efficiency have recently been gaining attention in terms of science and technology.

Photocatalysts and solar cells that mimic photosynthesis are considered as solutions to solve environmental and energy problems, and many researchers are conducting research to manufacture and characterize photomolecular devices using artificial photosynthesis.

For the efficient conversion of solar energy in molecular devices using artificial photosynthesis, molecules containing electron donor-electron acceptors similar to the natural world must be synthesized.

Porphyrin is a type of compound that constitutes a pigment component that plays an important role in redox reactions in vivo and is a macrocyclic compound including four pyrrole rings. The porphyrin absorbs long wavelengths of light, and is therefore used for photodynamic therapy using laser. In particular, with recent remarkable developments in the field of organic electronics, research into applied organic devices such as organic transistors and organic solar cells as semiconductor materials has been actively conducted. have.

Dye-response solar cells are high efficiency photoelectrochemical solar cells using the photosynthesis principle and were first developed by the Swiss Grachel Group in 1991. This solar cell using ruthenium-based complexes as dyes has attracted the attention of academics by exhibiting energy conversion efficiencies of more than 10%, but has not yet been commercialized due to the limitation of stability, the biggest problem of complex-based dyes.

In order to overcome this problem, new organic compounds have been studied as dyes, and many studies using porphyrin compounds known as photosynthetic materials as dyes have been made, but the efficiency was not as high as 1 to 3%. Durrant and his colleagues at Imperial University in the UK say that porphyrin dyes are less efficient than ruthenium complexes because the dipole dipole attraction between adjacent porphyrin compounds converts the excited porphyrin dyes to the ground state. Reported.

Japanese Patent Laid-Open Publication No. 2002-63949 discloses porphyrin-based conjugated polymers having a phenyl group substituted at positions 5, 10, 15, and 20 of porphyrin as porphyrin-based conjugated polymers having photoelectric conversion characteristics. .

However, the following porphyrin compounds have a disadvantage of showing low energy conversion efficiency due to recombination of exciton electrons between porphyrin dyes.

In addition, in order to increase the energy conversion efficiency in the solar cell, the light energy coming from the sun must be converted into electrical energy. Since dyes play a role in receiving and converting light energy, it is urgent to develop dyes that receive all the sun's light. In other words, when the dyes with high energy conversion efficiency are present, the absorption region is limited to the visible light region. In order to improve this problem, if a dye using porphyrin-based conjugated polymer having an absorption wavelength that other organic materials do not have, a high efficiency solar cell may be developed.

The present invention has led to the development of a porphyrin-based conjugated polymer and a method for producing the same, which can increase energy conversion efficiency by utilizing solar light in the infrared region.

It is an object of the present invention to provide a porphyrin-based conjugated polymer and its preparation method for use as a dye of a solar cell.

It is also an object of the present invention to provide a solar cell device comprising the porphyrin-based conjugated polymer.

[화학식 2]


[화학식 3]

[화학식 4]

[화학식 5]

The present invention provides a porphyrin-based conjugated polymer represented by the following Chemical Formulas 1 to 5.
[Formula 1]

(2)


(3)

[Chemical Formula 4]

[Chemical Formula 5]

이다.In Chemical Formulas 1 to 5, n is an integer of 5 to 50,

to be.

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The method of preparing the porphyrin-based conjugated polymer (Formula 1) is preferably the following Scheme 1.
[Reaction Scheme 1]

In Scheme 1, A) is MgBr _2; B) is BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl _2, 3-trimethylsilylpropynal ); C) is Tetra-n-butylammonium fluoride (TBAF), CaCl ₂ 2H ₂ O, Tetrahydrofuran (THF); D) is CuCl, TMEDA (Tetramethylethylenediamine), CH ₂ Cl ₂ .

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상기 반응식 2에서 a)는 1-bromohexadecane, K₂CO₃, KI, DMF(Dimethylformamide); b)는 LiAlH₄, THF(Tetrahydrofuran); c)는 PCC(pyridiniumchlorochromate), CH₂Cl₂; d)는 pyrrole, CH₂Cl₂; f)는 3-trimethylpropynal, BF₃OEt₂(Boron trifluoride diethyl ether), DDQ(2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH₂Cl₂이다.

[반응식 3]

In the method for preparing the porphyrin-based conjugated polymer (Formula 2), the following Schemes 2 and 3 are preferably performed sequentially.
[Reaction Scheme 2]

A) in Scheme 2 is 1-bromohexadecane, K ₂ CO ₃ , KI, DMF (Dimethylformamide); b) is LiAlH ₄ , THF (Tetrahydrofuran); c) is pyridinium chlorochromate (PCC), CH ₂ Cl ₂ ; d) is pyrrole, CH ₂ Cl ₂ ; f) is 3-trimethylpropynal, BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl ₂ .

[Reaction Scheme 3]

A) in Scheme 3 is Zn (OAc) ₂ , CHCl ₃ / MeOH; b) is Tetra-n-butylammonium fluoride (TBAF), CH ₂ Cl ₂ ; c) is CuCl, Tetramethylethylenediamine (TMEDA), CH ₂ Cl ₂ / pyridine.

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The method of preparing the porphyrin-based conjugated polymer (Formula 3) is preferably the following Scheme 4.
[Reaction Scheme 4]

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The preparation method of the porphyrin-based conjugated polymer (Formula 4) is preferably the following Scheme 5.
Scheme 5

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The method of preparing the porphyrin-based conjugated polymer (Formula 5) is preferably the following Scheme 6.
[Reaction Scheme 6]

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The present invention also provides a solar cell device comprising a porphyrin-based conjugated polymer represented by Formula 1 to Formula 5.

The solar cell may include an organic solar cell or a dye-sensitized solar cell.

The porphyrin-based conjugated polymer according to the present invention can be used as a dye having a low band gap in a solar cell and thus can utilize the sun's light to the infrared region, thereby increasing the energy conversion efficiency of the solar cell.

