KR20130134913A - Novel compound, polymer compounds that contain them, and organic solar cells containing the same - Google Patents

Abstract

The present invention relates to a novel compounds, that is a phenazine derivative, namely, phenazine derivatives and a method of producing the same. The polymeric compound by using the compound of the present invention as a unit and organic solar cells including polymeric compounds are also provided. The compound of the present invention has side chains increasing solubility useful for a solution process basis and organic solar cells according to the present invention have high efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, a polymer compound containing the compound, and an organic solar cell containing the compound,

The present invention relates to a novel compound, a polymer compound containing the same, and an organic solar cell containing the same. More particularly, the present invention relates to a novel electron donor compound, a method for producing the same, and a polymer compound containing a novel electron donor compound as a unit And an organic solar cell containing such a polymer compound.

Solar cells are devices that directly convert light energy into electrical energy. They are made of various kinds of materials, but the most widely used material is monocrystalline Si.

However, monocrystalline Si solar photovoltaic cells are limited in their production cost and manufacturing cost because they can no longer lower the production cost, and thin film solar cells have been actively developed recently.

The dual organic solar cell has advantages such as being flexible, large-sized, light, and inexpensive, and so much research is being conducted in this field. Organic solar cells consist largely of both electrodes and photoactive layer. The photoactive layer can be divided into an electron donor material and an electron acceptor material, and the electron donor material is divided into a single molecule and a polymer. In the case of monomolecular materials, phthalocyanine based CuPc and ZnPc are stacked one after another by thermal deposition. On the other hand, polymers are typically used for PPV (poly (para-phenylene vinylene)) and PF (polyfluorene) materials. Recently, polymer materials with low band gap energy such as PFDTBT and PCPDTBT have been studied by alternately polymerizing the electron donor / acceptor Unlike single-molecule materials, polymers use spin coating, ink-jet printing, and gravure printing. They can be easily processed at room temperature.

The principle of polymer solar cells is that the polymer as an electron donor material absorbs light to form an exciton, and excitons are separated from the electron donor / acceptor interface, which is divided into electrons and holes. The separated electrons and holes move to the respective electrodes to produce electricity.

That is, the development of an electron donor material having a low band gap energy can utilize more solar energy and form more excitons, which is a good way to increase the solar efficiency. P3HT (Eg = 1.9 eV ~ 2.0 eV), which has been investigated so far, shows a limitation in efficiency due to inconsistency with the solar spectrum. Therefore, many researchers have maintained the direction of the polymer to develop materials having lower band gap energy , And the conjugation length is being increased. For example, Korean Patent Laid-Open Publication No. 2011-0098303 can be cited.

However, it is still required to study materials for high heat and chemical stability and high efficiency.

Korean Patent Publication No. 2011-0098303

The present invention provides novel compounds and processes for their preparation.

The present invention also provides a polymer compound prepared using a novel compound as a unit and an organic solar cell containing the same.

The present invention provides novel compounds, i.e., phenazine derivatives, and processes for their preparation.

The phenazine derivative of the present invention is represented by the following formula (1).

[Formula 1]

[In the above formula (1)

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, ≪ / RTI > and a silyl group,

and n and m are integers of 0 to 4.]

Preferably, in the formula (I), wherein R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ Alkyl or C ₁ -C ₂₀ alkoxy, n and m may be an integer of 0 to 2, and more preferably Z may be S.

      The present invention also provides a method for preparing a phenazine derivative, which comprises reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) to prepare a compound represented by the following formula (4)

Reacting a compound represented by the following formula (4) with a compound represented by the following formula (5) to prepare a compound represented by the following formula (6); And

Reacting a compound represented by the following formula (6) with a compound represented by the following formula (7) to prepare a compound represented by the formula (1).

[Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

R-OA

[Chemical Formula 6]

[Formula 7]

[In Formulas 1 to 7,

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >

X is halogen;

A is hydrogen or a paratoluenesulfonyl group;

n and m are integers of 0 to 4]

Preferably, in the process for producing a phenazine derivative of the present invention, Z is S; R may be a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkylcarbonyl group, or a C ₆ -C ₂₀ arylcarbonyl group.

