KR102335394B1 - Organic Blue Dyes featuring a Diketopyrrolopyrrole, Preparation Method Thereof, and Dye-sensitized Solar Cells Comprising the Same - Google Patents

Abstract

이고, 여기서 상기 R₃ 및 R₄는 각각 독립적으로, 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 또는 치환 또는 비치환의 C1-C20 알콕시이며;
π'(π' spacer)는 -π'₁-π'₂-이고, 여기서 상기 π'₁ 및 π'₂는 각각 독립적으로 치환 또는 비치환의 C2-C6 알켄, C2 알킨, 치환 또는 비치환의 C4-C10 아릴, 또는 치환 또는 비치환의 C3-C10 헤테로아릴이며;
A'는 앵커링 그룹(Anchoring group)이고;
치환기는 할로겐 원소, 히드록시, C1-C10 알킬, 및 C1-C10 알콕시로 이루어진 군에서 선택되는 하나 이상이며; 및
헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상일 수 있다.
상기 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환의 C1-C5 알킬, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴이며; 여기서 치환기는 C1-C5 알킬, 및 C1-C5 알콕시로 이루어진 군에서 선택되는 하나 이상일 수 있다.
상기 π₁, π₂, π'₁, 및 π'₂는 각각 독립적으로 C2 알킨, 치환 또는 비치환의 C6 아릴, 또는 치환 또는 비치환의 C4-C5 헤테로아릴이며; 여기서 치환기는 C1-C2 알킬 및 C1-C2 알콕시로 이루어진 군에서 선택되는 하나 이상이고; 및 헤테로 원자는 N, O 및 S로 이루어진 군에서 선택된 하나 이상일 수 있다. The present invention is
It provides a method for producing a diketopyrrolopyrrole (DPP)-based organic blue dye represented by the following formula (1) and a dye-sensitized solar cell comprising the same.
D-π-A-π'-A' Formula (1)
In the above formula (1),
D(donor) is (R ₁ )(R ₂ )NC ₆ H ₅ -, wherein R ₁ and R ₂ are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1 -C20 alkoxy, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
π (π spacer) is -π ₁ -π ₂ -, wherein π ₁ and π ₂ are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A is

wherein R ₃ and R ₄ are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted C1-C20 alkoxy;
π'(π' spacer) is -π' ₁ -π' ₂ -, wherein π' ₁ and π' ₂ are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4- C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;
A' is an anchoring group;
the substituent is at least one selected from the group consisting of a halogen atom, hydroxy, C1-C10 alkyl, and C1-C10 alkoxy; and
The hetero atom may be at least one selected from the group consisting of N, O and S.
wherein R ₁ and R ₂ are each independently substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; Here, the substituent may be at least one selected from the group consisting of C1-C5 alkyl, and C1-C5 alkoxy.
π ₁ , π ₂ , π′ ₁ , and π′ ₂ are each independently C2 alkyne, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; wherein the substituent is at least one selected from the group consisting of C1-C2 alkyl and C1-C2 alkoxy; And the hetero atom may be one or more selected from the group consisting of N, O and S.

Description

Organic Blue Dyes featuring a Diketopyrrolopyrrole, Preparation Method Thereof, and Dye-sensitized Solar Cells Comprising the Same}

The present invention relates to a diketopyrrolopy (DPP)-based organic blue dye, a method for preparing the same, and a dye-sensitized solar cell comprising the same, and more particularly, to a diketopyrrolopy (DPP) capable of absorbing up to the near-infrared region. )-based organic blue dye, a manufacturing method thereof, and a dye-sensitized solar cell having excellent photoelectric conversion efficiency including the same.

Recently, as the demand for energy increases, various studies on environmentally friendly solar cells are being conducted.

However, silicon solar cells have a problem of supply and demand of raw materials due to the high production cost of Si, and the battery efficiency is quite insufficient. Interest in dye-sensitized solar cells is increasing.

The dye-sensitized solar cell is a mechanism that generates electron-hole pairs by absorbing the light energy of visible light. Compared to silicon solar cells, the manufacturing cost is lower, and due to its transparent characteristics, it has the advantage of being applicable to glass windows or glass greenhouses on the exterior walls of buildings.

