WO2015174774A2

WO2015174774A2 - Novel porphyrin-based derivative, organic dye for dye-sensitized solar cell comprising same derivative, and dye-sensitized solar cell comprising same organic dye

Info

Publication number: WO2015174774A2
Application number: PCT/KR2015/004880
Authority: WO
Inventors: 김환규; 강성호; 정승영
Original assignee: 고려대학교 산학협력단
Priority date: 2014-05-15
Filing date: 2015-05-15
Publication date: 2015-11-19
Also published as: WO2015174774A3

Abstract

The present invention relates to a novel porphyrin-based derivative, an organic dye for a dye-sensitized solar cell, comprising the porphyrin-based derivative, and a dye-sensitized solar cell comprising the organic dye. More specifically, the porphyrin-based derivative can be used for an organic dye for a novel high-efficiency dye-sensitized solar cell with improved long-term stability and energy conversion efficiency since, in the porphyrin-based derivative, 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 porphyrin. Further, a high-efficiency dye-sensitized solar cell can be manufactured using the dye containing the porphyrin-based derivative of the present invention.

Description

Novel porphyrin derivatives, organic dyes for dye-sensitized solar cells comprising the same, and dye-sensitized solar cells comprising the same

The present invention relates to a novel porphyrin-based derivative for organic electronic devices, an organic dye for a dye-sensitized solar cell including the porphyrin-based derivative, and a dye-sensitized solar cell including the organic dye, and more specifically, various electron donors and porphyrins. Porphyrin derivatives having carbon-carbon triple bonds or single bonds introduced at the same time, carbon-carbon triple bonds or single bonds introduced between various electron acceptors and porphyrins, and new high efficiency with improved long-term stability and energy conversion efficiency An organic dye for a dye-sensitized solar cell and a high efficiency dye-sensitized solar cell comprising the same.

Due to environmental and energy issues such as fossil fuel depletion, environmental pollution, and CO ₂ and SO ₂ generation, solar energy is spotlighted as the next generation of environmentally friendly alternative energy as infinitely clean energy. Solar cells are devices that can convert sunlight directly into current (voltage), and research on low-cost organic solar cells in addition to pn junction solar cells using pn junctions of existing inorganic semiconductors is actively underway. The advantages of organic solar cells, besides being inexpensive and environmentally friendly, are transparent, thin and light properties that can realize indoor applications and power windows. Dye-sensitized solar cells (DSSCs) are used for dye-sensitization solar cells using dye-sensitization by adsorbing dyes absorbing visible light in a semiconductor having a wide bandgap. to be.

DSSC was first developed in 1991 by the Gratzel Group, Switzerland, by adsorbing Ru (II) -based complexes to TiO ₂ metal oxides with optically transparent nanoparticle sizes (15-20 nm). It consists of a layer metal oxide, dye photosensitive agent, electrolyte, and an electrode.

Specifically, a transparent conducting oxide electrode such as fluorinated tin oxide (FTO) and indium tin oxide (ITO), which are used as substrates of both electrodes, and an oxide semiconductor layer not forming fine particles such as TiO ₂ and ZnO ( metal salts such as nonoparticulated oxide semi-conductor layers, dye-sensitization such as inorganic or organic dyes such as ruthenium, electrolytes containing electrolytes and redox couples, and metal salts such as platinum, which act as counter electrodes Is generated.

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 these problems, new organic compounds have been studied as dyes, and many studies using porphyrin compounds known as photosynthetic materials as dyes have been conducted, but the efficiency was not as high as 1 to 3%. Durur 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 dye to the ground state. Reported.

On the other hand, Japanese Patent Application Laid-Open No. 2002-063949 discloses porphyrin derivatives in which phenyl groups are substituted at

positions

5, 10, 15, and 20 of porphyrin as porphyrin conductors having photoelectric conversion characteristics. However, the following porphyrin compounds (R = hydrogen atom or acidic substituent) have a disadvantage of showing low energy conversion efficiency due to recombination of exciton electrons between porphyrin dyes.