1 shows the structure and UV-vis absorption spectrum of Porphyrin.
Figure 2 relates to 5,15-Bis- (2,4,6-trimethylphenyl) -10,20-bis-[(trimethylsilyl)] ethynyl porphyrin ¹ H NMR spectra.
3 is 5,15-Bis- (2,4,6-trimethylphenyl) -10,20-bis (ethynyl) porphyrin
Relates to a ¹ H NMR spectrum.
Figure 4 relates to the UV-vis spectrum ((a) Monomer (solvent: THF) -5,15-Bis- (2,4,6-trimethylphenyl) -10,20-bis-[(trimethylsilyl)] ethynyl porphyrin (b) Polymer (solvent: THF) -5,15-Bis- (2,4,6-trimethylphenyl) -10,20-bis (ethynyl) porphyrin).
5 is Methyl 3,4,5-Tris (hexadecyloxy) benzoate ¹ H NMR spectrum.
Figure 6 is a 3,4,5-Tris (hexadecyloxy) benzyl alcohol ¹ H NMR spectrum.
7 is a 3,4,5-Tris (hexadecyloxy) benzaldehyde ¹ H NMR spectrum.
FIG. 8 is a 2,2 ′-{[3,4,5-Tris (hexadecyloxy) phenyl] methylene} bis ( 1H- pyrrole) ¹ H NMR spectrum.
9 is a ¹ H NMR speactrum of long chain porphyrin monomers.
10 is a ¹ H NMR speactrum of long chain porphyrin polymers.
11 is a UV-vis spectrum (solvent: CH ₂ Cl ₂ ): (a) Monomer (b) Polymer.
12 is a Fluorescence spectra (solvent: CH ₂ Cl _{2 ,} λ _exc = 426 nm) ((a) porphyrin monomer (b) porphyrin polymer).
Figure 13 shows the spectroscopic characteristics of Copolymer 1 ((a) UV-vis spectrum of Anthracene (solvent: CH ₂ Cl ₂ ) (b) UV-vis spectrum of Copolymer 1 (solvent: CH ₂ Cl ₂ ) (c) Fluorescence spectrum (solvent: CH ₂ Cl _{2 ,} λ _exc = 426 nm).
14 shows the spectroscopic characteristics of Copolymer 2 ((a) UV-vis spectrum of Phenothiazinebenzothiadiazol (solvent: CH ₂ Cl ₂ ) (b) UV-vis spectrum of Copolymer 2 (solvent: CH ₂ Cl ₂ ) (c) Fluorescence spectrum (solvent: CH ₂ Cl _{2 ,} λ _exc = 426 nm).
15 shows the spectroscopic characteristics of Copolymer 3 ((a) UV-vis spectrum of Phenothiazine (solvent: CH ₂ Cl ₂ ) (b) UV-vis spectrum of Copolymer 3 (solvent: CH ₂ Cl ₂ ) (c) Fluorescence spectrum (solvent: CH ₂ Cl _{2 ,} λ _exc = 426 nm).
16 shows Copolymer 1 ¹ H NMR spectrum.
17 shows Copolymer 2 ¹ H NMR spectrum.
18 shows Copolymer 3 ¹ H NMR spectrum.
19 is a TGA graph (20 ° C./min) ((a) Zn-polymer (b) Copolymer 1).
20 is Cyclic voltammograms ((a) Zn-polymer (b) Copolymer 1).
21 is a photocurrent action spectra ((a) Zn-polymer (b) Copolymer).
22 is JV curve (Copolymer 1 + PC ₇₀ BM (1: 5), AM 1.5, 100 mW / cm ² ).
23 is a porphyrin-based conjugated polymer according to one embodiment of the present invention.

The present invention provides a porphyrin-based conjugated polymer for use as a dye of a solar cell. In order to improve energy conversion efficiency in solar cells, light energy coming from the sun must be converted into electric energy. In other words, the dyes with high energy conversion efficiency currently provide a dye using a porphyrin-based conjugated polymer having an absorption wavelength that is limited to the visible light region but is not included in other organic materials.

Porphyrin is a generic term for macrocyclic compounds in which four pyrrole units are connected by methine groups. This macrocyclic compound is based on porphin as shown in FIG. 1. Porphyrinic macrocycles are conjugated with 11 double bonds and have a planar structure that satisfies the aromaticity of Huckel's "4n + 2". Various porphyrins compounds can be synthesized by introducing several functional groups at the meso and β-pyrrole positions of porphin.

In addition, two hydrogen ions inside porphin are lost and become divalent anions to form metalloporphyrins by binding metal ions to the empty space in the center. Porphyrin usually acts as a four-digit donor ligand, and central metal ions can bind to other ligands in the axial direction. It absorbs light in the ultraviolet-visible region and exhibits a strong absorption band called "Soret" near 400 nm and a weak absorption band called "Q" between 500 and 600 nm. In addition, due to its high conjugation, it is attracting attention as an optoelectronic material due to its excellent electrochemical properties.

[화학식 2]

[화학식 3]

[화학식 4]

[화학식 5]

More specifically, the present invention provides a porphyrin-based conjugated polymer represented by the following Chemical Formulas 1 to 5.
[Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

이다.In Chemical Formulas 1 to 5, n is an integer of 5 to 50,

to be.

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In another aspect, the present invention provides a method for preparing a porphyrin-based conjugated polymer represented by Formula 1 to Formula 5.

The method of preparing the porphyrin-based conjugated polymer (Formula 1) is preferably the following Scheme 1.
[Reaction Scheme 1]

In Scheme 1, A) is MgBr _2; B) is BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl _2, 3-trimethylsilylpropynal ); C) is Tetra-n-butylammonium fluoride (TBAF), CaCl ₂ 2H ₂ O, Tetrahydrofuran (THF); D) is CuCl, TMEDA (Tetramethylethylenediamine), CH ₂ Cl ₂ .

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상기 반응식 2에서 a)는 1-bromohexadecane, K₂CO₃, KI, DMF(Dimethylformamide); b)는 LiAlH₄, THF(Tetrahydrofuran); c)는 PCC(pyridiniumchlorochromate), CH₂Cl₂; d)는 pyrrole, CH₂Cl₂; f)는 3-trimethylpropynal, BF₃OEt₂(Boron trifluoride diethyl ether), DDQ(2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH₂Cl₂이다.

[반응식 3]

In the method for preparing the porphyrin-based conjugated polymer (Formula 2), the following Schemes 2 and 3 are preferably performed sequentially.
[Reaction Scheme 2]

A) in Scheme 2 is 1-bromohexadecane, K ₂ CO ₃ , KI, DMF (Dimethylformamide); b) is LiAlH ₄ , THF (Tetrahydrofuran); c) is pyridinium chlorochromate (PCC), CH ₂ Cl ₂ ; d) is pyrrole, CH ₂ Cl ₂ ; f) is 3-trimethylpropynal, BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl ₂ .