In such a dye-sensitized solar cell, a photosensitizer dye is an important factor in determining stability and light conversion efficiency. However, the conventionally used metal complex-based dye has a problem in that it is not environmentally friendly, including metal, and has a relatively high manufacturing cost.

Accordingly, a non-metallic organic blue dye that has a high molar extinction coefficient and can be easily synthesized and separated, which is highly economical and environmentally friendly, has been proposed as an alternative.

For example, Korean Patent Application Laid-Open No. 10-2010-0136931 is used as a dye-sensitized photoelectric conversion element in a dye-sensitized solar cell and exhibits improved molar extinction coefficient, Jsc (single-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes. An organic blue dye capable of greatly improving the efficiency of a solar cell is disclosed.

However, the conventional organic blue dyes as described above have a problem in that the long-term stability is not good and the solar cell does not exhibit sufficient power conversion efficiency when it is used as an optical sensor.

Korean Patent Publication No. 10-2010-0136931

An object of the present invention is to solve the problems of the prior art as described above and the technical problems that have been requested from the past.

An object of the present invention is to provide an organic blue dye based on diketopyrrolopy (DPP) that can absorb up to the near infrared region.

Another object of the present invention is to provide a method for manufacturing a diketopyrrolopy (DPP)-based organic blue dye simply and efficiently.

Another object of the present invention is to provide a dye-sensitized solar cell having excellent photoelectric conversion efficiency including the organic blue dye.

The present invention is

It provides an organic blue dye based on diketopyrrolopyrrole (DPP) represented by the following formula (1).

D-π-A-π'-A' Formula (1)

In the above formula (1),

D(donor) is (R ₁ )(R ₂ )NC ₆ H ₅ -, wherein R ₁ and R ₂ are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1 -C20 alkoxy, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;

π (π spacer) is -π ₁ -π ₂ -, wherein π ₁ and π ₂ are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;

이고, 여기서 상기 R₃ 및 R₄는 각각 독립적으로, 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 또는 치환 또는 비치환의 C1-C20 알콕시이며;A is

wherein R ₃ and R ₄ are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted C1-C20 alkoxy;

π'(π' spacer) is -π' ₁ -π' ₂ -, wherein π' ₁ and π' ₂ are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4- C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;

A' is an anchoring group;

the substituent is at least one selected from the group consisting of a halogen atom, hydroxy, C1-C10 alkyl, and C1-C10 alkoxy; and

The hetero atom may be at least one selected from the group consisting of N, O and S.

wherein R ₁ and R ₂ are each independently substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; Here, the substituent may be at least one selected from the group consisting of C1-C5 alkyl, and C1-C5 alkoxy.

π ₁ , π ₂ , π′ ₁ , and π′ ₂ are each independently C2 alkyne, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl; wherein the substituent is at least one selected from the group consisting of C1-C2 alkyl and C1-C2 alkoxy; And the hetero atom may be at least one selected from the group consisting of N, O and S.

wherein R ₃ and R ₄ are each independently hydrogen, or substituted or unsubstituted C1-C10 alkyl; Here, the substituent may be at least one selected from the group consisting of C1-C5 alkyl.

The anchoring group may be at least one selected from the group consisting of cyanoacrylic acid anchors, Catechol anchors, Pyridyl anchors, Phosphonate anchors, 2-Hydroxylbenzonitrile anchors, Pyridine-N-oxide anchors, Hydroxamate anchors and Sulfonate anchors. have.

The organic blue dye may be at least one or two of Formulas (1-1) and (1-2).

화학식 (1-1)

Formula (1-1)

화학식 (1-2)

Formula (1-2)

On the other hand, the present invention is a method for producing an organic blue dye of formula (1),

(A) preparing D-π-A-π'-CHO through Sonogashira coupling reaction of D-π ₁ and X-π ₂ -A-π' ₁ -π' _{2 -CHO;} and

(B) coupling an anchoring group to the end through Knoevenagel condensation reaction of D-π-A-π'-CHO prepared in step (a) (in the above, π, π ₁ , π ₂ , A, π', π' ₁ , and π' are as defined in claim 1, and X is a halogen element); provides a manufacturing method comprising:

D-π-A-π'-A' Formula (1)

형 태양전지를 제공한다.On the other hand, the present invention is a dye, characterized in that it contains the organic blue dye.

type solar cell.

