KR101493823B1 - Fullerene dimer derivatives and organic electronic devices containing them - Google Patents

Fullerene dimer derivatives and organic electronic devices containing them Download PDF

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KR101493823B1
KR101493823B1 KR20140118116A KR20140118116A KR101493823B1 KR 101493823 B1 KR101493823 B1 KR 101493823B1 KR 20140118116 A KR20140118116 A KR 20140118116A KR 20140118116 A KR20140118116 A KR 20140118116A KR 101493823 B1 KR101493823 B1 KR 101493823B1
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fullerene
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이종철
문상진
신원석
이상규
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한국화학연구원
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Abstract

The present invention relates to a fullerene dimer derivative and an organic electronic device containing the same. More specifically, the fullerene dimer derivative having a pyrrolidine group according to the present invention has excellent compatibility with an electron-donating polymer material, The organic electronic device can provide a higher level of open circuit voltage and provide an organic electronic device with improved energy conversion efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to fullerene dimer derivatives and organic electronic devices containing the same,

The present invention relates to a novel fullerene dimer derivative and an organic electronic device including the same. More particularly, the present invention relates to a pyrrolidine-bonded fullerene dimer derivative and an organic light emitting device, an organic solar cell, an organic transistor, An organic memory, or an organophotoreceptor (OPC).

Fullerene has been of great interest because of its unique physico-chemical properties. Fullerene represented by C 60 and C 70 is a molecule having high symmetry due to a bond due to an intermolecular force. All carbon atoms in the molecule are equivalent, covalently bonded to each other, and are highly stable crystals.

Based on these properties, fullerene is expected to be applied to various applications as a new carbon-based material. Thus, it is the most potent and long-lived antioxidant, and has recently been attracting attention in biomedical fields due to its anticancer efficacy.

In particular, fullerene such as C 60 is attracting interest in applications of superconducting materials, catalyst materials, lubricant materials, biomaterials, and nonlinear optical materials due to metallic mechanical properties such as plastic deformation and work hardening properties.

Since fullerene molecules having a pentavalent carbon-carbon double bond and having hexagonal shape are not aromatic but have an alkene structure, a variety of new fullerene derivatives are produced through various alkene addition reactions to fullerene molecules Recently, there have been many attempts to develop fullerene-containing derivatives through chemical functionalization of fullerene as well as research on fullerene itself.

Further, by using the property of fullerene which has no change in structure due to electron transfer at the time of reduction, applicability as an electron acceptor can be expected. Through the increase of physicochemical properties of fullerene through chemical functionalization, Development is underway.

A typical example is a dielectric solar cell. BACKGROUND ART [0002] Oil-field type solar cells are new solar cells that have remarkably improved their technical possibilities in recent years. Oil-based solar cells have a junction structure of an electron donor and an electron acceptor. Is a very fast charge transfer phenomenon called photoinduced charge transfer (PICT), which manifests the photovoltaic effect.

The organic semiconductors used as the electron donors may include a material of polyparaphenylene vinylene (PPV) and a material of polythiophene (hereinafter referred to as PT) Various derivatives have been used. As the electron acceptor, C 60 fullerene itself or C 60 fullerene derivative designed to dissolve C 60 fullerene in an organic solvent is used.

Since the C 60 fullerene has a low solubility in an organic solvent, phase separation occurs when it is mixed with a polymer, and therefore the efficiency of the outline is low overall. As a method for solving this problem, C 60 fullerene is being studied to use a C 60 fullerene derivative having its side chain attached so as to be well soluble in an organic solvent.

That is, not only the solubility of the C 60 fullerene can be increased, but also the mixing degree of the semiconductor polymer and the C 60 fullerene can be made very high compared with the conventional method, so that a photovoltaic device with improved energy conversion efficiency can be developed.

In for example US Patent Publication No. 2006-0011233 call as an electron donor of poly (3-hexylthiophene) (P3HT) and an electron acceptor, [6,6] -phenyl -C 61 - butyric acid methyl ester (C 60 -PCMB ), And a photoelectric conversion layer is introduced by a spin coating method.