The present invention also provides a polymer compound comprising a phenazine derivative represented by the above formula (1) as a unit.

Specifically, the polymer compound according to one embodiment of the present invention can be represented by the following general formula (11).

[Formula 11]

[In Formula 11,

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >

T is C ₆ -C ₂₀ arylene or C ₃ -C ₂₀ heteroarylene;

n and m are integers of from 0 to 4;

and s is an integer of 1 to 500.]

More specifically, in Formula 11 according to an embodiment of the present invention, T may be one or more selected from the following structures.

[In the above formula,

Z is S or Se;

R 'and R " are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl or C ₆ -C ₂₀ aryl C ₁ -C ₂₀ alkyl;

R ₁₁ to R ₁₄ are independently, hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ ahreu C ₁ -C ₂₀ alkyl together, R 'and R "alkyl group, Aryl, heteroaryl and aralkyl and the alkyl, alkoxy and aralkyl of R ₁₁ to R ₁₄ are independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy , An amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group;

o, p and q are integers from 1 to 2.]

Preferably, Formula 11 according to an embodiment of the present invention may be selected from the following formulas.

[In the above formula,

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >

R ₁₁ to R ₁₂ are independently of each other hydrogen, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl;

The alkyl group, alkoxy and aralkyl of R ₁₁ to R ₁₂ are independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, Which may be further substituted with one or more substituents selected from halogen, cyano, nitro, trifluoromethyl and silyl groups;

n and m are integers of from 0 to 4;

and s is an integer of 1 to 500.]

The present invention also provides a substrate; A first electrode and a second electrode formed on the substrate; And a photoactive layer formed on the first electrode and the second electrode and containing the polymer compound according to the present invention.

The compound of the present invention has a self-assembly ability as a phenazine derivative and has advantages of being applicable to a solution process based on its side chain and high solubility as well as charge mobility and also being able to be used as a unit for polymer synthesis .

In addition, the organic solar cell containing the polymer compound prepared by using the compound according to the present invention has high charge mobility and the organic solar cell containing the polymer compound according to the present invention has excellent efficiency and performance.

1 is a schematic diagram showing an example of an organic solar cell manufactured according to the present invention.
FIG. 2 is a graph showing the thermogravimetric analysis (TGA) of the polymeric compound prepared in Example 21 and Example 22. FIG.

The present invention provides a phenazine derivative which is an electron donor compound which can be used for an organic solar cell suitable for a solution process because of its high charge mobility and high solubility.

The phenazine derivative of the present invention is represented by the following formula (1).

[Formula 1]

[In the above formula (1)

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, ≪ / RTI > and a silyl group,

and n and m are integers of 0 to 4.]

The phenazine derivative of the present invention has a high charge mobility due to the fusion of a pyrazine ring between two benzene rings. When applied to a photoactive layer of an organic solar cell employing the polymer compound employing the same, the organic solar cell has high efficiency, In addition, solubility is increased by introduction of a side chain into a benzene ring of a phenazine derivative, which is advantageous for a solution process.

Preferably, R is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkylcarbonyl group, or a C ₆ -C ₂₀ arylcarbonyl group, which is a phenazine derivative according to an embodiment of the present invention, Alkyl, aryl and aralkyl may be further substituted with C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ alkoxy, n and m may be integers from 0 to 2, more preferably, Z may be S .

The phenazine derivative of the present invention may be prepared by reacting a compound represented by the following formula (2) and a compound represented by the following formula (3)

Reacting a compound represented by the following formula (4) with a compound represented by the following formula (5) to prepare a compound represented by the following formula (6); And

Reacting a compound represented by the following formula (6) with a compound represented by the following formula (7) to prepare a compound represented by the formula (1).

[Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

R-OA

[Chemical Formula 6]

[Formula 7]

[In Formulas 1 to 7,

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >

X is halogen;

A is hydrogen or a paratoluenesulfonyl group;

n and m are integers of 0 to 4]

Preferably, in the process for producing a phenazine derivative of the present invention, Z is S; R may be a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkylcarbonyl group, or a C ₆ -C ₂₀ arylcarbonyl group.

The present invention also provides a polymer compound comprising a compound represented by the above formula (1) as a unit.

The polymer compound comprising the compound of the present invention as a unit is provided as a photoactive layer of an organic solar cell and has high efficiency.

Specifically, the polymer compound according to one embodiment of the present invention can be represented by the following general formula (11).

[Formula 11]

[In Formula 11,

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >

T is C ₆ -C ₂₀ arylene or C ₃ -C ₂₀ heteroarylene;

n and m are integers of from 0 to 4;

and s is an integer of 1 to 500.]

More specifically, in Formula 11 according to an embodiment of the present invention, T may be one or more selected from the following structures.

[In the above formula,

Z is S or Se;

R 'and R " are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl or C ₆ -C ₂₀ aryl C ₁ -C ₂₀ alkyl;

R ₁₁ to R ₁₄ are independently, hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ ahreu C ₁ -C ₂₀ alkyl together, R 'and R "alkyl group, Aryl, heteroaryl and aralkyl and the alkyl, alkoxy and aralkyl of R ₁₁ to R ₁₄ are independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy , An amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group;

o, p and q are integers from 1 to 2.]

Preferably, Formula 11 according to an embodiment of the present invention may be selected from the following formulas.

[In the above formula,

Z is S or Se;

R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >

R ₁₁ to R ₁₂ are independently of each other hydrogen, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl;

The alkyl group, alkoxy and aralkyl of R ₁₁ to R ₁₂ are independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, Which may be further substituted with one or more substituents selected from halogen, cyano, nitro, trifluoromethyl and silyl groups;

n and m are integers of from 0 to 4;

and s is an integer of 1 to 500.]

The present invention also provides a substrate; A first electrode and a second electrode formed on the substrate; And a photoactive layer formed on the first electrode and the second electrode and containing the polymer compound according to the present invention.

The photoactive layer containing the polymer compound of the present invention can be realized in various forms. The polymer compound according to the present invention can be used as an electron donor material in a one-layer structure of a mixed layer with various electron acceptor materials, And a two-layer structure in which electron acceptor materials are stacked on each other.

The electron acceptor materials of the present invention include, but are not limited to, [6,6] -phenyl-C61-butyric acid methyl ether (PCBM), [6,6] 6] -phenyl-C71-butyric acid methyl ether (PC70BM), perylene derivatives such as perylene and 3,4,9,10- Perylene derivatives such as 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), fullerene (C60), semiconductor nanoparticles such as CdS, CdSe, CdTe, or ZnSe Is used. The size of the nanoparticles may be about 1 to 200 nm.

A substrate in accordance with one embodiment of the present invention is soda lime as a transparent glass substrate or a polyester, may be such as polyimide, on such substrate _{In 2 O 3, ITO (indium} -tin oxide), IGZO (indium-gallium _{-zincoxide), Ga 2 O 3 -In} 2 O 3, ZnO, ZnO-In 2 O 3, AZO (Aluminium-zinc oxide; ZnO: Al), Zn 2 In 2 O 5 -In 4 Sn 3 O 12, SnO _{2, FTO (Fluorine-doped tin} oxide; SnO 2: F), ATO (Aluminium-tin oxide; SnO 2: Al) indium (In), tin (Sn), gallium (Ga), zinc (Zn), such as, A transparent electrode which is a single or complex oxide of a metal such as aluminum (Al) may be formed, and the transparent electrode may be formed by atomic layer deposition, sol-gel coating, chemical vapor deposition, or the like.

The first electrode according to an embodiment of the present invention may be ITO as a transparent electrode, and Al or Ca having a low work function may be used as the second electrode.

Hereinafter, specific embodiments of the present invention will be described, but these embodiments are not intended to limit the scope of the present invention.