The organic blue dye based on diketopyrrolopy (DPP) having a D-π-A-π'-A' structure according to the present invention has excellent power-conversion efficiency and can be absorbed up to the near-infrared region. . In addition, it is eco-friendly, has a low manufacturing cost, and has excellent long-term stability.

Such a diketopyrrolopy (DPP)-based organic blue dye can be synthesized in a simple and efficient way, and a high-efficiency dye-sensitized solar cell can be manufactured using it.

1 is a schematic cross-sectional view of a dye-sensitized solar cell including an organic blue dye according to the present invention;
2 is a result of measuring UV-vis absorption spectra of CSD-08 of Example 1 and CSD-09 of Example 2 in Experimental Example 1;
3 is a current density-voltage (JV) characteristic of a solar cell using CSD-08 of Example 1 and CSD-09 of Example 2 in Experimental Example 2; and
FIG. 4 shows the measurement of External Quantum Efficiency (EQE) of solar cells using CSD-08 of Example 1 and CSD-09 of Example 2 in Experimental Example 3, and is shown in FIG. 4 below.

Organic blue dye based on diketopyrrolopyrrole (DPP)

As described above, photosensitizer dyes are a major factor in determining the stability and light conversion efficiency of dye-sensitized solar cells, and numerous non-metal organic blue dyes such as coumarin-based, fluorine-based, polypyridyl-based, and porphyrin-based dyes have been used in the past. has been developed The non-metallic organic blue dye has a low manufacturing cost and is environmentally friendly, but exhibits a limited absorption region with a typical donor-π conjugation spacer-acceptor (D-π-A) structure, resulting in low energy conversion efficiency. indicated.

Accordingly, the inventors of the present invention, as described later after continuing in-depth research and various experiments, a diketopyrrolopy-based donor-pi binding spacer-acceptor-pi binding spacer'-acceptor' (donor-π conjugation) The non-metallic organic blue dye with the spacer-acceptor-π conjugation spacer'-acceptor', D-π-A-π'-A') structure shows high light conversion efficiency and long-term stability. It was confirmed that it can be prepared, the present invention has been completed based on these findings.

Specifically, the present invention,

It provides an organic blue dye based on diketopyrrolopyrrole (DPP) represented by the following formula (1).

D-π-A-π'-A' Formula (1)

In the above formula (1),

D(donor) is (R ₁ )(R ₂ )NC ₆ H ₅ -, wherein R ₁ and R ₂ are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1 -C20 alkoxy, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;

π (π spacer) is -π ₁ -π ₂ -, wherein π ₁ and π ₂ are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4-C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;

이고, 여기서 상기 R₃ 및 R₄는 각각 독립적으로, 수소, 할로겐 원소, 치환 또는 비치환의 C1-C20 알킬, 또는 치환 또는 비치환의 C1-C20 알콕시이며;A is

wherein R ₃ and R ₄ are each independently hydrogen, a halogen atom, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted C1-C20 alkoxy;

π'(π' spacer) is -π' ₁ -π' ₂ -, wherein π' ₁ and π' ₂ are each independently a substituted or unsubstituted C2-C6 alkene, C2 alkyne, substituted or unsubstituted C4- C10 aryl, or substituted or unsubstituted C3-C10 heteroaryl;

A' is an anchoring group;

the substituent is at least one selected from the group consisting of a halogen atom, hydroxy, C1-C10 alkyl, and C1-C10 alkoxy; and

The hetero atom is at least one selected from the group consisting of N, O and S.

On the other hand, the terminology of the present specification will be described below.

The term “alkyl” refers to an aliphatic hydrocarbon group. In the present invention, alkyl is "saturated alkyl" meaning that it does not contain any alkene or alkyne moiety, and "unsaturated alkyl" means that it contains at least one alkene or alkyne moiety. It is used as a concept including all of them, and in detail, may be "saturated alkyl". The alkyl may include branched, straight-chain or cyclic, and also includes structural isomers, so, for example, in the case of C3 alkyl, it may mean propyl or isopropyl.