[Reaction Scheme 3]

A) in Scheme 3 is Zn (OAc) ₂ , CHCl ₃ / MeOH; b) is Tetra-n-butylammonium fluoride (TBAF), CH ₂ Cl ₂ ; c) is CuCl, Tetramethylethylenediamine (TMEDA), CH ₂ Cl ₂ / pyridine.

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The method of preparing the porphyrin-based conjugated polymer (Formula 3) is preferably the following Scheme 4.
[Reaction Scheme 4]

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The preparation method of the porphyrin-based conjugated polymer (Formula 4) is preferably the following Scheme 5.
Scheme 5

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The method of preparing the porphyrin-based conjugated polymer (Formula 5) is preferably the following Scheme 6.
[Reaction Scheme 6]

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In addition, the present invention also provides a solar cell device comprising a porphyrin-based conjugated polymer represented by Formula 1 to Formula 5.

The solar cell may include an organic solar cell or a dye-sensitized solar cell.

The solar cell or photovoltaic cell in this invention means the apparatus which can convert solar energy into electrical energy. When the semiconductor junction region having the PN junction surface is irradiated with energy of greater than the prohibition band, electrons and holes are generated, and the internal electric field formed in the junction region moves electrons to N-type semiconductor and holes to P-type semiconductor to generate electromotive force. do. The electrodes to which the N-type semiconductor and the P-type semiconductor are respectively attached become the negative electrode and the positive electrode, so that the direct current can be taken.

The organic solar cell of the present invention is composed of an organic material having an electron donor (D) and an electron acceptor (A) characteristic, and when absorbing light, an electron-hole pair is generated and an electron-hole pair Is moved to the DA interface to separate charges, electrons to electron acceptors, and holes to electron donors to generate current.

Dye-sensitized solar cell in the present invention, when the n-type nanoparticle semiconductor oxide electrode with dye molecules chemically adsorbed on the surface absorbs light, the dye molecules produce electron-hole pairs, and electrons are injected into the conduction band of the semiconductor oxide The electrons injected into the semiconductor oxide electrode are transferred to the transparent conductive film through the nanoparticle interface to generate a current. Holes generated in the dye molecule are electrons are reduced by the redox electrolyte and reduced again.

Hereinafter, the present invention will be described in detail through examples. The following examples are only illustrative of the present invention, and the scope of the present invention is not limited thereby.

< Example  1>

1. Experimental materials and measuring equipment

Magnesium bromide (98%), N , N , N ' , N' -tetramethylethylene diamine ( N , N , N' , N'- tetramethylethylene diamine (99%)), 2,4,6 Trimethylbenzaldehyde (2,4,6-Trimthylbenzaldehyde (98%)), tetrabutyl-ammonium fluoride, copper chloride (99.995%), 9,10-dibromo- Anthracene (9,10-Dibromo-anthracene (98%)) was purchased from Aldrich, pyridium chlorochromate (98%), pyrrole (98%), LiAlH ₄ (97%), 3-trimethylsilylpropynal (97% ) And 1-bromohexadecane (97%) were purchased from Alfa Aesar. Dry DMF, THF and chloroform were obtained by distillation with CaH ₂ . Dry pyrrole was also obtained by vacuum distillation with calcium hydride (CaH ₂ ).

UV-vis absorption spectra were obtained using a UV-VIS-NIR spectrophotometer UV-3600 manufactured by SHIMADZU. ¹ H NMR spectra were obtained using an AVANCE III 400 Micro Bay spectrometer from Bruker. Fluorescence spectra were obtained using an RF-5301PC spectrofluorophotometer from SHIMADZU. Molecular weight of the polymer was measured by Alliance e2695 of Waters, and TGA analysis was performed by Auto-TGA Q500 of TA Instruments.

2. Free base - Porphyrin Polymer synthesis

5- Mesityldipyrromethane (1) Synthesis of

A mixture of mesitaldehyde (3.71 g, 2.5 mmol) and pyrrole (173.5 mL, 25.0 mmol) in a 500-mL single-neck round-bottomed flask was vacuumed with argon for 10 minutes.

MgBr ₂ (2.3 g, 12.5 mmol) was added and the mixture was stirred at ambient temperature for 1.5 hours. The tan mixture was treated with powdered NaOH (5 g, 0.125 mol). The mixture was stirred for 1 hour and then filtered. The filtrate was concentrated to recover pyrrole. The crude solid obtained by removing pyrrole was extracted with 20% ethyl acetate / hexanes (7 × 100 mL). The extract was gravity filtered through a pad of silica (80 g). The eluted solution was concentrated to yield a yellow solid. Crystals [ethanol / water (4: 1)] were obtained as pale yellow crystals (3.79 g, 57%).

¹ H NMR (CDCl ₃ , 400 MHz) d 7.90 (br s, 2H, NH), 6.8 (s, 2H, m -Ph), 6.68 (br dd, 2H, pyrrole H), 6.14 (dd, 2H, pyrrole H), 5.98 (dd, 2H, pyrrole H), 5.90 (s, 1H, benzyl H), 2.26 (s, 3H, p -ph), 2.0 (s, 6H, o -ph)

5,15- Bis (2,4,6- trimethylphenyl ) -10,20-Bis [( trimethylsilyl )] ethynyl porphyrin Synthesis of (2)

Under argon, a solution of CHCl ₃ (200 mL) in which BF ₃ OEt ₂ (25 μl, 0.2 mmol) was dissolved in 5-Mesityldipyrromethane (1) (529 mg, 2.0 mmol)) and 3-trimethylsilylpropynal (275 μl, 2.0 mmol) Was added and the solution was stirred at room temperature for 1 minute. In addition, DDQ (340 mg, 0.15 mmol) was added and stirring was continued for 5 more minutes. The solution was filtered through a short plug of silica and the solvent was removed to yield a purple crystalline solid (168 mg, 11%) under reduced pressure.

