KR20090113607A - Methanofullerene Compounds Having Etyleneoxy Substituents and Its Use for Organic Electronics - Google Patents

Abstract

PURPOSE: A methanofullerene compound containing an ethyleneoxy group is provided to improve solubility for organic solvent, electron affinity, and self-organization between ethyleneoxy groups, thereby obtaining excellent photoelectric conversion efficiency. CONSTITUTION: A methanofullerene compound has a structure represented by the formula 1. In formula 1, A is C60, C72, C76, C78 or C84 as a fullerene derivative; R^1 is (C6-C30) aryl or (C4-C30) heteroaryl; R^2 is -L1-(CH2CH2O)b-R12-; and n is an integer of 1-7. An organic electronic device comprises the methanofullerene compound. The organic electronic device is selected from the group consisting of an organic light-emitting device, organic solar cell, organophotoreceptor(OPC), organic memory and organic transistor.

Description

Methanofullerene Compounds Having Etyleneoxy Substituents and Its Use for Organic Electronics}

The present invention relates to a methafullerene compound (methanofullerene) comprising a novel ethyleneoxy group and an organic electronic device comprising the same.

Organic semiconductor materials using single molecules and polymers have made great strides in the past 25 years. Conventional inorganic semiconductor materials have excellent characteristics and reliability, but it is true that due to manufacturing shortcomings and difficulties in the device fabrication process, the role is gradually transferred to organic semiconductor materials. Compared with inorganic semiconductor materials, organic semiconductor materials are simpler in manufacturing process and can be inexpensive in device fabrication, and due to the characteristics of organic materials, it is easy to develop materials expressing superior characteristics through simple structure changes. Can be.

On the other hand, another example in which the organic semiconductor material is used is an organic solar cell. In general, a photovoltaic cell includes a semiconductor layer and an electrode in a basic configuration. In the photovoltaic cell, electrons and holes are generated inside the semiconductor layer by light from the outside, and the potential difference between the P pole and the N pole is generated due to the movement of charges to the P and N poles, respectively. It is a device using the principle that current flows when a load is connected to a battery. However, as described above, the semiconductor layer of the photovoltaic cell also has a tendency to apply an organic semiconductor material rather than an inorganic material that requires a high price, high temperature vacuum process. In particular, when applied to a solar cell device, not only the device can be manufactured by a spin coating process, but also the development of a semiconductor compound in which battery efficiency does not decrease as the amount of light increases.

In addition, conventional organic semiconductor materials show a big difference in the mobility of holes and electrons, and in most cases, the mobility of holes is reported to be 10 to 1000 times faster than electron mobility. Therefore, relatively little results have been reported for n -type materials using electron transfer among acceptors of organic semiconductors and organic photovoltaic cells used as channel materials such as OTFT. Representative n -type organic semiconductor materials include materials having the following structure.

Fred Wudl's group introduced {6} -1- (3- (methoxycarbonyl) propyl)-{5} -1-phenyl (5,6] C61 (1995), a metafullerene derivative well known as PCBM. Reported {6} -l- (3- (Methoxycarbonyl) propyl)-{5} -l-phenyl [5.6] C61 ( J. Org. Chem. , 1995 , 60 , 532). It can be used as an organic solar cell by mixing with polymer donor materials such as PPV, MDMO-PPV, and P3HT. Initially, it was elementized at a mixing ratio of about 1: 3 with a PPV derivative. By annealing the fabricated device at high temperature or controlling the evaporation rate of the solvent when the organic thin film is formed, it shows high energy conversion efficiency of about 4% or more, but this post-treatment process is difficult to guarantee reproducibility, If left unattended, the morphology of the organic film is likely to change and have a fatal effect on efficiency or other device characteristics.

Therefore, the present inventors have studied to solve the above problems, by introducing an ethyleneoxy group in the metano fullerene, a novel n -type organic semiconductor compound which can improve the solubility and electrochemically affinity of the electrochemically Newly discovered, the present invention has been found to be applicable to the use as an active component of organic photovoltaic, organic thin film transistor (OTFT), organic light emitting device (OLED), organic memory device and the like.

Accordingly, it is an object of the present invention to provide a metanofullerene compound into which a novel ethyleneoxy group is introduced, and also by introducing an ethyleneoxy group into the metanofullerene compound to have a better electron mobility in a thin film state, thereby providing excellent n- It is to provide a material that can have the characteristics of a type organic semiconductor.

In addition, the present invention is a new metaethylene fullerene compound introduced into the ethyleneoxy group donor, that is, when mixed with the electron donor material, the interaction of the action period containing the ethyleneoxy group is more active, such as annealing (annealing) Another purpose is to implement a device having better characteristics even without the post-treatment process.