The term “alkoxy” refers to an alkyl group as described above attached through an oxygen linkage (—O—).

The term "aryl" refers to an aromatic substituent having at least one ring with a shared pi electron system. The term includes monocyclic or polycyclic (ie, rings that share adjacent pairs of carbon atoms) groups. When substituted, the substituent may be appropriately bonded at ortho (o), meta (m), or para (p) positions.

The term "heteroaryl" is a substituent in which part of the aryl ring as described above is substituted with oxygen, nitrogen, sulfur, or the like.

The term “halogen element” is an element belonging to group 17 of the periodic table, and specifically, may be fluorine, chlorine, bromine, or iodine.

The organic blue dye based on diketopyrrolopies according to the present invention is a donor-pi bonding spacer-acceptor-pi bonding spacer'-acceptor' (donor-π conjugation spacer-acceptor-π conjugation spacer'-acceptor', D-π -A- π'-A') structure, including two-terminated pi-bonded spacers, in which the receptor (A) and the receptor' (A') are connected, respectively.

In the diketopyrrolopy-based organic blue dye, the donor (D) contributes to intramolecular charge translation (ICT), and the acceptor (A) is an electron with strong electron pulling due to two lactam groups. It shows a shortage phenomenon and the acceptor '(A') acts as an electron trap. This structure promotes the separation of charges and the movement of electrons in the organic blue dye structure, so it can exhibit high light conversion efficiency and long-term stability.

In addition, as will be seen below, the organic blue dye based on diketopyrrolophy according to the present invention has excellent absorption rates in the red light and near-infrared regions, and thus can be preferably used as a blue dye.

In the diketopyrrolopy-based organic blue dye represented by Formula (1) according to the present invention, R ₁ and R ₂ are each independently a substituted or unsubstituted C1-C5 alkyl, a substituted or unsubstituted C6 aryl, or A substituted or unsubstituted C4-C5 heteroaryl, wherein the substituent may be at least one selected from the group consisting of C1-C5 alkyl, and C1-C5 alkoxy.

π ₁ , π ₂ , π′ ₁ , and π′ ₂ are each independently C2 alkyne, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C4-C5 heteroaryl, wherein the substituents are C1-C2 alkyl and C1 -C2 is at least one selected from the group consisting of alkoxy; And the hetero atom may be at least one selected from the group consisting of N, O and S.

R ₃ and R ₄ are each independently hydrogen, or a substituted or unsubstituted C1-C10 alkyl, wherein the substituent may be one or more selected from the group consisting of C1-C5 alkyl.

The anchoring group may be at least one selected from the group consisting of cyanoacrylic acid anchors, Catechol anchors, Pyridyl anchors, Phosphonate anchors, 2-Hydroxylbenzonitrile anchors, Pyridine-N-oxide anchors, Hydroxamate anchors and Sulfonate anchors. have. The structure of the anchoring group is known in the art, for example, Anchoring Groups for Dye-Sensitized Solar Cells, Lei Zhang?? and Jacqueline M. Cole, ACS Appl. Mater. Interfaces 2015, 7, 3427-3455.

Specifically, in the present invention, the anchoring group may be a cyanoacrylic acid anchor represented by one of the following structural formulas.

The diketopyrrolopy-based organic blue dye according to the present invention may be represented by the following Chemical Formulas (1-1), (1-2), or (1-1) and (1-2).

화학식 (1-1)

Formula (1-1)

화학식 (1-2)

Formula (1-2)

This organic blue dye can be used as a blue dye because it has excellent absorption in red light and near-infrared regions.

Diketopyrrolopy-based organic blue dye manufacturing method

Hereinafter, a method for preparing a diketopyrrolopy-based organic blue dye compound according to the present invention will be described.