_{^{1 H NMR (CDCl 3, 400}} MHz) d 9.51 ~ 9.50 (d, 4H, b -pyrrolic H), 8.63 ~ 8.62 (d, 4H, b -pyrrolic H), 7.26 (s, 4H, m -Ph), 2.61 (s, 6H, p -ph), 1.81 (s, 12H, o -ph), -2.16 (s, 2H, NH).

5,15- Bis (2,4,6- trimethylphenyl ) -10,20- Bis ( ethylnyl ) porphyrin Synthesis of (3)

TBAF (tetrabutyl-ammonium fluoride, 0.136 mL, 0.47 mmol) was added dropwise with THF solution (100 mg, 0.135 mmol) for 30 minutes. Then CaCl ₂ · 2H ₂ O was added and stirring was continued for 30 minutes more. After the solvent was removed, the product was CH ₂ Cl ₂ And Extracted with H ₂ O. An organic layer was obtained and dried over anhydrous Na ₂ SO ₄ . The filtrate was evaporated to yield a purple solid (68 mg, 84%) (5) .

_{^{1 H NMR (CDCl 3, 400}} MHz) d 9.56 ~ 9.55 (d, 4H, b -pyrrolic H), 8.66 ~ 8.67 (d, 4H, b -pyrrolic H), 7.26 (s, 4H, m -Ph), 4.14 (s, 2H, ethynyl), 2.61 (s, 6H, p -ph), 1.81 (s, 12H, o -ph), -2.16 (s, 2H, NH).

Porphyrins Polymer Synthesis of 4

CuCl (27 mg, 0.28 mmol) and TMEDA ( N , N , N ' , N'- tetramethylethylenediamine, 0.042 ml, 0.28 mmol) (3) CH ₂ Cl ₂ dissolved in (20 mg, 0.034 mmol) Foaming occurred when added into solution. After 30 minutes, the reaction mixture was extracted with CH ₂ Cl ₂ and H ₂ O. An organic layer (blue color) was obtained and dried over anhydrous Na ₂ SO ₄ . The filtrate was evaporated to yield a brown solid.

3. Zinc (II) Porphyrin Polymer Synthesis of

Methyl  3,4,5- tris ( hexadecyloxy ) benzoate (5) Synthesis of

of trihydroxylbenzoate methylester (3.0 g, 16.2 mmol), 1-bromohexadecane (30.0 g, 98.4 mmol), K ₂ CO ₃ (26.7 g, 194.4 mmol), and KI (16.2 g, 98.4 mmol) in dry DMF (300 ml) The mixture was heated to reflux for 24 h under argon atmosphere. DMF was evaporated in vacuo and the crude product was dissolved in CH ₂ Cl ₂ (1 L) and washed with water. The solvent was evaporated in vacuo. The residue was dissolved in a minimum amount of CH ₂ Cl ₂ , Precipitate by injecting with MeOH. Filtration, washing with MeOH and drying gave a white powder (10.8 g, 77%).

¹ H NMR (CDCl ₃ , 400 MHz): δ 0.87 (t, J = 6.71 Hz, 9 H), 1.25-1.30 (m, 72H), 1.40-1.55 (m, 6H), 1.65-1.85 (m, 6H ), 3.88 (s, 3H), 4.00 (t, J = 6.36 Hz, 6 H), 7.24 ppm (s, 2H)

3,4,5- Tris ( hexadecyloxy benzyl alcohol Synthesis of 6

Methyl 3,4,5-tris (hexadecyloxy) benzoate (5) (33.0 g, 38.5 mmol) in anhydrous THF (200 ml) solution was added to LiAlH ₄ in anhydrous THF (100 ml) solution at 0 ° C. (3.66 g, 96.2 mmol) was added dropwise to the suspension. The resulting mixture is then warmed to room temperature, stirred for 2 hours, excess LiAlH ₄ of Cooled back to 0 ° C. before adding water to cool. CH ₂ Cl ₂ The mixture was extracted with (100 ml) and then CH ₂ Cl ₂ was added. Mixed extracts Washed with H ₂ O, dried over Na ₂ SO ₄ and filtered. The filtrate was evaporated to dryness to afford 3,4,5-Tris (hexadecyloxy) benzyl alcohol (6) (28 g, 88%) as a white solid.

¹ H NMR (CDCl ₃ , 400 MHz): δ 0.87 (t, J = 6.71 Hz, 9H), 1.25-1.30 (m, 72H), 1.46-1.50 (m. 6H), 1.67-1.82 (m, 6H) , 3.89-3.99 (m, 6H), 4.58 (d, J = 5.51 Hz, 2H), 6.55 ppm (s, 2H)

3,4,5- Tris ( hexadecyloxy ) benzaldehyde (7) Synthesis of

Methylene chloride (200 ml) solution of 3,4,5-Tris (hexadecyloxy) benzyl alcohol (6) (20 g, 24.0 mol) was dissolved in pyridine chlorochromate (10.4 g, 48.0 mol) suspension and sodium acetate at 10 ℃. Dropwise was added into the mixed methylene chloride (100 ml). After stirring for 4 hours, diethyl ether (100 ml) was added followed by stirring for 1 hour. The solid was filtered off and washed with diethyl ether. The mixed filtrate was purified by SiO ₂ Chromatography (methylene chloride), and then the solvent was removed under vacuum distillation (20.0 g, 99%).

¹ H NMR (CDCl ₃ , 400 MHz): δ 0.87 (t, J = 6.71 Hz, 9H), 1.25-1.30 (m, 72H), 1.46-1.50 (m, 6H), 1.67-1.82 (m, 6H) , 4.08-3.99 (m, 6H), 7.08 (s, 2H), 9.83 ppm (s, 1H)

2,2?-{[3,4,5-Tris ( hexadecyloxy ) phenyl ] methylene } bis (One H - pyrrole Synthesis of 8

A solution of 3,4,5-tris (hexadecyloxy) benzaldehyde 7 (10 g, 12.0 mmol) dissolved in dry pyrrole (200 mL, 3.08 mmol) was evacuated and degassed three times with argon for 10 minutes. Trifluoroacetic acid (0.6 mL, 7.7 mmol) was added and the reaction stirred for 20 minutes to obtain an orange solution. The solution was diluted with dichloromethane and washed with aqueous NaOH solution and water. The organic layer was dried over anhydrous Na ₂ SO ₄ and filtered. After removal of the low-boiling solvent, excess pyrrole was recovered by distillation under vacuum. The residue is CH ₂ Cl ₂ (100 ml) and precipitated by addition of MeOH. The suspension was filtered and dried under vacuum to give a white powder (11.0 g, 97%).