[Example 1] Preparation of Compound 1

Preparation of 1,2-Diamino-3,6-dibromobenzene (Compound 1-1)

4,7-Dibromobenzo [c] [1,2,5] thiadiazole (1.0 g, 3.4 mmol) was dissolved in EtOH (25 mL). To the solution was slowly added NaBH ₄ (2.18 g, 58.0 mmol). The mixture was stirred at room temperature for 24 hours and the mixture was extracted with diethyl ether (3 times) and brine. The organic layer was dried over MgSO ₄ and purified through a column to obtain the title compound 1-1 (75%) as a white solid.

Preparation of 1,4-Dibromo-7,8-bis (decyloxy) phenazine (Compound 1-2)

1,2-diamino-3,6-dibromobenzene (Compound 1-1) (676 mg, 2.54 mmol) and 2,5-dihydroxyl-1,4-benzoquinone (356 mg, 2.54 mmol) were dissolved in EtOH And refluxed under nitrogen for 24 hours. The solution was cooled to room temperature and the solvent was removed. K ₂ CO ₃ (1.69 g, 7.62 mmol) and 1-bromodecane (1.69 g, 7.62 mmol) were added to DMF (50 mL) without further purification, and the solution was stirred at 60 ^° C for 24 hours. And then cooled to room temperature. The precipitated solid was filtered and purified through a column (MC: n-hexane = 1: 1) to obtain the title compound 1-2.

Preparation of 1,4-di (thiophen-2-yl) -7,8-bis (decyloxy) phenazine (Compound 1)

Compound 1-2 (2.33 g, 3.59 mmol) and tetrakis (triphenylphosphine) palladium (0) (97 mg, 0.084 mmol) are placed in a round bottom flask and under vacuum, nitrogen is added three times. Add toluene to the flask and stir at 110 ^° C. Add 2- (tri-n-butylstannyl) thiophene (2.95 g, 7.85 mmol) and stir the mixture for 24 hours. The mixture was extracted with water and chloroform, and MgSO ₄ was added and stirred. The mixture was redeposited several times in MeOH to obtain the title compound 1 (81%) as a red solid.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.08 (s; 2H), 7.94 (d; 2H), 7.53 (d; 2H), 7.38 (s; 2H), 7.21 (t; 2H), 4.23 (t; 4H), 1.97 (m, 4H), 1.58-1.29 (m, 28H), 0.88 (t, 6H).

[Example 2]

Preparation of 7,8-bis (2- (2-ethoxyethoxy) ethoxy) -1,4-di (thiophen-2-yl) phenazine

Preparation of Compound 2-1

P-toluenesulfonyl chloride (2.03 g, 10.65 mmol) is dissolved in MC (12 mL) into a 25 mL 1 neck round bottom flask. Then, diethylene glycol monoethyl ether (1.41 g, 10.55 mmol) and triethylamine (1.48 mL, 10.65 mmol) are added. The solution is stirred at room temperature for 24 hours. The reaction is followed by extraction with CHCl ₃ and water (200 mL). MgSO ₄ was added to the organic layer, and the mixture was stirred and purified through a column to obtain the title compound (67%) as a white solid.

Preparation of Compound 2-2

Compound 1-1 (2.54 mmol) and 2,5-dihydroxyl-1,4-benzoquinone (2.54 mmol) were added to EtOH (55 mL) and the mixture was refluxed under nitrogen for 24 hours. The solution is cooled to room temperature and the solvent is removed. K ₂ CO ₃ (7.62 mmol) and compound 2-1 (7.62 mmol) were added to the mixture without further purification, and the solution was stirred at 60 ^° C for 24 hours, and then the solution was cooled to room temperature. The precipitated solid was filtered and separated into a column (MC: n-hexane = 1: 2) to obtain the title compound 2-2 (42%).

Preparation of 2 compounds

Compound 2 was prepared (75%) in the same manner as in the preparation of 1 compound of Example 1, except that compound 2-2 was used instead of compound 1-2.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.06 (s; 2H), 7.93 (d; 2H), 7.51 (d; 2H), 7.37 (s; 2H), 7.18 (t; 2H), 4.35 (t; 4H), 4.02 (t, 4H), 3.78-3.46 (m, 12H), 1.38 (t, 6H).