The present invention is an organic blue dye based on diketopyrrolopy represented by formula (1),

(A) preparing D-π-A-π'-CHO through Sonogashira coupling reaction of D-π ₁ and X-π ₂ -A-π' ₁ -π' _{2 -CHO;} and

(B) coupling an anchoring group to the end through Knoevenagel condensation reaction of D-π-A-π'-CHO prepared in step (a) (in the above, π, π ₁ , π ₂ , A, π′, π′ ₁ , and π′ are as defined in claim 1 , and X is a halogen element);

It can be prepared including

D-π-A-π'-A' Formula (1)

As a catalyst in step (a), Pd(PPh ₃ ) ₂ Cl ₂ , Pd(PPh ₃ ) ₄ , Pd(PPh ₃ ) ₂ Br ₂ , Co(PPh ₃ ) ₂ Cl ₂ , Co (PPh ₃ ) ₄ , And Co(PPh ₃ ) ₂ Br ₂ One selected from the group consisting of may be used, but is not limited thereto. These catalysts can be used together with CuI, PPh _{3 .}

In step (b), the anchoring group is coupled to the end of D-π-A-π'-CHO through Knoevenagel condensation reaction. This can be carried out using an amine such as piperidine, and an organic acid such as formic acid and acetic acid in a reaction solvent such as dichloromethane, 1,2-dichloroethane, acetonitrile, tetrahydrofuran, ethyl ether, benzene, and toluene. .

In step (b), the anchoring group is as defined above.

Dye-sensitized solar cell

1 is a schematic cross-sectional view of a dye-sensitized solar cell including an organic blue dye according to the present invention.

1, the present invention provides a dye-sensitized solar cell including the organic blue dye.

The dye-sensitized solar cell includes a first electrode 100 , an electrolyte layer 200 formed on the first electrode 100 , and a second electrode 300 formed on the electrolyte layer 200 . .

Each of the first electrode 100 and the second electrode 300 may be a transparent electrode, for example, a conductive metal oxide, metal, metal alloy, or carbon material. Specifically, indium tin oxide (ITO), fluorine tin oxide (FTO), indium zinc oxide (ISO), antimontine oxide (ATO), fluorine doped tin oxide (FTO), platinum nanoparticles are formed FTO, SnO ₂ , ZnO, or a combination thereof; It may be platinum, silver, gold, or copper iodide, but is not limited thereto.

The electrolyte layer 200 may use a redox electrolyte. Specifically, as the electrolyte, a halogen redox electrolyte composed of a halogen compound and halogen molecules, a metal redox electrolyte such as a metal complex such as ferrocyanate-ferrocyanate, ferrocene-ferricinium ion, or cobalt complex , alkylthiol-alkyldisulfide, viologen dye, an organic redox electrolyte such as hydroquinone-quinone, and the like, and preferably a halogen redox electrolyte.

In addition, the halogen molecule may be an iodine molecule, and as the halogen compound, a _{metal halide salt such as LiI, NaI, CaI 2} , MgI ₂ , CuI, or an organic halogen such as tetraalkylammonium iodine, imidazolium iodine, pyridium iodine, etc. It may be an ammonium salt, or I ₂

In addition, the redox electrolyte may be configured in the form of a solution containing the same. In this case, as a solvent constituting the solution, a cell-chemically inactive solvent may be used. For example, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate , 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like. Specifically, it may be acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone, and these solvents are one type or can be mixed

The electrolyte layer 200 may include a semiconductor material 210 and an organic blue dye 220 according to the present invention. In the electrolyte layer 200, the semiconductor material 210 and the organic blue dye 220 may have a simple mixture or a structure coated and adsorbed on any one material. Specifically, the semiconductor material 210 has a maximum The organic blue dye 220 , which generates excitation electrons by absorbing light up to a near-infrared region of 600 to 700 nm and exhibits blue color, may be adsorbed.

The semiconductor material 210 may use a metal oxide selected from the group consisting of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, and vanadium, specifically titanium oxide, tin oxide, It may be zinc oxide, niobium oxide, strontium titanium oxide, or a mixture thereof.

The absorption characteristics of the solar cell are affected by the incident photonto-current conversion efficiency (IPCE) or light-harvesting efficiency (LHE) according to the absorption wavelength of the organic blue dye used. Therefore, the sensitized solar cell according to the present invention, including a photoelectrode carrying an organic blue dye with high light collection efficiency, has high absorption rates in red light and infrared region, and shows blue color and high energy conversion efficiency.