¹ H NMR (CDCl ₃ , 400 MHz) δ 0.87 (t, J = 6.71 Hz, 9H), 1.24-1.32 (m, 72H), 1.46-1.50 (m, 6H), 1.68-1.86 (m, 6H), 3.81-3.90 (m, 6H), 5.41 (s, 1H), 5.90 (m, 2H), 6.16 (m, 2H), 6.71 (m, 2H), 6.80 (s, 2H), 8.15 ppm (brs, 2H )

5,15- Bis -[3,4,5-tris ( hexadecyloxy ) phenyl ] -10,20-bis [2- (trimethylsilyl) ethynyl] porphyrin (9) Synthesis

BF ₃ · OEt ₂ (0.39 mL) was mixed with dipyrromethane (8) (13.4 g, 14.2 mmol) and trimethylsilylpropynal (3.1 mL, 22.1 mmol) and degassed CH ₂ Cl ₂ (1.4 L) at 0 ° C. Added. After stirring for 1 hour at 0 ° C., 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ; 5.5 g, 24.2 mmol) was added and stirring was continued at room temperature for 30 minutes. The reaction mixture was concentrated and the product was purified by using silica gel chromatography using CH ₂ Cl ₂ / hexane (1: 1) as eluent. Pure product was obtained which was a purple solid (6.5 g, 43%).

¹ H NMR (CDCl ₃ , 400 MHz): δ 2.20 (s, 2H), 0.60 (s, 18H), 0.85-0.88 (m, 18H), 1.88-1.21 (m, 144H), 4.11 (m, 8H) , 4.30 (m, 4H), 7.38 (s, 4H), 8.92 (d, J = 4.4 Hz, 4H), 9.58 ppm (d, J = 4.4 Hz, 4H)

{5,15- Bis -[3,4,5-tris ( hexadecyloxy ) phenyl Synthesis of] -10,20-bis [2- (trimethylsilyl) ethynyl] porphinato} -zinc (II) (10)

A solution of MeOH (50 mL) in Zn (OAc) ₂ H ₂ O (1.32 g, 7.2 mmol) was added with CHCl ₃ (250 mL) in (9) (5.0 g, 2.4 mmol) and the mixture was Stir at room temperature for 4 hours. The solvent was removed in vacuo. The residue was dissolved in CH ₂ Cl ₂ and filtered through celite. The solvent of the filtrate was evaporated under reduced pressure to yield the crude product. It was then recrystallized from CH ₂ Cl ₂ / MeOH solution to yield product crystalline solid (4.9 g, 95%).

¹ H NMR (CDCl ₃ , 400 MHz): δ 0.60 (s, 18H), 0.85-0.88 (m, 18H), 2.00-1.21 (m, 144H), 4.11-4.07 (m, 8H), 4.26-4.30 ( m, 4H), 7.38 (s, 4H), 8.97 (d, J = 4.4 Hz, 4H), 9.64 ppm (d, J = 4.4 Hz, 4H)

{5,15-Bis [3,4,5-tris ( hexadecyloxy ) phenyl ] -10,20-bis ( ethynyl ) porphinato }-Synthesis of zinc (II) (11)

TBAF (98 mL, 1.0 m in THF, 0.098 mmol) was added into a solution of CH ₂ Cl ₂ (150 mL) in which (10) (1.0 g, 0.46 mmol) was dissolved. After 30 minutes, CaCl ₂ · 2H ₂ O was added and the mixture was evaporated to dry. The reaction mixture was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. After recrystallization with CH ₂ Cl ₂ / MeOH the product (910 mg, 95%) was obtained.

¹ H NMR (CDCl ₃ , 400 MHz): δ 0.85-0.88 (m, 18H), 2.00-1.21 (m, 144H), 4.11-3.95 (m, 8H), 4.16 (s, 2H), 4.30-4.20 ( m, 4H), 7.35 (s , 4H), 9.05 (d, J = 4.4 Hz, 4 H), 9.72 ppm (d, J = 4.4 Hz, 4H)

Polymer - zinc Synthesis of (II) (12)

CuCl (1.02 g, 10.27 mmol) and TMEDA (1.55 mL, 10.27 mmol) were added into a mixture of CH ₂ Cl ₂ (200 mL) and pyridine (1.9 mL) in which (11) (0.25 g, 0.12 mmol) was dissolved. The mixture was stirred vigorously and passed through dry air. After 30 minutes, the reaction mixture was washed repeatedly with water and the solvent was evaporated. The residue was dissolved in a minimum amount of chloroform / 1% pyridine and precipitated by the addition of methanol. The precipitate was washed twice with methanol (2 × 50 mL) and dried in vacuo to yield a polymer.

¹ H NMR (CDCl ₃ /1% [D ₅ ] pyridine, 400 MHz): δ 0.86-0.81 (m, 18 H), 2.00-1.19 (m, 144H), 4.19 (brs, 8H), 4.35 (brs, 4H), 7.42 (s, 4H), 9.08 (brs, 4H), 9.90 ppm (brs, 4H)

4. Copolymer Synthesis of

Poly [ porphyrin - bottom - anthracene ] (13) Copolymer  One)

Mixture in anhydrous toluene / triethylamine (1: 1, 10 mL) solution under argon (7) (500 mg, 0.25 mmol), 9,10-dibromoanthracene (73 mg, 0.25 mmol), tri (dibenzyldeneacetone) dipalladium (23 mg, 0.025 mmol ), And triphenylarsine (38 mg, 0.125 mmol) were placed in a 50 mL round-bottom flask, and the reaction mixture was refluxed for 2 days. The solvent was evaporated to dry under reduced pressure. The crude residue was CH ₂ Cl ₂ Was chromatographed using silica gel as eluent. The solvent was evaporated and the residue was dissolved to a minimum amount of chloroform and precipitated with methanol. The precipitate was washed twice with methanol (2 × 50 mL) and dried in vacuo to yield a polymer.

Poly [ porphyrin - bottom - phenothiazine (14) Copolymer  2)

Poly [porphyrin- alt- phenothiazine] was synthesized in the same manner as the above method (Poly [porphyrin- alt -anthracene] production method).