[6,6] -phenyl-C 71 -butyric acid methyl ester (C 70 -PCMB), which is a C 70 fullerene derivative superior in light absorption ability to C 60 fullerene, is used as a photoelectric conversion layer in Nature Materials 6, 497-500 And the photoelectric conversion performance is improved.

However, in order to meet the requirements in the fields of superconducting materials, catalyst materials, lubricant materials, biomaterials and nonlinear optical materials, it is necessary to manufacture fullerene derivatives excellent in electrochemical stability and physicochemical properties while maintaining intrinsic properties of fullerene to be.

The present inventors have found that the phase separation of electron donor (polymer or single molecule) and electron acceptor (fullerene) in the device structure greatly influences the energy conversion efficiency due to the characteristics of the organic solar cell using fullerene, In order to increase the characteristics of the organic solar cell device and to maximize its efficiency, proper phase separation by proper aggregation (aggregation) of the fullerene derivative has been intensively studied. The fullerene dimer derivative is prepared, It is possible to improve the electrochemical stability and physico-chemical properties of the polymer, and to improve the energy conversion efficiency by being highly compatible with the semiconductor polymer. Thus, the present invention has been completed.

U.S. Published Patent Application No. 2006-0011233

Nature Materials 6, 497 - 500 (2007)

An object of the present invention is to provide a novel fullerene dimer derivative and an organic electronic device, and more particularly, to use a fullerene dimer derivative having a pyrrolidine group, And to provide an organic electronic device having improved energy conversion efficiency.

The present invention provides a fullerene dimer derivative represented by the following general formula (1).

[Chemical Formula 1]

Figure 112014085074913-pat00001

[In the above formula (1)

A is fullerene of C60, C70, C72, C76, C78 or C84;

R 1 to R 6 are each independently selected from the group consisting of hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, (C 1 -C 20) alkoxy, (C 1 -C 20) alkylcarbonyl, (C 1 -C 20) alkoxycarbonyl (C1-C20) alkylcarbonyl, (C1-C20) alkylcarbonyl, (C1-C20) alkoxycarbonyl Alkoxy, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl.

The fullerene dimer derivative according to an embodiment of the present invention may be represented by the following formula (2).

(2)

Figure 112014085074913-pat00002

[In the formula (2)

A is fullerene of C60, C70, C72, C76, C78 or C84;

R 11 and R 12 are each independently (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;

R 13 and R 14 are each independently (C 1 -C 20) alkyl;

and n is an integer of 1 to 9.]

In the fullerene dimer derivative represented by Formula 2 according to an embodiment of the present invention, R 11 and R 12 are each independently (C 1 -C 10) alkoxy, and R 13 and R 14 are each independently (C 1 -C 10) alkyl Lt; / RTI >

In the fullerene dimer derivative represented by Formula 2 according to an embodiment of the present invention, A may be C60 or C70 fullerene, and n may be an integer of 1 to 5.

The fullerene dimer derivative according to an embodiment of the present invention may be selected from the following structures.

Figure 112014085074913-pat00003

[In the above structure,

A is a fullerene of C60 or C70.]

The present invention relates to a process for preparing a compound represented by the general formula (2) by dissolving a compound represented by the following general formula (3), fullerene and a compound represented by the following general formula (4) in an organic solvent, The present invention provides a method for producing a fullerene dimer derivative.

(3)

Figure 112014085074913-pat00004

[Chemical Formula 4]

Figure 112014085074913-pat00005

(2)

Figure 112014085074913-pat00006

[In the above Chemical Formulas 2 to 4,

A is fullerene of C60, C70, C72, C76, C78 or C84;

R 11 and R 12 are each independently (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;

R 13 and R 14 are each independently (C 1 -C 20) alkyl;

and n is an integer of 1 to 9.]

In the method for preparing a fullerene dimer derivative according to an embodiment of the present invention, the step of preparing the compound represented by Formula 2 may be performed at a temperature ranging from 100 to 150 ° C.

In the method for producing a fullerene dimer derivative according to an embodiment of the present invention, the organic solvent is selected from the group consisting of benzene, toluene, benzonitrile, tetrahydronaphthalene, decalin, carbon disulfide, anisole, chlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, xylene or mixtures thereof.