Hereinafter, the present invention will be described in detail through Examples, but the following Examples and Experimental Examples are merely illustrative of one aspect of the present invention, and the scope of the present invention is not limited by the Examples and Experimental Examples .

The synthesizing process of diketopyrrolopy-based organic blue dye according to the present invention is shown below.

Example 1 Synthesis of CSD-08 (Formula 1-1)

compound 2

In a 3-neck flask, π-spacer (1.8 g, 2.54 mmol), TEA/toluene (30 mL/30 mL), Pd(PPh ₃ ) ₂ Cl ₂ (0.09 g, 0.127 mmol), PPh ₃ (0.013 g, 0.05) mmol), CuI (0.046 g, 0.1 mmol) and 4-ethynyl-N,N-dimethylaniline (0.55 g, 3.82 mmol) were added and refluxed for 5 hr under nitrogen condition. When the reaction is complete, water (250 mL) and MC (2 Х 250 mL) are added at room temperature to move the product to the organic layer, and the product is extracted _{to remove moisture with MgSO 4 ,} and then the solvent is distilled off. The obtained solution was purified by column chromatography using silica gel to obtain an indigo blue solid (1.3 g). (66.17 %) ¹ H NMR (300 MHz, Chloroform-d) δ 10.04 (s, 1H), 8.97 (dd, J = 12.8, 4.2 Hz, 2H), 7.94 (d, J = 8.0 Hz, 2H), 7.83 (d, J = 8.1 Hz, 2H), 7.60 (d, J = 4.1 Hz, 1H), 7.42 (d, J = 8.6 Hz, 2H), 7.31 (s, 1H), 6.67 (d, J = 8.6 Hz, 2H), 3.02 (s, 6H), 2.03 (d, J = 6.5 Hz, 2H), 1.60 (s, 4H), 1.25 (s, 16H), 0.88 (s, 12H). ¹³ C NMR (75 MHz, CDCL ₃ )δ 217.71, 197.58, 189.16, 176.87, 169.96, 163.46, 158.31, 155.36, 149.62, 140.99, 133.73, 133.73, 129.32, 127.18, 125.96, 118.54, 108.3739 112.54, 106.39 112. , 103.53, 103.17, 99.12, 98.43, 95.93, 94.66, 79.20, 78.96, 78.23, 77.80, 77.38, 76.87, 76.46, 76.40, 74.03, 72.78, 69.76, 62.78, 57.51, 30.78, 29.08, 14.86, 30.78, 40.86. , 11.15, -3.74.; HRMS m/z (FAB) calc. for C ₄₇ H ₅₃ N ₃ O ₃ S ₂ [M+]: 771.3528, found: 771.3533.

CSD-08

In a 2-neck flask, add Compound 2 (1.3 g, 1.684 mmol), 2-cyanoacetic acid (215 mg, 2.526 mmol) , ammonium acetate (1 g, 12.967 mmol) and acetic acid (130 mL) at 90 °C. React for 6-8 hours. When the reaction is complete, the solution is cooled at room temperature and poured into water. When a precipitate was formed in water, it was filtered to obtain 1.06 g of an indigo blue solid (75 %). ¹ H NMR (300 MHz, Chloroform-d) δ 8.84 (s, 2H), 7.90 (d, J = 9.1 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.56 (s, 1H), 7.36 (d, J = 9.2 Hz, 2H), 6.67 (d, J = 9.5 Hz, 2H), 4.03 (s, 4H), 3.07 - 2.95 (m, 7H), 2.52 (d, J = 5.5 Hz, 2H) ), 1.36 (s, 9H), 1.26 (s, 13H), 0.94 - 0.82 (m, 16H). ¹³ C NMR (75 MHz, CDCL3) δ 164.39, 161.32, 126.66, 126.62, 126.59, 126.53, 126.43, 112.78, 84.18, 81.73, 81.60, 81.08, 80.90, 80.86, 80.40, 80.17, 80.27, 80.17, 79.95 79.69, 79.56, 79.41, 79.27, 79.22, 79.21, 79.19, 79.17, 79.09, 78.01, 77.58, 77.16, 75.24, 75.19, 74.22, 73.41, 73.33, 65.12, 56.51, 40.77, 40. 23.54, 22.10, 16.78, 14.60, 14.53, 14.47, 11.00, 10.92.; HRMS m/z (FAB) calc. for C ₅₀ H ₅₄ N ₄ O ₄ S ₂ [M+]: 838.3586, found: 838.3590.