Another object of the present invention is to provide an acceptor for an organic solar cell, that is, an electron acceptor material, in which an energy conversion efficiency is improved through a combination with a general donor, that is, an electron donor material.

The present invention relates to a novel metafullerene compound (methanofullerene) represented by the following formula (1) and an organic electronic device comprising the same.

[Formula 1]

[Wherein A is a fullerene derivative, C60, C72, C76, C78 or C84;

로터 선택된 하나 이상의 치환기로 더 치환될 수 있으며; R ¹ is (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, wherein the aryl or heteroaryl of R ¹ is (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) 3- to 7-membered saturated or unsaturated containing ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen or sulfur in the heterocycle Heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, Phenoxy, cyano, nitro or

May be further substituted with one or more substituents selected from the rotor;

이며;R ² is

Is;

R ₁₁ and R ₁₂ independently of one another are (C ₁ -C ₃₀ ) alkyl, (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, alkyl, aryl or hetero of R ₁₁ and R ₁₂ Aryl is (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C _1- C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, 3- to 7-membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, containing oxygen, nitrogen or sulfur in the heterocycle, (C _1- One or more selected from C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano or nit;

L ₁ is a chemical bond, (C ₂ -C ₃₀ ) alkylene, (C ₂ -C ₃₀ ) alkenylene, (C ₂ -C ₃₀ ) alkynylene, (C ₆ -C ₃₀ ) arylene or (C ₄ -C ₃₀₎ and heteroarylene, alkylene, alkenylene, arylene, heterocyclic arylene wherein L ₁ is (C ₁ -C ₃₀₎ alkyl, (C ₁ -C ₃₀₎ alkoxy, (C ₆ -C ₃₀ ) Aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀₎ alkoxy, (C ₄ -C ₃₀₎ heteroaryl, (C ₃ -C ₃₀₎ cycloalkyl, saturation of the oxygen, nitrogen or sulfur-containing 3-to 7-membered in the heterocyclic or unsaturated heterocycloalkyl, hydroxy , Carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano, One or more selected from nitro or halogen may be further substituted;

a and b are each independently an integer from 1 to 100;

n is an integer of 1 to 7.]

Substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described herein include both straight and pulverized forms.

"Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes the system. Specific examples include phenyl, naphthyl, biphenyl, anthryl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl And the like, but are not limited thereto.

"Heteroaryl" described in the present invention means an aryl group containing 1 to 4 heteroatoms selected from N, O, P, S or Si as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon. To 6-membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. The heteroaryl includes divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized, for example to form N-oxides or quaternary salts. Representative examples include furyl, pyranyl, isobenzofuranyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizine 1, isoindolyl, indolyl, indazolyl, quinolizinyl, isoquinolyl, quinolyl, carbazolyl, phenantridinyl and their corresponding N -oxides (eg, pyridyl N -oxides, quinolyl N -oxides), quaternary salts thereof, and the like, but is not limited thereto.

로터 선택된 하나 이상의 치환기가 치환될 수 있으며, 구체적으로는 하기의 아릴 또는 헤테로아릴 화합물로서 예시될 수 있으나, 하기의 아릴 또는 헤테로아릴 화합물이 본 발명의 범위를 한정하는 것은 아니다.The aryl or heteroaryl of R ₁ is a monocyclic or fused ring, for each ring (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen or sulfur, 3-7 membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino , Mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano, nitro or

One or more substituents selected from the rotor may be substituted and specifically exemplified as the following aryl or heteroaryl compounds, but the following aryl or heteroaryl compounds are not intended to limit the scope of the present invention.

이고; R₁₁은 (C₁-C₃₀)알킬, (C₆-C₃₀)아릴 또는 (C₄-C₃₀)헤테로아릴이고, 상기 R₁₁의 알킬, 아릴 또는 헤테로아릴은 (C₁-C₃₀)알킬, (C₁-C₃₀)알콕시, (C₆-C₃₀)아릴, (C₆-C₃₀)아르(C₁-C₃₀)알킬, (C₁-C₃₀)알킬(C₆-C₃₀)아릴, (C₆-C₃₀)아르(C₁-C₃₀)알콕시, (C₄-C₃₀)헤테로아릴, (C₃-C₃₀)시클로알킬, 산소, 질소 또는 황을 헤테로고리 안에 포함하는 3원 내지 7원의 포화 또는 불포화 헤테로시클로알킬, 히드록시, 카르복실산, 아미노, 모노 또는 디 (C₁-C₃₀)알킬아미노, (C₁-C₃₀)알킬카보닐, (C₁-C₃₀)알콕시카보닐, 벤조일, 페녹시, 시아노 또는 니트로부터 선택된 하나 이상이 더 치환될 수 있고; a는 1 내지 100의ㅏ 정수이고; x는 1 내지 5의 정수이고; y는 1 내지 3의 정수이고; p는 1 내지 4의 정수이고; q는 1 내지 3의 정수이고; r은 1 또는 2의 정수이고; s는 1 내지 3의 정수이다.][Wherein, X, Y and Z are independently hydrogen, (C ₁ -C ₃₀₎ alkyl, (C ₁ -C ₃₀₎ koksi Al, (C ₆ -C ₃₀₎ aryl, (C ₆ -C ₃₀₎ with each other Ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ Heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen, or sulfur containing from 3 to 7 membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano, nitro or