The present invention provides an organic electronic device containing the fullerene dimer derivative.

The organic electronic device according to an exemplary embodiment of the present invention may be an organic light emitting device, an organic solar cell, an organic transistor, an organic memory, or an organic photoconductor (OPC).

The fullerene dimer derivative of the present invention is a compound in which two molecules of fullerene are connected using a pyrrolidine group. In addition, the fullerene dimer derivative is excellent in solubility in an organic solvent while maintaining intrinsic properties of fullerene, And is thermally stable.

In addition, it is possible to provide an organic electronic device having improved energy conversion efficiency because it is excellent in compatibility with an electron-donating polymer material and can realize a higher level of open circuit voltage.

1 is a schematic view of an organic solar cell according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. Unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the following description, And a description of the known function and configuration will be omitted.

The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

The term "cycloalkyl" in the present invention means a saturated hydrocarbon ring, preferably an alicyclic ring having 5 to 7 members, and includes a case where an aromatic or alicyclic ring is fused.

In order to achieve the above object, the present invention provides a fullerene dimer derivative represented by the following general formula (1).

[Chemical Formula 1]

Figure 112014085074913-pat00007

[In the above formula (1)

A is fullerene of C60, C70, C72, C76, C78 or C84;

R 1 to R 6 are each independently selected from the group consisting of hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, (C 1 -C 20) alkoxy, (C 1 -C 20) alkylcarbonyl, (C 1 -C 20) alkoxycarbonyl (C1-C20) alkylcarbonyl, (C1-C20) alkylcarbonyl, (C1-C20) alkoxycarbonyl Alkoxy, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl.

In the fullerene dimer derivative represented by Formula 1 according to an embodiment of the present invention, preferably, R 1 to R 6 are each independently selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) (C1-C10) alkoxy, (C1-C10) alkylcarbonyl, (C1-C10) alkoxycarbonyl, (C1-C10) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl or (C3- -C20) may be a heteroaryl group, and more preferably from R 1 to R 4 are each independently hydrogen, (C1-C8) alkyl, (C1-C8) haloalkyl or (C1-C8) alkoxy; R 5 to R 6 are each independently (C1-C8) alkylcarbonyl, (C1-C8) alkoxycarbonyl, (C1-C8) alkylcarbonyl (C1-C8) alkyl, (C1-C8) alkylcarbonyl (C1-C8) alkoxy, (C1-C8) alkoxycarbonyl (C1-C8) alkyl or (C1-C8) alkoxycarbonyl (C1-C8) alkoxy.

The fullerene dimer derivative according to the present invention has a structure in which fullerene 2 molecules are linked using a pyrrolidine group, and the appropriate phase separation by aggregation (aggregation) of the fullerene dimer derivative in the active layer of the organic electronic device, Can be induced and can have an advantage that compatibility with an electron-donating polymer material can be improved.

The fullerene dimer derivative according to an embodiment of the present invention may be a derivative represented by the following formula (2) in order to increase solubility in an organic solvent.

(2)

Figure 112014085074913-pat00008

[In the formula (2)

A is fullerene of C60, C70, C72, C76, C78 or C84;

R 11 and R 12 are each independently (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;

R 13 and R 14 are each independently (C 1 -C 20) alkyl;

and n is an integer of 1 to 9.]

The fullerene dimer derivative represented by Formula 2 according to the present invention has a high solubility in an organic solvent and has a high solubility and can be applied to a large area printing process such as printing, .

In the fullerene dimer derivative according to an embodiment of the present invention, R 11 and R 12 in Formula 2 are each independently (C 1 -C 10) alkoxy in view of the thermally stable and excellent electron mobility, and R 13 and R 14 may each independently be (C1-C10) alkyl.

In addition, the above-mentioned fullerene dimer derivatives may be C60 or C70 fullerenes in view of better light absorption ability, and n may be an integer of 1 to 5 in order to increase solubility in an organic solvent.

The fullerene dimer derivative according to an embodiment of the present invention may be a fullerene dimer derivative selected from the following structures in view of improving the open-circuit voltage characteristic of the organic electronic device having a high LUMO energy level, But is not limited thereto.