Accordingly, there is an increasing need for developing porphyrin derivatives for dye-sensitized solar cells having superior long-term stability compared to conventional ruthenium-based dyes and excellent photoelectric conversion rates compared to conventional porphyrin-based dyes.

An object of the present invention is to solve the above problems, it is easy to synthesize and excellent in the photoelectric conversion rate as well as by introducing a variety of substituents or carbon-carbon triple bonds in porphyrin derivatives, the largest existing ruthenium-based dye It is to provide a porphyrin derivative that can solve the problem of device application due to lack of long-term stability and overcome the low efficiency of the solar cell using a conventional porphyrin derivative.

In addition, another object of the present invention is to provide a dye for a high efficiency dye-sensitized solar cell prepared using a novel porphyrin-based derivative according to the present invention and a dye-sensitized solar cell comprising the dye.

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

[Formula 1]

In Chemical 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 (C6-C20) arylene, which arylene may be further substituted with (C1-C20) alkyl;

m is an integer of 0 or 1;

A is selected from the following structures;

If n is 0 then B is

ego;

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

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 high efficiency dye-sensitized solar cell including the porphyrin-based derivative of the present invention shows long-term stability even in the external environment, alkoxy-substituted phenyl derivative having strong electron donor ability, arylamine derivative substituted with alkoxy or carbon Intramolecular electron transfer through carbon triple bonds is strengthened, and light absorption in the near-infrared region can be absorbed by increasing the planarity and conjugation of the molecule, thereby securing a large absorption range from the visible to the near-infrared region. There is an advantage to obtain energy conversion efficiency.

1 and 2 are UV absorption and emission spectra of the porphyrin-based compounds of Examples 1 to 3.

3 is a UV absorption spectrum of the porphyrin-based compound of Example 4.

Figure 4 is a graph showing the current density of the solar cell using the porphyrin compound of Examples 1 to 3.

5 is a graph showing the current conversion efficiency (IPCE) of the solar cell using the porphyrin-based compound of Examples 1 to 3.

6 is a graph showing the current conversion efficiency (IPCE) of the solar cell using the porphyrin-based compound of Example 4.

7 is a graph showing the current density of the solar cell using the porphyrin-based compound of Example 4.

Unless otherwise defined in the technical and scientific terms used in the present invention, it can be interpreted as having a meaning commonly understood by those skilled in the art.

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

[Formula 1]

In Chemical 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;

m is an integer of 0 or 1;

A is selected from the following structures;

If n is 0 then B is

ego;

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

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

Porphyrin-based derivatives according to the present invention are intended to overcome the difficulties in device applications due to lack of long-term stability, which is the biggest problem of conventional ruthenium-based dyes, and to overcome the low efficiency of solar cells using conventional porphyrin derivatives. The porphyrin derivatives according to the present invention have a phenyl group substituted with two (C1-C20) alkoxy substituents at positions 5 and 15 of porphyrin and one or two (C1-C20) alkoxy substitutions at position 10 of porphyrin. It is characterized by a structure in which a substituted arylamino group in which phenyl is substituted is introduced, and in some cases, may have a carbon-carbon triple bond between the arylamino group and porphyrin.

The solar cell using the new porphyrin derivative according to the present invention shows long-term stability even in the external environment, and has a strong electron donating ability, alkoxy-substituted phenyl derivative, alkoxy-substituted arylamine derivative or carbon-carbon triple bond. The electron transfer is stronger and the light absorption in the near infrared region is possible by increasing the planarity and conjugation of the molecule, so that the high energy conversion efficiency can be obtained by securing the wide absorption region from the visible light to the near infrared region. There is this.

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

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

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 are selected from the following structures:

R is (C1-C20) alkyl.

In one embodiment of the invention, the porphyrin-based derivatives may be specifically illustrated by the following structure:

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

Scheme 1

Scheme 2

The porphyrin derivatives represented by Formula 1 may be usefully used as dyes for dye-sensitized solar cells. Accordingly, the present invention provides a dye for a solar cell dye containing a porphyrin derivative of the 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 is not limited thereto, but may have the following configuration:

A first electrode comprising a conductive transparent substrate;

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

A second electrode disposed to face the first electrode on which the light absorption layer is formed; And

An electrolyte located in the space between the first electrode and the second electrode.