ego; R ₁₁ is (C ₁ -C ₃₀ ) alkyl, (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, wherein the alkyl, aryl or heteroaryl of R ₁₁ is (C ₁ -C ₃₀ ) Alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen or sulfur in the heterocycle 3- to 7-membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀₎ alkoxycarbonyl, and the at least one selected from benzoyl, phenoxy, cyano, or knitted may be further substituted; a is an integer of 1 to 100; x is an integer from 1 to 5; y is an integer from 1 to 3; p is an integer from 1 to 4; q is an integer from 1 to 3; r is an integer of 1 or 2; s is an integer of 1 to 3.]

The metano fullerene compound according to the present invention may be specifically exemplified as the following compound, but the following compound does not limit the scope of the present invention.

[5,6] isomers

[6,6] isomers

The metano fullerene compound of formula 1 according to the present invention is prepared as shown in Scheme 1 below. Specifically, after an esterification reaction of an aryl or heteroaryl-substituted oxocarboxylic acid with an alcohol derivative including one or more ethyleneoxy groups under a sulfuric acid (H ₂ SO ₄ ) catalyst, p -toluenesulfonyl hydrazide ( p -toluenesulfonyl through reaction with hydrazide) p - to form a tosyl hydrazone (p -tosylhydrazone) derivative. When fullerene is added and heated under pyridine, p -tosylhydrazone derivatives are decomposed and carbene formed through the azide form is reacted with fullerene to give fullerene carbon number. [5,6] -isomers (compound a ) in the form of bonds to junctions of five and six rings can be prepared. In addition, the resulting [5,6] -isomer (Compound a ) was refluxed in a 1,2-dichlorobenzene solvent to prepare the [6,6] -Isomer (Compound b ) in a form bonded to a junction between six rings. can do.

Scheme 1

The organic electronic device including the meta-no fullerene compound of Formula 1 according to the present invention is characterized in that it is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic memory and an organic transistor.

The metanofullerene derivative including the novel ethyleneoxy group according to the present invention has improved solubility by introducing an ethyleneoxy substituent into fullerene, and more effectively electron mobility can be improved by self-assembly of ethyleneoxy period. These novel compounds are useful for use as electron transport layers of organic light emitting devices, electron acceptors of organic solar cells, electron transport layers of organic photoconductors (OPCs), n -type organic semiconductors of organic memories and organic transistors, and the like.

Hereinafter, for the detailed understanding of the present invention, the meta-no fullerene compound according to the present invention will be described for the representative compounds of the present invention, and methods for preparing the same, and the characteristics of the device, which are merely intended to illustrate the embodiments of the present invention. It does not limit the scope of.

Preparation Example 1 Compound PC ₆₀ Synthesis of BE-I [6,6] Isomers

Synthesis of 2-methoxyethyl 5-oxo-5-phenylpentanoate

In a three-neck 100 ml round bottom flask, 2.00 g (10.41 mmol) of 4-benzoylbutyryl acid, 0.95 g (12.49 mmol) of ethylene glycol monomethyl ether and 0.25 g (2.50 mmol) of concentrated sulfuric acid were added to 15 ml of toluene. The reaction was carried out at reflux for a time. The reaction solution was cooled, washed three times with 10% sodium carbonate solution (40 ml), and washed three times with distilled water (30 ml). The organic layer was separated, dried over magnesium sulfate, and the solvent was removed under vacuum to obtain 2-methoxyethyl 5-oxo-5-phenylpentanoate (2.29 g, 87%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.98-7.95 (m, 2H), 7.56-7.53 (m, 1H), 7.48-7.43 (m, 2H), 4.25 (t, J = 4.8 Hz, 2H) , 3.59 (t, J = 4.8 Hz, 2H), 3.38 (s, 3H), 3.07 (t, J = 7.2 Hz, 2H), 2.49 (t, J = 7.2 Hz, 2H), 2.13-2.06 (m, 2H)