Figure 112014085074913-pat00009

The present invention also provides a process for preparing the above-described fullerene dimer derivative. The fullerene dimer derivatives represented by the following formula (2) according to the present invention can be prepared by dissolving the compound represented by the following formula (3), fullerene and the compound represented by the following formula (4) in an organic solvent and then reacting them. Needless to say, it can be synthesized by a recognizable method.

(3)

Figure 112014085074913-pat00010

[Chemical Formula 4]

Figure 112014085074913-pat00011

(2)

Figure 112014085074913-pat00012

[In the above Chemical Formulas 2 to 4,

A is fullerene of C60, C70, C72, C76, C78 or C84;

R 11 and R 12 are each independently (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;

R 13 and R 14 are each independently (C 1 -C 20) alkyl;

and n is an integer of 1 to 9.]

The step of preparing the fullerene dimer derivative represented by Formula 2 according to an embodiment of the present invention may be performed under reflux of an organic solvent at atmospheric pressure and may be carried out at a temperature of 5 to 10 ° C It is preferable to perform it in a high temperature range. A non-limiting example of the temperature range may be performed at 100-150 < 0 > C, but is not limited thereto.

The organic solvent may be a protic solvent such as methanol, ethanol, propanol, butanol, 2-propanol; And an aprotic solvent such as benzene, toluene, benzonitrile, tetrahydronaphthalene, decalin, carbon disulfide, anisole, chlorobenzene, 1,2-dichlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, xylene; ≪ / RTI > Here, benzene, toluene, chlorobenzene, xylene, or a mixture thereof may be used in view of high solubility of the fullerene dimer derivative.

The present invention provides an organic electronic device containing the above-described fullerene dimer derivative.

The organic electronic device according to an embodiment of the present invention may be an organic solar cell, an organic thin film transistor, an organic memory, or an organic photoreceptor, preferably an organic solar cell or an organic thin film transistor.

Hereinafter, a general organic solar cell containing the fullerene dimer derivative of the present invention according to an embodiment of the present invention will be described with reference to FIG. 1, but the present invention is not limited thereto.

The organic photovoltaic device shown in Fig. 1 can be manufactured as follows.

The first electrode 120, the buffer layer 130, the photoelectric conversion layer 140, and the second electrode 150 are stacked from the bottom. An electron transport layer, a hole blocking layer or an optical space layer may be introduced between the photoelectric conversion layer 140 and the second electrode 150.

The substrate 110 may be made of a transparent material such as glass or plastic including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyamide (PI), triacetylcellulose Material, and is preferably made of glass.

The first electrode 120 is formed by applying a transparent material to one surface of the substrate 110 by using a method such as sputtering or spin coating or by coating the first electrode 120 with a film. The first electrode 120 may function as an anode, and may be made of any material having transparency and conductivity as a material having a lower work function than the second electrode 150 described later. For example, ITO (indium-tin oxide) , Fluorine doped tin oxide (FTO), ZnO- (Ga 2 O 3 or Al 2 O 3 ), SnO 2 -Sb 2 O 3, etc., but ITO is preferably used.

The buffer layer 130 is introduced onto the first electrode 120 through a method such as spin coating. In the present invention, for example, poly (3,4-ethylene) doped with poly (styrenesulfonate) Can be used to improve the hole mobility.

On top of the buffer layer 130, a photoelectric conversion layer 140 introduced by spin coating or the like is deposited. The conductive polymer and the fullerene dimer derivative represented by Formula 1 are mixed at a weight ratio of 1: 0.5 to 1: 4 A photoelectric material in combination can be used. A solution obtained by dissolving the photoelectric conversion material thus compounded in one organic solvent or two or more organic solvents having different boiling points is introduced into the photoelectric conversion layer 140 having a thickness of about 80 nm or more by spin coating or the like. The photoelectric conversion layer may be formed by a variety of methods including, but not limited to, spin coating, pipetting, blade coating, bar or rod coating, But are not limited to, a roll coating, a spray coating, a curtain coating, a dip coating, a flow coating, a comma coating, a slot die coating, a dispensing, Knife coating, gravure (micro), flexo, nozzle printing or inkjet printing. The fullerene dimer derivative according to the present invention is excellent in solubility in an organic solvent and has advantages such as roll coating, nozzle printing or inkjet printing in addition to the spin coating method.