Referring to the materials constituting the solar cell as an example.

The first electrode including the conductive transparent substrate is a translucent 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 It may be a glass substrate or a plastic substrate comprising a.

The light absorption layer necessarily includes an organic dye for a dye-sensitized solar cell including the porphyrin-based derivative represented by Formula 1, and may further include a semiconductor fine particle, a dye, a compound having hole conductivity. The semiconductor fine particles are not limited thereto, but may be formed of nanoparticle oxides such as titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ), and zinc oxide (ZnO). The dye adsorbed on the semiconductor fine particles may absorb light in the visible light region, form a strong chemical bond with the surface of the nanooxide, and may be used without limitation as long as it has thermal and optical stability. Representative examples include ruthenium-based organometallic compounds. The light absorbing layer may further include a co-adsorber, and the co-adsorber fills the hole formed in the dye that absorbs the light, and becomes a hole again, and then fills the hole by the electrolyte.

As the second electrode, the same electrode as the first electrode may be used, and a current collector layer further formed of platinum or the like may be used on the light transmitting electrode of the first electrode.

Hereinafter, the present invention will be described in detail through examples. However, these examples are only presented to explain the present invention more clearly, and are not intended to limit the scope of the present invention. The scope of the invention will be defined by the technical spirit of the claims below.

Preparation Example 1 Preparation of Compound 6

compound 44 Manufacture

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 quickly added through a syringe, followed by stirring 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 then the crude product was eluted through chloroform shot pads. 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 = volume ratio 20/1) to yield a dark brown red solid. 4 (0.6 g, 11%) was obtained.

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 10.248 (1 H, s, meso-Ar-H), 9.355 (2 H, d, J = 4.8 Hz, Ar-H), 9.038 (2 H, d, J = 4.5 Hz, Ar-H), 8.931 (2H, d, J = 4.8 Hz, Ar-H), 8.821 (2H, d, J = 4.8 Hz, Ar-H), 8.442 (2H , 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 (6H, m, Ar -H), 3.918 (8H, m, -OCH ₂ ), 0.440-0.951 (60H), -2.76 (2H, s). FT-IR (KBr) [cm ⁻¹ ] 2230 (−CN).

compound 55 Manufacture

Compound 4 (500 mg, 0.46 mmol) was dissolved in CHCl ₃ (150 mL), NBS (N-bromosuccinimide) (100 mg, 0.56 mmol) was added and the reaction mixture was refluxed for 12 hours, followed by distilled water. Was terminated. The organic layer was washed several times with brine and dried over anhydrous sodium sulfate. After evaporation of the solvent under vacuum 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 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 3.918 (8H, m, -OCH ₂ ), 0.440-0.951 (60 H), -2.76 (2 H, s). FT-IR (KBr) [cm ⁻¹ ] 2230 (−CN).

compound 66 Manufacture

Compound 5 (500 mg, 0.11 mmol) was dissolved in THF (100 mL), zinc acetate dihydrate (350 mg, 0.54 mmol) was added and then refluxed for 12 h. After evaporation of the solvent 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 yield Compound 6 (360 mg, 94%) as a purple solid.

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 3.918 (8H, 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 ', 4'-bis (hexyloxy) biphenyl-4-amine (2.5 g, 4.55 mmol), 2,4-bis (hexyloxy) -4'-iodobiphenyl (2.32 g) under a nitrogen atmosphere , 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) was 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 under vacuum and purified by silica gel column chromatography (eluent CH ₂ Cl ₂ : n- hexane = 3: 1) to afford compound 7 (3.5 g, 81%).

¹ H-NMR (300 MHz; (CDCl ₃ ; TMS) δ 7.415-7.452 (4H, d, J = 8.4 Hz, Ar-H), 7.153-7.231 (6H, 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 (8H, 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

1010 Manufacture

Compound 6 (Preparation Example 1, 500 mg, 0.71 mmol), Compound 7 (Preparation Example 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 h. The solvent was evaporated and extracted several times with CH ₂ Cl ₂ and brine. The organic layer was dried over anhydrous sodium sulfate and filtered and the filtrate was evaporated under vacuum. Then purified by flash column chromatography using chloroform as eluent to afford compound 10 (170 mg, 25%) as dark green oil.