Example 3 Preparation of Compound 3

Preparation of Compound 3-1

화합물 1-1 (2.54 mmol)과 2,5-dihydroxyl-1,4-benzoquinone (2.54 mmol)을 EtOH (55 mL)에 넣고 질소하에서 24시간 동안 환류시킨다. 용액을 상온까지 시킨 뒤 용매를 제거한다. 추후 정제과정 없이 혼합물에 4-(heptyloxy)benzoic acid (7.62 mmol), DMAP (0.12 g, 1.0 mmol)과 DCC (2.38 g, 11.5 mmol)을 MC (50 mL)에 넣는다. 용액은 상온에서 12 시간 동안 교반한다. 반응 후 용매를 제거한다. 혼합물은 CHCl₃와 물 (200 mL)을 넣고 추출한 후 혼합물은 컬럼을 통해 정제하여 표제 화합물 3-1을 얻었다(47.4 %).

Compound 1-1 (2.54 mmol) and 2,5-dihydroxyl-1,4-benzoquinone (2.54 mmol) were added to EtOH (55 mL) and refluxed under nitrogen for 24 hours. The solution is allowed to reach room temperature and the solvent is removed. Add 4- (heptyloxy) benzoic acid (7.62 mmol), DMAP (0.12 g, 1.0 mmol) and DCC (2.38 g, 11.5 mmol) to the mixture without further purification in MC (50 mL). The solution is stirred at room temperature for 12 hours. After the reaction, the solvent is removed. The mixture was extracted with CHCl ₃ and water (200 mL), and the mixture was purified through a column to obtain the title compound 3-1 (47.4%).

Preparation of Compound 3

Compound (3) was prepared in the same manner as Compound (1) of Example 1 except that Compound (3-1) was used instead of Compound (1-2). Compound (3) was prepared (65.1%).

_{^{1 H-NMR (CDCl 3)}} : δ = 8.16 (s; 2H), 8.11 (d; 4H), 8.07 (s; 2H), 7.93 (d; 2H), 7.37 (s; 2H), 7.18 (t; 2H), 7.04 (d, 4H), 4.15 (t, 4H), 1.98 (m, 4H), 1.38-1.26 (m, 16H), 1.03 (t, 6H).

[Example 4] Preparation of Compound 4

In the same manner as in Example 3 except that heptanoic acid was used instead of 4- (heptyloxy) benzoic acid in Example 3, the title compound 4 was obtained (72.4%).

_{^{1 H-NMR (CDCl 3)}} : δ = 8.07 (s; 2H), 7.93 (d; 2H), 7.81 (d; 2H), 7.37 (s; 2H), 7.18 (t; 2H), 2.65 (t; 4H), 1.73 (m, 4H), 1.43-1.36 (m, 12H), 1.08 (t, 6H).

[Example 5] Preparation of Compound 5

In the same manner as in Example 3 except that 4-heptyloxybenzoic acid was used instead of 4- (heptyloxy) benzoic acid in Example 3, the title compound 5 was obtained (72.4%).

_{^{1 H-NMR (CDCl 3)}} : δ = 8.16 (s; 2H), 8.11 (d; 4H), 8.07 (s; 2H), 7.93 (d; 2H), 7.37 (s; 2H), 7.30 (d, 4H), 7.18 (t, 2H), 2.63 (m, 4H), 1.68 (m, 4H), 1.35-1.29 (m, 16H), 1.02 (t, 6H).

[Examples 6 to 10] Preparation of phenazine derivatives

Compound 6 (2.49 mmol) is added to CHCl ₃ and light is blocked. The solution is stirred at 0 ^° C and then slowly added N-bromosuccinimide (4.98 mmol). The solution is stirred for 3 hours. The mixture is extracted with chloroform and water. The mixture was purified via column and re-triturated again with MeOH to give compound 6 (75%).