In addition, the second electrode 150 may be formed by vacuum-depositing a metal material such as aluminum at a degree of vacuum of about 10 -7 torr or less in a state where the photoelectric conversion layer 140 is introduced at a vacuum of 100-200 nm, And then post-treated at 150 캜 for about 10 minutes or more to be laminated on the photoelectric conversion layer 140. The material that can be used for the second electrode 150 includes gold, aluminum, copper, silver or an alloy thereof, a calcium / aluminum alloy, a magnesium / silver alloy, an aluminum / lithium alloy, Aluminum / calcium alloy.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

[Example 1] Synthesis of C 60 fullerene dimer derivative

Step 1. Synthesis of 2,5-dimethoxyterephthalaldehyde

Figure 112014085074913-pat00013

1.6 M BuLi was slowly added dropwise to a solution of 1,4-Dibromo-2,5-dimethoxybenzene (2.0 g, 6.76 mmol) in 35 mL of THF at -78 ° C. The reaction solution was stirred at -78 ° C for 2 hours and then DMF (2.8 mL, 33.7 mmol) was added dropwise. The reaction solution is stirred at room temperature (20 ° C) for 15 hours. 20 mL of 2 N HCl was slowly added to the reaction mixture and stirred. The resulting solid was filtered under reduced pressure and dried to obtain 267 mg (30%) of 2,5-dimethoxyterephthalaldehyde.

MS (LC): m / z 195.2 (M < + & gt ; ).

1 H-NMR (CDCl 3, 300MHz): δ 10.50 (s, 2H), 7.46 (s, 2H), 3.94 (s, 6H).

Step 2. Synthesis of C 60 fullerene dimer derivatives

Figure 112014085074913-pat00014

C60 (1.1 g, 1.54 mmol) was dissolved in 680 mL of chlorobenzene and purged with nitrogen gas. Then, 2 - ((6-methoxy-6-oxohexyl) amino) acetic acid (854 mg, 4.20 mmol), 2,5- 130 mg, 0.70 mmol). The reaction mixture was refluxed at 135 ° C for 16 hours, and then the reaction solution was concentrated and purified by silica column chromatography (CHCl 3 : Acetonitrile = 20: 0.1). The obtained compound was recrystallized from CHCl 3 and MeOH to obtain the desired fullerene dimer 118 mg (4%) of the compound (Example 1) was obtained.

MS (MALDI): m / z 1934.208 (M + ), 719.944 (C60).

1 H-NMR (CDCl 3, 300MHz): δ 7.62 (s, 2H), 5.64 (s, 2H), 5.02 (d, J = 9.3Hz, 2H), 3.74 (s, 6H), 3.63 (s, 6H ), 3.06-2.91 (m, 2H), 2.57-2. 41 (m, 2H), 2.30 (t, J = 10.1 Hz, 4H), 1.95-1.59 (m, 12H).

13 C-NMR (CDCl 3 , 300 MHz): δ 173.90, 156.96, 154.77, 154.55, 154.06, 153.06, 147.36, 147.31, 146.70, 146.62, 146.33, 146.28, 146.23, 146.20, 146.11, 146.08, 146.02, 145.99, 145.63, 145.59, 145.39, 145.35, 145.29, 145.21, 145.13, 144.65, 144.60, 144.46, 144.44, 143.16, 143.07, 142.75, 142.70, 142.62, 142.41, 142.36, 142.24, 142.20, 142.17, 142.04, 142.01, 141.82, 141.77, 141.64, 141.56, 140.26, 140.18, 139.45, 139.29, 136.39, 136.31, 136.14, 134.86, 126.50, 113.51, 76.06, 74.23, 69.19, 66.69, 56.26, 52.94, 51.55, 34.09, 28.09, 27.40, 25.10.