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 7.415-7.452 (4H, 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), 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).

compound 1111 Manufacture

Compound 10 (130 mg, 0.14 mmol) was added to anhydrous CH ₂ Cl ₂ (25 mL), followed by dropping DIBAL-H solution (Diisobutylaluminium hydride, 1 M in hexanes, 0.27 mL, 0.27 mmol) under nitrogen atmosphere at 0 ° C. -Added drop-wise. The reaction mixture was stirred at room temperature for 4 hours, then quenched with aqueous NH ₄ Cl solution (200 mL) and further stirred for 2 hours. After removing the aqueous layer, the organic layer was washed with brine and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography (eluent CHCl ₃ ) yielded 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 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, d, J = 4.5 Hz, Ar-H), 8.931 (2H, d, J = 4.8 Hz, Ar-H), 8.821 (2H, d, J = 4.8 Hz, Ar-H), 8.442 (2H, 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 (6H, m, Ar-H), 7.415-7.452 (4H, d, J = 8.4 Hz, Ar-H), 7.153-7.231 (6H, d, J = 8.7 Hz, Ar-H), 6.545-6.612 (4H d, J = 8.7 Hz, 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

1212 Manufacture

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 then 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 afford 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 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, d, J = 4.5 Hz, Ar-H), 8.931 (2H, d, J = 4.8 Hz, Ar-H), 8.821 (2H, d, J = 4.8 Hz, Ar-H), 8.442 (2H, 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 (6H, m, Ar-H), 7.415-7.452 (4H, d, J = 8.4 Hz, Ar-H), 7.153-7.231 (6H, d, J = 8.7 Hz, Ar-H), 6.545-6.612 (4H d, J = 8.7 Hz, 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 is J. Mater. Chem. Prepared according to A, 2013,1, 9848.

compound 1313 Manufacture

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

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 7.70 (8H, m, Ar-H ), 7.43 (2H, d, J = 8.1 HzAr-H), 7.31 (2H, d, J = 8.4 Hz, Ar-H), 7.17 (2H, d, J = 8.1 Hz, Ar-H) , 6.63 (4H, m, Ar-H), 3.918 (16H, m, -OCH ₂ ), 0.440-0.951 (104H, m-CH ₂ , -CH ₃ ). FT-IR (KBr) [cm ⁻¹ ] 2230 (−CN).

compound 1414 Manufacture

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

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 7.70 (8H, m, Ar-H ), 7.43 (2H, d, J = 8.1 Hz, Ar-H), 7.31 (2H, d, J = 8.4 Hz, Ar-H), 7.17 (2H, d, J = 8.1 Hz, Ar-H ), 6.63 (4H, m, Ar-H), 3.918 (16H, m, -OCH ₂ ), 0.440-0.951 (104H, 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

1515 Manufacture

Compound

15 was obtained by the same method as the preparation method of compound 12 of Example 1.

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 7.70 (8H, m, Ar-H ), 7.43 (2H, d, J = 8.1 Hz, Ar-H), 7.31 (2H, d, J = 8.4 Hz, Ar-H), 7.17 (2H, d, J = 8.1 Hz, Ar- H), 6.63 (4H, m, Ar-H), 3.918 (16H, m, -OCH ₂ ), 0.440-0.951 (104H, 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 1616 Manufacture

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

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 6.968-6.938 (4H, d, J = 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 1717 Manufacture

Compound 17 was obtained by the same method as the preparation method of compound 11 of Example 1.

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 6.968-6.938 (4H, d, J = 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

1818 Manufacture

Compound

18 was obtained by the same method as the preparation method of compound 12 of Example 1.