Poly [ porphyrin - bottom - benzothiadiazole Of (15) Copolymer  3)

Poly [porphyrin- alt- benzothiadiazole] was synthesized in the same manner as the above method (Poly [porphyrin- alt -anthracene] production method).

5. Results

Free base - Porphyrin Polymer

Polymerization of porphyrin units resulted in the synthesis and conjugation of polymers. Porphyrin-based free polymers were synthesized according to Scheme 1 using porphyrin-based conjugated polymers.
[Reaction Scheme 1]

In Scheme 1, A) is MgBr _2; B) is BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl _2, 3-trimethylsilylpropynal ); C) is Tetra-n-butylammonium fluoride (TBAF), CaCl ₂ 2H ₂ O, Tetrahydrofuran (THF); D) is CuCl, TMEDA (Tetramethylethylenediamine), CH ₂ Cl ₂ .

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To synthesize the porphyrin polymer, 5-mesityldipyrromethane was synthesized using 2,4,6-trimethylbenzaldehyde and excess pyrrole. In the case of dipyrromethane, the synthesis catalyst used TFA, InCl _3, etc., but the yield was different depending on the type of aldehyde. It was confirmed that a substance other than the desired substance was produced, which was determined as tripyrromethane. In addition, distillation was performed by using excess pyrrole to separate dipyrromethane and pyrrole. At this time, the external temperature was maintained by maintaining 40-50 ℃, when distillation at a higher temperature than the dipyrromethane and pyrrole is distilled together and the yield is lowered.

The synthesized 5-mesityldipyrromethane and 3-trimethylsilylpropynal were used for the Lindsey's method. TMS group which is a protecting group to use 5,15-bis- [3,4,5-tris (hexadecyloxy) phenyl] -10,20-bis [2- (trimethylsilyl) ethynyl] porphyrin synthesized as a monomer of a polymer Was removed using TBAF. The reaction was confirmed using TLC and the reaction was terminated. As can be seen from ¹ H-NMR, the protecting group was removed and the 0.6 ppm peak shown in FIG. 2 appeared at about 4.1 ppm in FIG. 3.

The porphyrin monomer thus synthesized was a porphyrin polymer through Glaser-Hay coupling. In the process of polymer synthesis, TLC was used to confirm that no porphyrin monomer was present and the reaction was terminated. After completion of the reaction was confirmed whether the synthesis using UV-vis spectrum and ¹ H-NMR.

In Figure 4 it can be seen that the strong absorption (Soret band) appears in the vicinity of 400nm monomer, the weak absorption (Q band) appeared between 500 ~ 700 nm. However, in the case of porphyrin polymer, 'Soret band' and 'Q band' red shifted and the area was widened. In the case of the 'Q band', the absorption intensity is compared with the 'Soret band', indicating that the polymer is higher than the momomer. The red shift means that the conjugation of the molecule is extended, and the absorption intensity of the 'Q band' increases as the molecular weight of the polymer increases, that is, the conjugation of the molecule increases.

However, the porphyrin polymer had poor solubility, which was not easy to increase the molecular weight of the polymer. The longer the reaction time was, the higher the molecular weight, and thus, when the molecular weight was higher than a certain molecular weight, the solubility was found to be precipitated as a solid.

Zinc (II) Porphyrin Polymer

In order to secure the shortcomings of the free base porphyrin polymer, a long chain was introduced to increase the solubility. The synthesis was started by referring to a paper that increased the solubility by synthesizing the porphyrin polymer using a long chain.
[Reaction Scheme 2]

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A) in Scheme 2 is 1-bromohexadecane, K ₂ CO ₃ , KI, DMF (Dimethylformamide); b) is LiAlH ₄ , THF (Tetrahydrofuran); c) is pyridinium chlorochromate (PCC), CH ₂ Cl ₂ ; d) is pyrrole, CH ₂ Cl ₂ ; f) is 3-trimethylpropynal, BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl ₂ .

First, an alkylation reaction was performed to make aldehyde substituted with a long chain. ¹ H-NMR measurement of the product showed a long chain at 2 ~ 0.8 ppm (Fig. 5).

Then the reaction was made to make benzoate alcohol. It should be noted that Lithium aluminum hydride (LiAlH ₄ ) is sensitive to moisture and should be treated with care for a long time in small amounts when quenching to complete the reaction. In addition, NaCl or NaHCO ₃ can be conveniently used because the separation of water and layers is difficult during the extraction process. In addition, when measured by ¹ H-NMR, -OCH ₃ at 3.8 ppm shown in benzoate The peak disappeared and a new peak appeared in the 4.5 ppm region (FIG. 6).

Benzaldehyde could be easily synthesized using pyridium chlorochromate (PCC). The materials synthesized through the above process were confirmed by ¹ H-NMR. The peak in the 4.5 ppm region disappeared, and the aldehyde peak appeared in the 9.8 ppm region (FIG. 7).

Dipyrromethane was made using aldehyde and pyrrole. Since excess pyrrole was used, the synthesis of the aldehyde peak of ¹ H-NMR could be determined (FIG. 8).

The synthesized dipyrromethane and 3-trimethylsilylpropynal were used for the Lindsey? S method.
[Reaction Scheme 3]

A) in Scheme 3 is Zn (OAc) ₂ , CHCl ₃ / MeOH; b) is Tetra-n-butylammonium fluoride (TBAF), CH ₂ Cl ₂ ; c) is CuCl, Tetramethylethylenediamine (TMEDA), CH ₂ Cl ₂ / pyridine.

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In order to use the monomer as a polymer, the protecting group TMS was removed using TBAF (Scheme 3-Zn (II) -Porphyrin Polymer synthesis).

In FIG. 9, a new peak appears at 4.1 ppm due to removal of the protecting group from 0.6 ppm of ¹ H NMR peak. Porphyrin polymer was synthesized by Glaser-Hay coupling using the synthesized polymer monomer. TLC was used to confirm the absence of porphyrin monomer and the reaction was terminated. The reaction time was long until the monomer disappeared.

Experimental results show that even if the reaction time of the polymer polymerization reaction is prolonged, it does not significantly influence molecular weight increase.