Compounds 7 to 10 were prepared in the same manner as Compound 6 by using 2 to 5 instead of Compound 1 to give Compounds 7 to 10, respectively.

Compound ^{6: 1 H-NMR (CDCl} 3): δ = 7.95 (s; 2H), 7.53 (d; 2H), 7.30 (s; 2H), 7.13 (d; 2H), 4.25 (t; 4H), 2.00 (m, 4H), 1.56-1.30 (m, 28H), 0.89 (t, 6H).

[Examples 11 to 20] Preparation of phenazine derivatives

Preparation of Compound 11-1

5-bromo-2,2'-bithiophene (0.172 mmol) was dissolved in THF (4.0 mL) and stirred at -78 ^° C. To the solution is added n-butyllithium (2.5 M in hexane, 0.076 mL, 0.189 mmol) and the mixture is stirred for 1 hour. Trimethyltin chloride solution (0.20 mL, 0.20 mmol) is slowly added to the solution. The solution is warmed to room temperature and extracted with diethyl ether and water (30 mL). The organic layer was dried over MgSO ₄ , filtered and then the solvent was removed to give the title compound 11-1 (52%).

Preparation of compounds 11 to 15

Add 3 drops of compound 1 '(3.59 mmol) and tetrakis (triphenylphosphine) palladium (0) (97 mg, 0.084 mmol) in a round bottom flask. After adding toluene to the flask and stirring at 110 ^° C, compound 11-1 (7.85 mmol) was added and the solution was stirred for 24 hours. The mixture was extracted with water and chloroform, and MgSO ₄ was added thereto. After stirring, the mixture was repeatedly refluxed in MeOH to obtain Compound 11.

Compounds 12 to 15 were prepared in the same manner as Compound 11 by using 2 'to 5' instead of Compound 1 ', respectively, to give Compounds 12 to 15.

Preparation of compounds 16 to 20

Compound 11 (2.49 mmol) is added to CHCl ₃ and light is blocked. The solution is stirred at 0 ^° C and N-bromosuccinimide (0.895 g, 4.98 mmol) is slowly added. The mixed solution is stirred for 3 hours and then extracted with chloroform and water. The mixture was purified through a column and again redeposited in MeOH to give compound 16.

Compounds 17 to 20 were prepared in the same manner as Compound 16 by using 12 to 15 instead of Compound 11 to give Compounds 17 to 20, respectively.

Compound ^{16: 1 H-NMR (CDCl} 3): δ = 7.97 (s; 2H), 7.51 (d; 2H), 7.30 (s; 2H), 7.13 (d; 2H), 7.01 (d; 2H), 6.81 (d, 2H) 4.21 (t, 4H), 1.90 (m, 4H), 1.37-1.29 (m, 28H), 0.88 (t, 6H).

[Example 21] Production of polymer compound (P2) containing a phenazine derivative

Preparation of Compound 21-1

9,9-Dihexyl-2,7-dibromofluorene (2.56 g, 5 mmol) was added to a round bottomed flask and dissolved in THF. Then, t-BuLi (6.45 mL, 11 mmol) was slowly dropped under an atmosphere of argon at -78 ^° C I will. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.23 g, 12 mmol) is added thereto. After stirring the mixture at room temperature for 24 hours, the mixed solution is extracted with ethyl acetate (60 mL × 4). Thereafter, MgSO ₄ was added, dried and purified through a column (n-hexane: EA = 8: 1) to give the title compound 21-1 as a white solid (53%).

Preparation of Compound 21 (P2)

Compound 21-1 (0.326 g, 0.400 mmol), compound 1 (0.235 g, 0.400 mmol), tricyclohexyl phosphine (6.8 mg, 0.024 mmol) and Pd (OAc) ₂ (10.8 mg) are placed in a round bottomed flask. Vacuum the flask and repeat the process of flowing nitrogen. Add toluene (8 mL) and tetraethyl ammonium hydroxide solution (1.30 g) under nitrogen. The mixed solution is stirred at 95 ^° C under nitrogen for 24 hours. After the reaction, re-immerse the solution in MeOH (200 mL) and 1 N HCl (20 mL). The precipitated solid is dissolved in o- dichlorobenzene and re-dissolved in MeOH. The polymer is subjected to Soxhlet extraction in acetone for 24 hours. The obtained polymer is purified through a column (CHCl ₃ ).