¹ H-NMR (300 MHz; CDCl ₃ ; TMS) δ 9.355 (2H, d, J = 4.8 Hz, Ar-H), 9.038 (2H, 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 (6H, m, Ar-H), 6.968-6.938 (4H, d, J = 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 reference NATURE CHEMISTRY, 2014, 6, 242.

compound

2020 Manufacture

60% NaH (0.43 g, 10.62 mmol), Pd (OAc) ₂ (0.03 g, 27 mmol), DPEphos (0.18 g, 0.34 mmol), compound 19 (0.5 g, 0.71 mmol) and compound 8 (1.8 g, 2.48 mmol) The 250 mL Schlenk flask containing) was equipped with a cooler and dried under vacuum. After drying, anhydrous THF (50 mL) was added under nitrogen reflux, and the mixture was refluxed and stirred at 80 ° 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 residue was separated by column chromatography (eluent CHCl ₃ ) to give compound 20 (20%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 9.59 (d, J = 4.4 Hz, 2H), 9.11 (d, J = 4.4 Hz, 2H), 8.80 (d, J = 4.8 Hz), 2H), 8.65 (d, J = 4.8 Hz, 2H), 8.46 (t, J = 8.4 Hz, 2H), 7.20 (d, J = 8.6 Hz, 4H), 7.15-7.07 (m, 6H), 6.96 (d, J = 8.4 Hz, 4H), 6.48 (d, J = 6.6 Hz, 4H), 6.44 (d, J = 2.2 Hz, 1H), 6.42, (d. J = 2.2 Hz, 1H), 3.91 (t, J = 6.6 Hz, 4H), 3.89 (t, J = 6.6 Hz, 4H), 3.82 (t, J = 6.6 Hz, 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 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 2222 Manufacture

Compound 20 (222 mg, 0.1475 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1M 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 using distilled water and CH ₂ Cl ₂ , and the organic layer was dried over sodium sulfate. AsPH 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 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 = 4.4 Hz, 2H), 8.80 (d, J = 4.8 Hz), 2H), 8.65 (d, J = 4.8 Hz, 2H), 8.46 (t, J = 8.4 Hz, 2H), 8.46 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 8.6 Hz, 4H), 7.15-7.07 (m, 6H), 6.96 (d, J = 8.4 Hz, 4H), 6.48 (d, J = 6.6 Hz, 4H), 6.44 (d, J = 2.2 Hz, 1H), 6.42, (d. J = 2.2 Hz, 1H), 3.91 (t, J = 6.6 Hz, 4H), 3.89 (t, J = 6.6 Hz, 4H), 3.82 (t, J = 6.6 Hz, 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 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound

2323 Manufacturing Method

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 added to a round flask and stirred at 60 ° C. for 3 hours. When compound 22 disappeared by TLC, the reaction was terminated and neutralized to PH7 with 1M HCl. Then, the mixture was extracted with CH ₂ Cl ₂ and distilled water, and the organic layer was dried over sodium sulfate and filtered. The filtrate was evaporated under vacuum and the solid obtained was purified by silica column chromatography (eluent dichloromethane: methanol (10: 1)) to give compound 23 .

Example 5 Preparation of Compound 29

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

compound 2525 Manufacture

Compound 19 (146mg, 0.13 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1M in THF, 0.34mL, 0.340mmol) were added to a round flask containing THF (20mL) and stirred for 30 minutes. After stirring, the mixture was extracted using distilled water and CH ₂ Cl ₂ , and the organic layer was dried over sodium sulfate. To a solid obtained by evaporating the organic solvent of the dried organic layer, AsPH ₃ (78 mg, 0.260 mmol), Pd ₂ (dba) ₃ (23 mg, 0.030 mmol), Compound 24 (146 mg, 0.260 mmol), THF (40 mL), and Et ₃ N (3 mL) was added and 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 = 4.5 Hz, 2H), 8.867 (d, J = 4.5 Hz, 2H), 8.847 ( d, J = 4.5 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.688 (t, J = 8.4 Hz, 2H), 7.168 (d, J = 8.4 Hz, 4H), 7.063-7.034 ( d, 2H), 7.017-7.004 (d, J = 8.4 Hz, 4H), 6.904-6.873 (d, J = 6.6 Hz, 4H), 3.992 (t, J = 6.6 Hz, 4H), 3.854 (t, J = 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 (m, 16H ), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 2626 Manufacture