[Example 2] Synthesis of C 60 fullerene dimer derivative

Step 1. Synthesis of 1,4-dibromo-2,5-bis (hexyloxy) benzene

Figure 112014085074913-pat00015

Potassium carbonate (51.6 g, 373.28 mmol) and 1-bromohexane (13.0 mL, 93.32 mmol) were added to a solution of 2,5-dibromohydroquinone (10.0 g, 37.32 mmol) in 50 mL of DMF and stirred at 130 ° C for 16 hours . After the reaction mixture was treated with ethyl acetate and distilled water, the organic layer was separated, the water was removed with MgSO 4 and concentrated. The residue was purified by silica column chromatography (Hex) using 1,4-dibromo-2,5-bis 8.0 g (50%) was obtained.

EI-MS: m / z 434 < RTI ID = 0.0 > (M + ) <

1 H-NMR (CDCl 3, 300MHz): δ 7.08 (s, 2H), 3.94 (t, J = 6.5Hz, 4H), 1.79 (q, J = 9.2Hz, 4H), 1.60-1.21 (m, 12H ), 0.90 (t, J = 6.9 Hz, 6 H).

Step 2. Synthesis of 2,5-bis (hexyloxy) terephthalaldehyde

Figure 112014085074913-pat00016

1.6 M BuLi (22 mL, 34.39 mmol) was slowly added dropwise to a solution of 1,4-dibromo-2,5-bis (hexyloxy) benzene (3.0 g, 6.88 mmol) in 40 mL of THF at -78 ° C. The reaction solution was stirred at -78 ° C for 3 hours and then DMF (2.8 mL, 34.49 mmol) was added dropwise. After 30 minutes, the reaction solution was stirred at room temperature for 15 hours. 20 mL of 2 N HCl was slowly added to the reaction mixture and stirred. The resulting solid was filtered under reduced pressure and dried to obtain 389 mg (17%) of 2,5-bis (hexyloxy) terephthalaldehyde.

EI-MS: m / z 334 < RTI ID = 0.0 > (M + ) <

1 H-NMR (CDCl 3, 300MHz): δ 10.54 (s, 2H), 7.45 (s, 2H), 4.10 (t, J = 6.5Hz, 4H), 1.85 (q, J = 9.3Hz, 4H), 1.57-1.25 (m, 12H), 0.92 (t, J = 6.9 Hz, 6H)

Step 3. Synthesis of C 60 fullerene dimer derivatives

Figure 112014085074913-pat00017

C60 (1.2 g, 1.64 mmol) was dissolved in 700 mL of chlorobenzene and stirred while filling with nitrogen gas. Then, 2 - ((4-methoxy-4-oxobutyl) amino) acetic acid (786 mg, -bis (hexyloxy) terephthalaldehyde (250 mg, 0.75 mmol). After the reaction mixture was refluxed at 135 ° C for 16 hours, the reaction solution was concentrated and separated by silica column chromatography (CHCl 3 ) and concentrated. The obtained compound was recrystallized from CHCl 3 and MeOH to obtain 550 mg (20%) of a fullerene dimer compound (Example 2).

MS (MALDI): m / z 2018.274 (M + ), 719.958 (C60).

1 H-NMR (CDCl 3, 300MHz): δ 7.58 (s, 2H), 5.68 (s, 2H), 5.12 (d, J = 9.3Hz, 2H), 4.42 (s, 1H), 4.23-4.08 (m , 5H), 3.77 (s, 6H), 3.54 (q, J = 7.4Hz, 2H), 3.31 (q, J = 14.2Hz, 2H), 2.89-2.57 (m, 6H), 2.45-2.15 (m, 4H), 1.62-1.46 (m, 4H), 1.42-1.17 (m, 14H), 0.86 (t, J = 6.6Hz, 6H).

14 C-NMR (CDCl 3 , 300 MHz): δ 173.93, 156.77, 154.78, 154.23, 153.92, 152.30, 147.23, 146.64, 146.27, 146.23, 146.20, 146.15, 146.09, 146.04, 145.86, 145.58, 145.54, 145.50, 145.28, 145.16, 145.02, 144.83, 144.61, 144.45, 144.40, 144.35, 143.12, 143.04, 142.94, 142.65, 142.62, 142.50, 142.24, 142.21, 142.17, 142.12, 142.06, 141.87, 141.74, 141.67, 141.43, 141.01, 140.18, 140.13, 140.05, 139.46, 136.29, 136.05, 134.68, 126.11, 114.09, 75.82, 74.31, 69.03, 67.86, 66.47, 52.85, 51.73, 32.44, 31.81, 29.77, 29.25, 25.80, 23.66, 22.74, 14.26.