M _n = 17.8 × 10 ³ ; M _w = 34.7 × 10 ³ ; PDI = 1.95.

[Example 22] Production of polymer compound (P3) containing a phenazine derivative

Preparation of Compound 22-1

To a solution of 2,7-dibromo-9- (undecan-6-yl) -9H-carbazole (2.0 g, 4.17 mmol) in THF (30 mL) was slowly added t-BuLi (10.2 mL) Drop it. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxa-boralane (1.7 mL, 8.33 mmol) was slowly added to the solution and the temperature of the mixed solution was raised to room temperature. And extracted with EA, water and brine. The mixture was purified through a column and recrystallized with a solvent of MeOH: Acetone = 10: 1 to obtain the title compound 12-1 (31.4%).

Preparation of Compound 22 (P3)

Compound 1 (0.235 g, 0.400 mmol), compound 12-1 (0.229 g, 0.400 mmol), tricyclohexyl phosphine (6.8 mg, 0.024 mmol) and Pd (OAc) ₂ (10.8 mg) are placed in a round bottomed flask. Vacuum the flask and repeat the process of flowing nitrogen. Add toluene (8 mL) and tetraethyl ammonium hydroxide solution (1.30 g) under nitrogen. The solution is stirred at 95 ^° C under nitrogen for 24 hours. After the reaction, re-immerse the solution in MeOH (200 mL) and 1 N HCl (20 mL). The precipitated solid is dissolved in o- dichlorobenzene and re-dissolved in MeOH. The polymer is subjected to Soxhlet extraction in acetone for 24 hours. The obtained polymer is purified through a column (CHCl ₃ ).

M _n = 13.6 x 10 ³ ; M _w = 23.1 × 10 ³ ; PDI = 1.69.

Thermogravimetric analysis (TGA) was carried out under nitrogen at 25 ^o C to 500 ^o C to observe the change in weight of the polymer. Thermal analysis results are shown in Fig. In Example 11 (P2), a weight loss of 5 wt% occurred at about 366 ^° C, whereas Example (P3) showed a weight loss at 368 ^° C. Therefore, the polymer compound according to the present invention has a very high thermal stability and is suitable for application to organic solar cells.

[Example 23] Production of organic solar cell

The polymer obtained in Example 11 and Example 12 and PC ₇₁ BM (polymer prepared in Examples 11 to 12: PC ₇ 1 BM = 1: 0.5 to 4.0 weight ratio) were mixed in a weight ratio of 1,2-dichlorobenzene or chloro Benzene as a solvent to prepare a composite solution. The ITO coated glass substrate was cleaned by a general cleaning process, ultrasonic treatment in a cleaning agent and rinsing with distilled water, acetone and 2-propanol. The ITO surface was exposed to ozone for 10 minutes and then PEDOT: PSS (Baytron P) having a thickness of 45 nm was spin-coated on the ITO substrate. The PEDOT: PSS layer was baked on a hot plate at 120 DEG C for 20 minutes. The photoactive layer was filtered through a 0.45 μm (PTFE) syringe filter and then spin-coated with a pre-dissolved complex solution. The resulting device structure was completed by depositing 0.7 nm thick LiF or 2.0 nm thick Ca on the photoactive layer under a vacuum of 3 × 10 ^-6 torr in a thermal still, and 100 nm thick Al cathode as the top electrode. The current density-voltage (JV) characteristics of all polymer optoelectronic cells were measured under the illumination of sunlight with 100 mW / cm ² (AM 1.5 G) by Oriel 1000W solar simulator. The measurement results of Example 13 are summarized in Table 1. That is, the photovoltaic parameters of V _oc (open circuit voltage), short-circuit current density (J _SC ), fill factor (FF), and overall conversion efficiency (η) Respectively.