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) were placed in a Schlenk flask. After vacuuming for an hour, add 40 ml of dry toluene. Add Et ₃ N (64mg, 0.63mmol), add TIPS (Triisopropylsilylacetylene) (20ml, 0.08mmol) and reflux for 12 hours. The solvent was then evaporated and purified by column chromatography to give compound 26 (54 mg, 76%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 9.669 (d, J = 4.4 Hz, 2H), 9.646 (d, J = 4.4 Hz, 2H), 8.854 (d, J = 4.8 Hz), 2H), 8.839 (d, J = 4.8 Hz, 2H), 7.788 (d, J = 8.4 Hz, 2H), 7.701 (t, J = 8.6 Hz, 2H), 7.170 (d, 4H), 7.068 (d, J = 8.4 Hz , 2H), 6.996 (d, J = 6.6 Hz, 4H), 6.901 (d, J = 2.2 Hz, 4H), 3.992 (t, J = 6.6 Hz, 4H), 3.846 (t, J = 6.6 Hz, 8H ), 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, 16H), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 2828 Manufacture

Compound 26 (60mg, 0.04 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1M in THF, 0.35mL, 0.320mmol) were added to a round flask containing THF (20mL) and stirred for 30 minutes. After stirring, the mixture was extracted using distilled water and CH ₂ Cl ₂ , and the organic layer was dried over sodium sulfate. AsPH ₃ (24 mg, 0.080 mmol), Pd ₂ (dba) ₃ (7 mg, 0.010 mmol), Compound 27 (31 mg, 0.080 mmol), THF (20 mL), and Et ₃ N (0.68 mL) was added and 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 = 4.4 Hz, 2H), 8.952 (d, J = 4.8 Hz), 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 (m, 4H), 7.191 (d, J = 8.4 Hz, 4H), 7.122 (d, J = 8.4 Hz, 2H), 7.022 (d, J = 6.6 Hz, 4H), 6.909 (d, J = 2.2 Hz , 4H), 4.405 (t, J = 6.6 Hz, 2H), 3.995 (t, J = 6.6 Hz, 4H), 3.877 (t, J = 6.6 Hz, 8H), 1.811-1.65 (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 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 2929 Manufacture

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 added to a round flask and stirred at 60 ° C. for 3 hours. When compound 28 disappeared by TLC, the reaction was terminated and neutralized to PH7 with 1M HCl. Then, the mixture was extracted with CH ₂ Cl ₂ and distilled water, and the organic layer was dried over sodium sulfate and filtered. The filtrate was evaporated under vacuum and the solid obtained was purified by silica column chromatography (eluent dichloromethane: methanol (10: 1)) to give compound 29 .

¹ H NMR (300 MHz, CDCl ₃ ): δ 10.002 (d, J = 4.4 Hz, 2H), 9.659 (d, J = 4.4 Hz, 2H), 8.941 (d, J = 4.8 Hz), 2H), 8.848 (d, J = 4.8 Hz, 2H), 8.290 (t, J = 8.4 Hz, 2H), 8.164 (d, J = 8.4 Hz, 2H), 7.949 (d, J = 8.6 Hz, 1H), 7.783-7.598 (m, 4H), 7.183 (d, J = 8.4 Hz, 4H), 7.114 (d, J = 8.4 Hz, 2H), 7.014 (d, J = 6.6 Hz, 4H), 6.909 (d, J = 2.2 Hz , 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 ( m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 (m, 16H), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

Example 6 Preparation of Compound 34

Compound

30 was prepared according to ChemSus Chem, Volume 4, Issue 5, pages 591-594, May 23, 2011.