As shown in ¹ H NMR in Figure 10 it can be seen that the peak is wide overall. This is because the environment of each porphyrin unit before the polymerization reaction is the same, the resonance signal is constant, but when the polymer is synthesized through the polymerization reaction, the surrounding environment of each porphyrin unit is different. It was found that the polymerization of the polymer was carried out.

The absorption spectrum of porphyrin monomers shows the characteristic absorption bands of porphyrin. Strong Soret absorption bands at 400-460 nm and weak Q absorption bands at 550-650 nm. However, it was found that the wavelength of absorbance was greatly extended through the polymerization of porphyrin monomers. As shown in Fig. 11, a very strong Soret absorption band at 400-550 nm and a long and wide Q absorption band at 650-900 nm are generated. Due to the expansion of conjugation, the absorption capacity of the polymer is improved. This absorption feature is advantageous as a solar cell material. This is because the absorption area is wider than conventional organic materials, and thus can receive a lot of light. There is a possibility that the efficiency of solar cells can also increase as much light is received.

The fluorcence spectra of the synthesized porphyrin polymer showed peaks at nm for porphyrin monomers but no peak for porphyrin polymers. The peak appearing at about 850 nm was suspected to be a fluorescence spectra.

Although the fluorescence spectra is shown in the reference literature at about 800 nm, the conditions of the experiment using THF and exitation at 468 nm are slightly different. As a result, electrons are absorbed from each unit of porphyrin, and electrons are excited to conjugated neighboring porphyrin units.

It was judged that the fluorescence quenching of the product itself occurred by being transferred to another porphyrin unit serving as an electron acceptor to receive the electron transfer. Or it was determined that the emission signal was generated at a wavelength of more than 900 nm and could not be measured.

Copolymer

After confirming the results by the polymerization reaction, it was confirmed that the absorption capacity is insufficient in the region of 550 ~ 750 nm in the absorption spectrum of porphyrin polymer. Thus, in this experiment, the absorption region of 550-750 nm was expanded by adding organic materials other than porphyrin. Referring to the literature on the polymerization of porphyrin and organic materials [9 (a)], the sonogashira-cross coupling reaction was carried out (Scheme 7).

[Reaction Scheme 7]

As a result of synthesis, the absorption spectrum of the copolymer and the porphyrin polymer was different (Fig. 13).

The absorption spectra of organic materials show no absorption in the region above 400 nm. Porphyrin monomer showed absorption spectrum of Soret band at 400 ~ 450 nm. Thus, the reaction proceeded in anticipation of the absorption capacity in the region of 500 nm or more when the conjugation of the two materials was expanded.

As the polymerization proceeded for 2 days, the solubility was decreased as the molecular weight of the polymer increased, and when the precipitate was formed in RBF, the reaction was increased by adding only a small amount of THF. When the column is finished after the reaction, the product is first separated using CH ₂ Cl ₂ as a developing solution, and the residue remaining in the column is a different biomaterial as a result of analysis. Therefore, THF or other developing solutions should not be mixed together.

Different copolymers showed different absorption spectra, suggesting that the polymer conjugation effect of each organic material would be different.

In the fluorescence spectrum, three different organic materials were used, but similar peaks appeared at 500 ~ 700 nm, and the fluorescence spectrum did not appear above 800 nm. It was determined that fluorescence quenching of the product itself occurred by transfer to porphyrin units.

¹ H NMR analysis did not show the peak of the organic material was not accurate analysis whether the shift polymerization was performed (Fig. 16, 17).

< Example  Use as a 2-solar cell device>

Among the materials synthesized above, Zn-polymer and copolymer 1 impurities were fabricated and analyzed for their characteristics.

Thermal stability was analyzed through TGA prior to solar cell fabrication.

Synthesized polymer was well dissolved in commonly used organic solvents such as CHCl ₃ , THF or toluene, TGA was measured by raising the temperature to 20 ℃ per minute under nitrogen conditions. As a result of the TGA measurement, the 5% loss point of the initial weight is generally called a decomposition temperature (Decomposition Tempertature), and as shown in FIG.

Organic solar cells were fabricated to investigate the photovoltaic characteristics of organic solar cell devices. The device was fabricated as follows: [ITO / PEDOT: PSS / Polymer + PC ₇₀ BM / LiF / Al].

The solar cell device is made of polymer + PC ₇₀ BM in the active layer to know the photoelectric characteristics in order to investigate the effect of photoelectric efficiency characteristics according to the type of A (acceptor) and the ratio of D (donor): A (acceptor). The characteristics were examined by changing the D: A ratio to 1: 3 and 1: 5. In order to determine the difference in efficiency according to the thickness of the active layer, two types of porphyrin polymers were measured at different thicknesses.

As a result of fabrication and measurement of the device, the copolymer and PC ₇₀ BM were mixed in a 1: 5 ratio and the thinner the active layer was 43 nm, the higher the efficiency was. In general, Zn-porphyrin polymer shows the highest efficiency when the thickness of active layer is about 100 nm. However, the synthesized Zn-porphyrin polymer is not coated on PEDOT [Poly (3,4-ethylenedioxy thiophene)] in device fabrication. It was difficult to measure. In the case of copolymer 1, all ratios were not measured at 100 nm, but the thinner than the thicker active layer showed higher energy conversion efficiency.

Table 2 shows the energy conversion efficiency by introducing a post annealing method, which is a heat treatment process after making a solar cell device. As a result of the post annealing, the energy conversion efficiency was slightly increased.

20 is data measured to determine the band gap of the synthesized polymer.

First, in the case of Zn-polymer, HOMO was -5.442 eV and LUMO was -3.642 eV. Copolymer 1 measured HOMO of -5.486 eV and LUMO of -3.648 eV. Zn-polymer and copolymer 1 showed band gaps of 1.78eV and 1.83eV, respectively.

21 is Incident photon-to-current efficiency (IPCE) data. This data is a graph showing the energy conversion efficiency for each specific wavelength that absorbs sunlight. Zn-porphyrin polymer shows an IPCE efficiency of about 10% at 380 nm. This means that the Zn-porphyrin polymer receives 100 solar light at 380 nm and converts 10 to electrical electrons. In general, the IPCE graph has a graph pattern similar to the absorption spectrum. Because of the energy conversion efficiency for the area that absorbs sunlight, the efficiency does not appear in areas where sunlight is not absorbed. However, the Zn-porphyrin polymer and copolymer 1 show a large difference in the IPCE graph compared to the similar absorption graph. In addition, the absorption graph of the polymer has an absorption region at 700 ~ 900 nm, it can be seen that the peak does not appear in the IPCE graph.