Copolymer: PC ₇₁ BM J _sc
(mA / cm ² ) V _oc
(V) FF
(%) Efficiency
(%) P2 (1: 2) 4.67 0.77 30.5 1.09 P2 (1: 4) 4.78 0.77 35.4 1.30 P3 (1: 2) 8.21 0.84 50.2 3.46 P3 (1: 4) 8.74 0.83 56.3 4.08

As shown in Table 1, the organic solar cell employing the polymer compound prepared using the phenazine derivative as a unit, which is a novel compound of the present invention, has excellent efficiency.

100: organic optoelectronic device 110: substrate
120: first electrode 130: buffer layer
140: photoelectric conversion layer 150: second electrode

Claims (10)

A compound represented by the following formula (1):
[Chemical Formula 1]

[In the above formula (1)
Z is S or Se;
R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, ≪ / RTI > and a silyl group,
n and m are an integer of 0 to 4; The method of claim 1,
R is a C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkylcarbonyl group, C ₆ -C ₂₀ arylcarbonyl group, wherein the alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ alkoxy May be further substituted with
and n and m are an integer of 0 to 2. < The method of claim 1,
Wherein Z is S; Reacting a compound represented by Formula 2 and a compound represented by Formula 3 to prepare a compound represented by Formula 4 below;
Reacting a compound represented by the following formula (4) with a compound represented by the following formula (5) to prepare a compound represented by the following formula (6); And
(6) with a compound of the following formula (7) to prepare a compound of the formula (1).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]
R-OA
[Chemical Formula 6]

(7)

[In Formulas 1 to 7,
Z is S or Se;
R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >
X is halogen;
A is hydrogen or a paratoluenesulfonyl group;
n and m are integers of 0 to 4] 5. The method of claim 4,
Z is S;
R is a C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkylcarbonyl group, C ₆ -C ₂₀ arylcarbonyl group. A polymer compound comprising a compound represented by the following formula (1) as a unit.
[Chemical Formula 1]

[In the above formula (1)
Z is S or Se;
R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, ≪ / RTI > and a silyl group,
and n and m are integers of 0 to 4.] The method according to claim 6,
Wherein the polymer compound is represented by the following formula (11).
(11)

[In Formula 11,
Z is S or Se;
R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >
T is C ₆ -C ₂₀ arylene or C ₃ -C ₂₀ heteroarylene;
n and m are integers of from 0 to 4;
s is an integer from 1 to (500).] 8. The method of claim 7,
Wherein T is at least one selected from the following structures.

[In the above formula,
Z is S or Se;
R 'and R " are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl or C ₆ -C ₂₀ aryl C ₁ -C ₂₀ alkyl;
R ₁₁ to R ₁₄ are independently, hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ ahreu C ₁ -C ₂₀ alkyl together, R 'and R "alkyl group, Aryl, heteroaryl and aralkyl and the alkyl, alkoxy and aralkyl of R ₁₁ to R ₁₄ are independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy , An amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group;
o, p and q are integers of 1 to 2.] 8. The method of claim 7,
(11) is selected from the following structural formulas.

[In the above formula,
Z is S or Se;
R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group Beams, C ₆ -C ₂₀ aryl carbonyl group, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl group, said alkyl, aryl and aralkyl is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, a methyl group as a group, a trifluoromethyl nitro, And a silyl group; and < RTI ID = 0.0 > R < / RTI >
R ₁₁ to R ₁₂ are independently of each other hydrogen, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aralkyl C ₁ -C ₂₀ alkyl;
The alkyl group, alkoxy and aralkyl of R ₁₁ to R ₁₂ are independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, Which may be further substituted with one or more substituents selected from halogen, cyano, nitro, trifluoromethyl and silyl groups;
n and m are integers of from 0 to 4;
and s is an integer of 1 to 500.] Board;
A first electrode and a second electrode formed on the substrate;
And a photoactive layer formed on the first electrode and the second electrode, the photoactive layer containing the polymer compound according to any one of claims 6 to 8.

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