compound 3131 Manufacture

Compound 19 (100mg, 0.09 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1M in THF, 0.35mL, 0.320mmol) were added to a round flask containing THF (40mL) and stirred for 30 minutes. After stirring, the mixture was extracted using distilled water and CH ₂ Cl ₂ , and the organic layer was dried over sodium sulfate. 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 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 = 4.5 Hz, 2H), 8.883 (d, J = 4.5 Hz, 2H), 8.854 ( d, J = 4.5 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 ( m, J = 8.4 Hz, 10H), 7.005 (d, 4H), 6.574 (d, J = 8.4 Hz, 4H), 4.022 (t, J = 6.6 Hz, 8H), 3.858 (t, J = 6.6 Hz, 8H), 1.32-1.20 (m, 16H), 1.01-0.80 (m, 28H), 0.77-0.60 (m, 16H), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 3232 Manufacture

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) were placed in a Schlenk flask. After vacuuming for an hour, add 40 ml of dry toluene. Then add Et ₃ N (90ml, 0.66mmol), add TIPS (Triisopropylsilylacetylene) (30ml, 0.13mmol) and reflux for 12 hours. The solvent was then evaporated and purified by column chromatography to yield 32 (27 mg, 37%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 9.686 (d, J = 4.4 Hz, 2H), 9.648 (d, J = 4.4 Hz, 2H), 8.860 (d, J = 4.8 Hz, 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 (m, J = 8.4 Hz, 4H), 6.996 (d, J = 6.6 Hz, 4H), 6.574 (d, J = 2.2 Hz, 4H), 4.180 (t, J = 6.6 Hz, 8H), 3.966 (t, J = 6.6 Hz, 8H), 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, 16H), 0.60-0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 3333 Manufacture

Compound 32 (80 mg, 0.04 mmol) and TBAF (Tetra-n-butylammonium fluoride) (1M in THF, 0.04 mL, 0.040 mmol) were added to a round flask containing THF (20 mL) and stirred for 30 minutes. After stirring, the mixture was extracted using distilled water and CH ₂ Cl ₂ , and the organic layer was dried over sodium sulfate. 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 refluxed for 12 hours. The solvent was then evaporated and purified by column chromatography to give compound 33 (10 mg, 40%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 10.021 (d, J = 4.4 Hz, 2H), 9.689 (d, J = 4.4 Hz, 2H), 8.960 (d, J = 4.8 Hz), 2H), 8.869 (d, J = 4.8 Hz, 2H), 8.294 (t, J = 8.4 Hz, 2H), 8.157 (d, J = 8.4 Hz, 2H), 7.940 (d, J = 8.6 Hz, 1H), 7.878 (d , 2H), 7.735 (d, J = 8.4 Hz, 4H), 7.538 (d, J = 8.4 Hz, 2H), 7.026 (d, J = 6.6 Hz, 4H), 6.577 (d, J = 2.2 Hz, 4H ), 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), 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 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

compound 3434 Manufacture

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 added to a round flask and stirred at 60 ° C. for 3 hours. When compound 33 disappeared by TLC, the reaction was terminated and neutralized to PH7 with 1M HCl. Then, the mixture was extracted with CH ₂ Cl ₂ and distilled water, and the organic layer was dried over sodium sulfate and filtered. The filtrate was evaporated under vacuum and the solid obtained was purified by silica column chromatography (eluent dichloromethane: methanol (10: 1)) to give compound 34 .

¹ H NMR (300 MHz, CDCl ₃ ): δ 10.015 (d, J = 4.4 Hz, 2H), 9.686 (d, J = 4.4 Hz, 2H), 8.957 (d, J = 4.8 Hz, 2H), 8.866 ( d, J = 4.8 Hz, 2H), 8.292 (d, J = 8.4 Hz, 2H), 8.186 (d, J = 8.4 Hz, 2H), 7.952 (d, J = 8.6 Hz, 1H), 7.875 (d, 2H), 7.735 (t, J = 8.4 Hz, 2H), 7.535 (d, J = 8.4 Hz, 4H), 7.322-7.248 (m, J = 6.6 Hz, 4H), 7.026 (d, J = 2.2 Hz, 4H), 6.577-6.563 (m, J = 2.4 Hz, 4H), 4.025 (t, J = 6.6 Hz, 8H), 3.884 (t, J = 6.6 Hz, 8H), 2.791 (t, J = 6.3 Hz, 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 (m, 16H), 0.60- 0.38 (m, 16H) 0.55 (t, J = 7.3 Hz, 12H)

Spectroscopic evaluation

UV absorption spectra of porphyrin-based dye compounds 12 , 15 , 18 and 23 obtained in Examples 1 to 4 are shown in FIGS. 1 and 3. UV emission spectra of 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] Fabrication and Characterization of Dye-Sensitized Solar Cells

The dye-sensitized solar cell using a porphyrin-based compound was produced as follows.