[Example 3] Synthesis of C 60 fullerene dimer derivative

Figure 112014085074913-pat00018

6-methoxy-6-oxohexyl) aminoacetic acid (546 mg, 2.69 mmol) was dissolved in 450 mL of chlorobenzene and charged with nitrogen gas and stirred. 2,5-bis (hexyloxy) terephthalaldehyde (150 mg, 0.45 mmol) synthesized in Step 2 of Example 1 was added. The reaction mixture was refluxed for 16 hours to 135 ℃ eseo concentrate was separated by using silica column chromatography (CHCl 3). The separated compound was recrystallized from CHCl 3 and MeOH to obtain 372 mg (18%) of fullerene dimer compound (Example 3).

MS (MALDI): m / z 2074.388 (M + ), 719.974 (C60).

1 H-NMR (CDCl 3, 300MHz): δ 7.58 (s, 2H), 5.65 (s, 2H), 5.05 (d, J = 9.5Hz, 2H), 4.12 (q, J = 10.3Hz, 4H), (Q, J = 10.8 Hz, 2H), 3.32 (q, J = 14.6 Hz, 2H), 2.69-2.40 (m, 6H), 2.16-1.72 -1.48 (m, 6H), 1.43-1.12 (m, 12H), 0.86 (t, J = 6.3 Hz, 6H).

13 C-NMR (CDCl 3 , 300 MHz): δ 174.15, 156.92, 154.91, 154.35, 154.01, 152.20, 147.23, 147.20, 146.67, 146.38, 146.22, 146.18, 146.14, 146.08, 146.05, 146.02, 145.86, 145.82, 145.59, 145.56, 145.51, 145.48, 145.33, 145.26, 145.21, 145.16, 145.01, 144.83, 144.62, 144.43, 144.40, 144.33, 143.02, 142.92, 142.63, 142.47, 142.24, 142.22, 142.18, 142.15, 142.10, 141.84, 141.72, 141.68, 141.45, 141.00, 140.14, 140.08, 139.42, 136.38, 136.09, 134.68, 126.19, 114.09, 75.95, 74.43, 69.05, 66.65, 53.27, 51.59, 34.13, 31.81, 29.19, 28.39, 27.36, 25.79, 25.22, 22.69, 14.23.

[Example 4] Fabrication of organic solar cell

BATRON-P (PEDOT: PSS) (Bayer, Germany) dissolved in aqueous solution was spin-coated on ITO glass at 4000 rpm for 30 seconds and then heat-treated at 150 ° C for 10 minutes. Thereafter, a solution was prepared by dissolving an electron donor (poly-3-hexylthiophene (P 3 HT)): electron acceptor (Example 1) in 1 ml of chlorobenzene at a weight ratio of 1: 1.2, Coated for 15 seconds, and maintained at room temperature (20 캜) for 1 hour. Thereafter, aluminum was deposited at a thickness of 200 nm in the evaporator, and then heat-treated at 150 ° C for 30 minutes to produce an organic solar cell.

[Example 5] Production of organic solar cell

An organic solar cell was prepared in the same manner as in Example 4 except that Example 2 was used instead of Example 1 as an electron acceptor.

[Example 6] Production of organic solar cell

An organic solar cell was prepared in the same manner as in Example 4, except that Example 3 was used instead of Example 1 as an electron acceptor.

The characteristics of the organic solar cell fabricated by the above method are evaluated and shown in Table 1 below. In Table 1, V oc (V) and J sc (mA / cm 2 ) represent current values when the voltage and voltage of the fabricated organic solar cell are 0, respectively. At this time, the FF (fill factor) can be calculated from the following equation (1).

[Equation 1]

FF = V mpp J mpp / V oc J sc

In the above Equation 1, V mpp and J mpp respectively represent voltage and current values at a point indicating the maximum uniformity in the current-voltage measurement of the fabricated device, and V oc (V) and J sc (mA / cm 2 ) represents the voltage value when the current of the manufactured organic solar cell is 0 and the current value when the voltage is 0.