Example 2 Synthesis of CSD-09 (Formula 1-2)

compound 3

In a 3-neck flask, π-spacer (2.1 g, 2.974 mmol), Pd(PPh ₃ ) ₂ Cl ₂ (0.104 g, 0.149 mmol), PPh3 (0.016 g, 0.06 mmol), and 4-butoxy-N-(4 -butoxyphenyl)-N-(4-ethynylphenyl)benzenamine (1.845 g, 4.461 mmol) was added and refluxed for 5 hr under nitrogen condition. When the reaction is complete, water (250 mL) and MC (2Х250 mL) are added at room temperature to move the product to the organic layer, and the product is extracted _{to remove moisture with MgSO 4 ,} and then the solvent is distilled off. The solution thus obtained was purified through column chromatography using silica gel to obtain an indigo blue solid (1.6 g). (51.71%) ¹ H NMR (300 MHz, Chloroform-d) δ 8.95 (d, J = 2.9 Hz, 1H), 7.98 - 7.80 (m, 1H), 7.61 (s, 1H), 7.32 (s, 7H) , 7.08 (d, J = 8.9 Hz, 3H), 6.91 (s, 1H), 6.85 (d, J = 9.0 Hz, 7H), 3.94 (s, 4H), 2.17 (s, 2H), 1.98 - 1.96 ( m, 8H), 1.57 (s, 9H), 1.25 (s, 11H), 0.87 (s, 10H). ¹³ C NMR (75 MHz, CDCL ₃ ) δ 221.27, 177.04, 160.45, 156.36, 150.68, 147.69, 133.49, 127.35, 123.71, 119.85, 118.84, 112.85, 93.05, 82.12, 84.09, 82.52, 82.65, 82.76, 82.65 , 82.31, 82.05, 81.77, 81.63, 81.05, 80.91, 80.84, 80.80, 80.77, 80.74, 80.52, 80.43, 80.34, 80.23, 80.14, 80.06, 79.94, 79.83, 79.79, 77.16, 76.73. , 73.27, 71.42, 71.23, 70.77, 70.33, 70.21, 69.56, 69.24, 68.97, 68.64, 65.69, 61.94, 60.68, 57.36, 44.46, 41.82, 31.59, 31.35, 29.36, 29.31, 24.27, 22.34, 10.93. HRMS m/z (FAB) calc. for C ₆₅ H ₇₃ N ₃ O ₅ S ₂ [M+]: 1039.4992, found: 1039.4998.

CSD-09

Compound 3 (1.6 g, 1.538 mmol), 2-cyanoacetic acid (196 mg, 2.307 mmol)), ammonium acetate (912 mg, 11.843 mmol) and acetic acid (160 mL) were added to a 2-neck flask at 90 °C. react for 6-8 hours. When the reaction is complete, the solution is cooled at room temperature and poured into water. When a precipitate was formed in water, it was filtered to obtain 1.45 g of an indigo blue solid (85.18 %). ¹ H NMR (300 MHz, Chloroform-d) δ 8.80 (s, 1H), 8.08 (s, 1H), 7.93 (s, 2H), 7.71 (d, J = 7.3 Hz, 2H), 7.59 (s, 1H) ), 7.28 (s, 1H), 7.18 (s, 1H), 7.06 (d, J = 8.0 Hz, 4H), 6.83 (d, J = 8.9 Hz, 8H), 4.03 (s, 2H), 3.94 (t) , J = 6.0 Hz, 5H), 2.50 (s, 1H), 1.88 (s, 2H), 1.82 - 1.69 (m, 6H), 1.34 (s, 8H), 1.27 (s, 7H), 0.97 (t, J = 7.3 Hz, 8H), 0.93 - 0.83 (m, 14H). ¹³ C NMR (75 MHz, CDCL3) δ 206.87, 204.40, 201.09, 190.24, 189.39, 174.94, 167.59, 147.57, 142.82, 140.96, 127.51, 127.49, 126.06, 119.10, 115.58, 115.55, 111.53, 109.112. 107.07, 100.73, 96.07, 95.49, 95.34, 94.56, 89.82, 85.68, 83.06, 81.82, 77.58, 77.16, 76.74, 74.23, 71.46, 69.46, 68.05, 63.95, 63.08, 59.69, 59.81, 58.28 54.96, 41.97, 38.01, 33.81, 32.69, 31.44, 26.86, 24.64, 23.13, 23.09, 22.38, 21.98, 20.86, 20.33, 19.66, 19.55, 19.32, 17.93, 14.82, 14.15, 13.93, 12.92, 9.62, 2.69, 0.43, 0.03.; HRMS m/z (FAB) calc. for C ₆₈ H ₇₄ N ₄ O ₆ S ₂ [M+]: 1106.5050, found: 1106.5061.