This means that the energy conversion efficiency does not appear in the 700 ~ 900 nm.

22 shows the energy conversion efficiency of copolymer 1 through the JV curve. The curve below shows an active layer thickness of 43 nm and post annealing at 120 ° C for 10 minutes. FIG. 22 illustrates a bulk heterojuntion solar cell in which an donor and an acceptor are mixed to form an active layer. The data can be seen in Tables 2 and 3, and the devices consisted of ITO / PEDOT: PSS / polymer: PC ₇₀ BM / LiF / Al. An energy conversion efficiency may be calculated by checking an open cicuit voltage, a short circuit current density and a fill factor through FIG. 22.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (9)

A porphyrin-based conjugated polymer represented by any one of the following Chemical Formulas 1, 3, and 5.
[Formula 1]

(3)

[Chemical Formula 5]

In Chemical Formulas 1, 3, and 5, n is an integer of 5 to 50,

to be. 1) preparing compound 1-1 by reacting pyrrole (25 mmol), mestalaldehyde (2.5 mmol) and MgBr ₂ (12.5 mmol) under an inert gas;
2) Compound 1-2 by reacting Compound 1-1, 3-trimethylsilylpropynal, BF ₃ OEt ₂ and DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone) under inert gas Preparing a;
3) obtaining Compound 1-3 by reacting Compound 1-2 with TBAF (Tetra-n-butylammonium fluoride) in an organic solvent; And
4) preparing a compound of Chemical Formula 1 by reacting Compound 1-3 with TMEDA (Tetramethylethylenediamine); To include, a method of producing a porphyrin-based conjugated polymer represented by Scheme 1.
[Reaction Scheme 1]

In Scheme 1, A) is MgBr _2; B) is BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl _2, 3-trimethylsilylpropynal ); C) is Tetra-n-butylammonium fluoride (TBAF), CaCl ₂ 2H ₂ O, Tetrahydrofuran (THF); D) is CuCl, TMEDA (Tetramethylethylenediamine), CH ₂ Cl ₂ . 1) Trihydroxybenzoate methyl ester (16.2 mol), 1-bromohexadecane (98.4 mol), K ₂ CO ₃ (194.4 mmol) and KI (98.4 mmol) were reacted under an organic solvent under an organic solvent to give a compound 2 Preparing -1;
2) preparing Compound 2-2 by reacting Compound 2-1 and LiAlH ₄ in an organic solvent;
3) preparing Compound 2-3 by reacting Compound 2-2 and pyridine chlorochromate (48.0 mol) in an organic solvent;
4) preparing compound 2-4 by reacting compound 2-3 with pyrrole;
5) preparing compound 2-5 by reacting compound 2-4 and dipyro methane;
6) preparing Compound 2-6 by reacting Compound 2-5 and Zn (OAc) ₂ .2H ₂ O (7.2 mmol);
7) preparing a compound 2-7 by reacting the compound 2-6 and Tetra-n-butylammonium fluoride (TBAF); And
8) preparing a compound of Chemical Formula 2 by reacting Compound 2-7, CuCl, and TMEDA (Tetramethylethylenediamine) under an organic solvent; To include, a method of producing a porphyrin-based conjugated polymer represented by the reaction schemes 2 and 3.
[Reaction Scheme 2]

A) in Scheme 2 is 1-bromohexadecane, K ₂ CO ₃ , KI, DMF (Dimethylformamide); b) is LiAlH ₄ , THF (Tetrahydrofuran); c) is pyridinium chlorochromate (PCC), CH ₂ Cl ₂ ; d) is pyrrole, CH ₂ Cl ₂ ; f) is 3-trimethylpropynal, BF ₃ OEt ₂ (Boron trifluoride diethyl ether), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), CH ₂ Cl ₂ .

[Reaction Scheme 3]

A) in Scheme 3 is Zn (OAc) ₂ , CHCl ₃ / MeOH; b) is Tetra-n-butylammonium fluoride (TBAF), CH ₂ Cl ₂ ; c) is CuCl, Tetramethylethylenediamine (TMEDA), CH ₂ Cl ₂ / pyridine. 3,4,5-tris (hexadecyloxy) benzaldehyde (3,4,5-Tris (hexadecyloxy) benzaldehyde), 9,10-dibromoanthracene (9,10-dibromoanthracene), tri (dibenzydene A method of preparing a porphyrin-based conjugated polymer represented by Scheme 4, comprising the step of preparing a compound of Formula 3 by reacting acetone) dipalladium (tri (dibenzyldeneacetone) dipalladium) and triphenylarsine in an organic solvent.
[Reaction Scheme 4]

3,4,5-tris (hexadecyloxy) benzaldehyde (3,4,5-Tris (hexadecyloxy) benzaldehyde), 9,10-dibromophenothiazine, tri (dibenzydene A method of preparing a porphyrin-based conjugated polymer represented by Scheme 5, comprising the step of reacting acetone) dipalladium (tri (dibenzyldeneacetone) dipalladium) and triphenylarsine in an organic solvent to produce a compound of Formula 4.
Scheme 5

3,4,5-tris (hexadecyloxy) benzaldehyde (3,4,5-Tris (hexadecyloxy) benzaldehyde), 9,10-dibromobenzocothiadiazole (9,10-dibromobenzothiadiazole), tri (di Benzydene acetone) dipalladium (tri (dibenzyldeneacetone) dipalladium) and triphenylarsine (triphenylarsine) by reacting under an organic solvent to prepare a compound of formula 5, a porphyrin-based conjugated polymer manufacturing method represented by Scheme 6 .
[Reaction Scheme 6]

A solar cell device comprising the porphyrin-based conjugated polymer according to claim 1. 8. The method of claim 7,
The solar cell is a solar cell device, characterized in that the organic solar cell or dye-sensitized solar cell.
The organic solvent according to any one of claims 2 to 6, wherein the organic solvent used in each step is at least one selected from the group consisting of methylene chloride, tetrahydrofuran, chloroform, dimethylformimide, toluene, and triethylamine. Method for producing a porphyrin-based conjugated polymer, characterized in that.

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