Further, the energy conversion efficiency (PCE (%)) is calculated from the following equation (2).

&Quot; (2) "

Energy conversion efficiency (%) = 100 x FF x V oc J sc / P in

(FF, Voc, and < RTI ID = 0.0 > J sc is as defined in Equation (1), and P in represents the total energy of light incident on the device.

Figure 112014085074913-pat00019

As shown in Table 1, the fullerene dimer derivative of the present invention is mixed with poly-3-hexylthiophene (P 3 HT), which is a typical electron donor, and has an energy conversion efficiency of 4.14% Conversion efficiency is obtained.

Further, the fullerene dimer derivative according to the present invention has excellent solubility in an organic solvent and induces ideal phase separation with an electron-donating polymer material in the photoactive layer, and thus the organic electronic device employing the fullerene dimer derivative has a short circuit current (Jsc) (FF) characteristic, and high energy conversion efficiency can be obtained.

Claims (10)

A fullerene dimer derivative represented by the following formula (2).
(2)
Figure 112014123653728-pat00027

[In the formula (2)
A is fullerene of C60, C70, C72, C76, C78 or C84;
R 11 and R 12 are each independently (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;
R < 13 > is (C1-C20) alkyl;
and n is an integer of 1 to 9.] delete The method according to claim 1,
In the formula (2), R 11 and R 12 are each independently (C 1 -C 10) alkoxy, and R 13 is (C 1 -C 10) alkyl. The method of claim 3,
Wherein A is a fullerene of C60 or C70 and n is an integer of 1 to 5. 2. The fullerene derivative according to claim 1, 5. The method of claim 4,
Wherein the fullerene dimer derivative is selected from the following structures.
Figure 112014085074913-pat00022

[In the above structure,
A is a fullerene of C60 or C70.] Reacting a compound represented by the following formula (3), fullerene and a compound represented by the following formula (4) in an organic solvent and then reacting to prepare a compound represented by the formula (2); ≪ / RTI >
(3)
Figure 112014123653728-pat00023

[Chemical Formula 4]
Figure 112014123653728-pat00024

(2)
Figure 112014123653728-pat00028

[In the above Chemical Formulas 2 to 4,
A is fullerene of C60, C70, C72, C76, C78 or C84;
R 11 and R 12 are each independently (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;
R < 13 > is (C1-C20) alkyl;
and n is an integer of 1 to 9.] The method according to claim 6,
Wherein the step of preparing the compound represented by Formula 2 is carried out at a temperature ranging from 100 to 150 ° C. The method according to claim 6,
The organic solvent may be selected from the group consisting of benzene, toluene, benzonitrile, tetrahydronaphthalene, decalin, carbon disulfide, anisole, chlorobenzene, 1,2-dichlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, ≪ / RTI > 5. An organic electronic device comprising a fullerene dimer derivative according to any one of claims 1 and 3 to 5. 10. The method of claim 9,
Wherein the organic electronic device is an organic light emitting device, an organic solar cell, an organic transistor, an organic memory, or an organic photoconductor (OPC).
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100874208B1 (en) 2007-06-19 2008-12-15 한국화학연구원 Fullerene derivatives, manufacturing method thereof and organic solar cell using them
KR20090061613A (en) * 2009-05-14 2009-06-16 한국화학연구원 Methanofullerene compounds having fluorinated substituents and its use for organic electronics
JP2011184326A (en) 2010-03-05 2011-09-22 Japan Science & Technology Agency Fullerene dimer and method for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100874208B1 (en) 2007-06-19 2008-12-15 한국화학연구원 Fullerene derivatives, manufacturing method thereof and organic solar cell using them
KR20090061613A (en) * 2009-05-14 2009-06-16 한국화학연구원 Methanofullerene compounds having fluorinated substituents and its use for organic electronics
JP2011184326A (en) 2010-03-05 2011-09-22 Japan Science & Technology Agency Fullerene dimer and method for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthetic Metals, 133-134, pp. 679-683 (2003) *

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