<Experimental Example 1>

UV-vis absorption spectra of CSD-08 of Example 1 and CSD-09 of Example 2 were measured and shown in FIG. 2 below. Specifically, each was dissolved in dimethylformamide (DMF) and then measured.

In the case of CSD-08 and CSD-09, it can be seen that the ^{maximum light absorption wavelength (molar extinction coefficient (M -1} ·cm ^{-1 )) is shown at 615 nm (13,708) and 625 nm (14,215).} It can be seen that the molar extinction coefficient of CSD-09 is slightly higher.

<Experimental Example 2>

A fuel-sensitized solar cell was manufactured using CSD-08 of Example 1 and CSD-09 of Example 2

A dye-sensitized solar cell was manufactured by sealing the first electrode (photocathode) and the second electrode (counter electrode) in correspondence with each other, and filling an electrolyte between the first electrode and the second electrode.

Each of the electrodes was prepared on a glass substrate. At this time, the first electrode is composed of fluorine-doped tin oxide (FTO) coated with titanium dioxide (TiO2) nanoparticles, and the second electrode is FTO with platinum (Pt) nanoparticles formed thereon. , and an iodine-based liquid electrolyte (Solaronics AN-50) was used as the electrolyte.

(Before sealing) CSD-08 and CSD-09 were respectively adsorbed to TiO2 of the first electrode.

(Before sealing) Two holes for electrolyte injection were formed in a specific portion of the second electrode.

Then, a barrier rib with a thickness of about 25 μm was placed between the first electrode and the second electrode, and heat and pressure were applied to seal it. As the barrier rib material, Surlyn manufactured by Solaronix was used. Then, an electrolyte solution was filled in the space between the two electrodes through the micropores formed on the surface of the second electrode and the holes were sealed to prepare a dye-sensitized solar cell according to the present invention.

In this way, the current density-voltage (J-V) characteristics of the solar cells manufactured with CSD-08 and CSD-09 were measured, and the photovoltaic cell characteristics were evaluated, and are shown in FIG. 3 and Table 1 below.

Voc (V) Jsc (mA/cm2) F.F. (%) PCE (%) Example 1 (CSD-08) 0.510 10.02 62.5 3.20 Example 2 (CSD-09) 0.535 10.08 59.9 3.24

<Experimental Example 3>

In Experimental Example 2, the external quantum efficiency (External Quantum Efficiency, EQE) of the solar cells manufactured with CSD-08 and CSD-09 was measured and shown in FIG. 4 below.

According to FIG. 4 , in the wavelength range of 400 to 700 nm of visible light, it was confirmed that it was 40% or more, and it was confirmed that power generation was possible even in the near-infrared region.

Claims (8)

Diketopyrrolopyrrole (DPP)-based organic blue dye, characterized in that it is represented by at least one or two of the following formulas (1-1) and (1-2):

Formula (1-1)

Formula (1-2) delete delete delete delete delete delete A dye-sensitized solar cell comprising the organic blue dye according to claim 1 .

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