A dispersion of titanium oxide particles having an average particle diameter of 13 nm on the conductive film made of ITO of the first electrode was applied to an area of 0.25 cm 2 using a doctor blade method, and then subjected to a heat treatment baking process at 450 ° C. for 30 minutes. A microporous membrane was prepared.

Subsequently, the resultant was maintained at 80 ° C., and each of the porphyrin-based compounds obtained in Examples 1 to 4 was immersed in a 0.3 mM dye dispersion dissolved in ethanol to perform dye adsorption for 12 hours or more.

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

Separately, the second electrode deposited a second conductive film made of Pt using a sputter on the first conductive film made of ITO, and made a fine hole using a 0.75 mm diameter drill to inject the electrolyte.

Subsequently, the two electrodes were joined by pressing a support table made of a thermoplastic polymer film having a thickness of 60 μm between the first electrode and the second electrode on which the porous membrane was formed and pressing at 80 ° C. for 16 seconds. Then, an 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 manufacture a dye-sensitized solar cell. In this case, the electrolyte used was 1-methyl-3-propylimidazolium iodide, 0.1M lithium iodide, 0.05M iodine, 0.5M 4-tert-butylpyridine. It was prepared by dissolving in 3-methoxypropionitrile.

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

Table 1

	Porphyrin derivatives	J _sc [mA cm ^-2 ]	V _oc [mV]	FF (%)	η (%)
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, the dye-sensitized solar cells of Examples 5 to 8 have two (C1-C20) alkoxy-substituted phenyl groups introduced at positions 5 and 15 of porphyrin, and at position 10 of porphyrin. It was found that the porphyrin derivatives of Examples 1 to 4 in which one or two (C 1 -C 20) alkoxy-substituted phenyl-substituted arylamino groups were introduced were used as dyes, so that they had excellent light conversion efficiency. Particularly, in Example 8, one or two (C 1 -C 20) alkoxy is substituted at the 10 position of porphyrin in addition to the two (C 1 -C 20) alkoxy substituted phenyl groups introduced at positions 5 and 15 of the porphyrin. Compound 23 having a carbon-carbon triple bond between the arylamino group substituted with phenyl and porphyrin was used as a dye, which showed better light conversion efficiency.

The battery prepared using the porphyrin-based compound according to the present invention is a phenyl derivative substituted with alkoxy, arylamine substituted with alkoxy, or carbon-carbon triple based on a porphyrin dye having high stability against light and heat, having a strong electron donating ability. By introducing the bond, it was found that the dye-sensitized solar cell can be driven with high efficiency.

Claims

Porphyrin derivatives represented by Formula 1 below:

[Formula 1]

In Chemical 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 (C6-C20) arylene, which arylene may be further substituted with (C1-C20) alkyl;

m is an integer of 0 or 1;

A is selected from the following structures;

If n is 0 then B is
ego;

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

R 7 is hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy.
The method of claim 1,

Porphyrin derivatives represented by the following formula (2), (3), (4) or (5):

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

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 claim 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 of claim 2,

L 1 and L 2 are each independently a single bond or a porphyrin derivative selected from the following structures:

R is (C1-C20) alkyl.
The method of claim 2,

Porphyrin derivatives selected from the following structures:
Dye-sensitized solar cell dye comprising a porphyrin-based derivative of any one of claims 1 to 4.
A dye-sensitized solar cell comprising the dye for dye-sensitized solar cell of claim 5.
The method of claim 6,

The dye-sensitized solar cell

A first electrode comprising a conductive transparent substrate;

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

A second electrode disposed to face the first electrode on which the light absorption layer is formed; And

Dye-sensitized solar cell comprising an electrolyte located in the space between the first electrode and the second electrode.