Synthesis of 2-methoxyethyl 5- (2-tosylhydrazono) -5-phenylpentanoate

2-methoxyethyl 5-oxo-5-phenyl-pentanoate 2.26 g (9.03 mmol), p - Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 2.52 g ( 13.55 mmol) in methanol (15 mL) It dissolved and refluxed and reacted for 4 hours. After cooling to −15 ° C., stirring for further 2 hours, washing with cold methanol gave 2-methoxyethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (3.28 g, 86%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 9.21 (s, 1H), 7.91 (d, J = 8.1 Hz, 2H), 7.66-7.63 (m, 2H), 7.35-7.28 (m, 5H), 4.39 (t, J = 4.5 Hz, 2H), 3.66 (t, J = 4.5 Hz, 2H), 3.41 (s, 3H), 2.63 (t, J = 8.1 Hz, 2H), 2.41 (s, 3H), 2.38 -2.35 (m, 2H), 1.74-1.69 (m, 2H)

{6} -l- (3- (2'-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61 ({6} -l- (3- (2'-methoxyethyloxycarbonyl ) propyl)-{5} -l-phenyl [5.6] -C61)

2-methoxyethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (3.27 g, 7.81 mmol) was dissolved in 10 ml of dried pyridine in a nitrogen-substituted 100 ml three-necked round bottom flask. Stirred. NaOMe (0.44 g, 8.12 mmol) was slowly added thereto for 30 minutes, and then fullerene (Fullerene, 2.81 g, 3.91 mmol) was dissolved in 100 ml of 1,2-dichlorobenzene and injected for 24 hours at 65-70 ° C. Reacted for a while. After the reaction was completed, the solvent was concentrated to about 30 ml under reduced pressure, and then developed using a silica gel (40 x 10 cm) using a 1: 4 mixed solvent of ethyl acetate and hexane to form a brown solid {6}-. l- (3- (2'-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl- [5.6] -C61 (330 mg, 8%) was obtained.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.97 (d, J = 6.9 Hz, 2H), 7.61-7.41 (m, 3H), 4.19-4.16 (m, 2H), 3.56-3.53 (m, 2H) , 3.38 (s, 3H), 2.18 (t, J = 7.5 Hz, 2H), 1.67-1.62 (m, 2H), 1.55-1.52 (m, 2H)

{6} -l- (3- (2’- Methoxyethyloxycarbonyl ) Propyl)-{5} -l- Phenyl [6.6]- C61  ({6} -l- (3- (2'-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl [6.6]- C61 ) (Compound PC ₆₀ BE -I [6,6] -isomer)

In a 100 mL two-neck round bottom flask under nitrogen atmosphere, 330 mg of {6} -l- (3- (2-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 A dark purple solution dissolved in, 2-dichlorobenzene solvent (30 mL) was refluxed for 24 hours to convert the [5,6] isomer to the [6,6] isomer through isomerization. After the temperature was lowered to room temperature, the solvent was concentrated to about 5 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (2'-methoxyethyloxycarbonyl) propyl. )-{5} -l-phenyl [6.6] -C61 (Compound PC ₆₀ BE-I [6,6] -isomer) was obtained (yield: 92%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.92 (d, J = 6.9 Hz, 2H), 7.57-7.44 (m, 3H), 4.26-4.22 (m, 2H), 3.60-3.57 (m, 2H), 3.38 (s, 3H), 2.94-2.89 (m, 2H), 2.57 (t, J = 7.5 Hz, 2H), 2.22-2.17 (m, 2H)

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.07, 147.78, 145.17, 145.06, 144.77, 144.66, 144.48, 144.41, 143.98, 143.74, 143.01, 142.96, 142.91, 142.22, 142.11, 142.11. 128.42, 128.23, 79.85, 70.40, 63.56, 59.02, 51.85, 33.94, 30.92, 22.34

FABMS m / z : 954 (M ⁺ H): calcd. (C ₁₄ H ₂₀ O ₃ ), 955

[ Production Example  2] compound PC ₆₀ BE - II  Synthesis of [6,6] -isomers

2- (2- Methoxyethoxy Ethyl 5-oxo-5- Phenylpentanoate  (2- (2- methoxyethoxy ) ethyl  5- oxo -5-phenylpentanoate) Synthesis

In a three-neck 100 ml round bottom flask, 2.0 g (10.41 mmol) of 4-benzoylbutyryl acid, 1.5 g (12.49 mmol) of diethylene glycol methyl ether, and 0.25 g (2.50 mmol) of concentrated sulfuric acid were used in the same manner as in Preparation Example 1. 2- (2-methoxyethoxy) ethyl 5-oxo-5-phenylpentanoate (2.62 g, 85%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.98-7.95 (m, 2H), 7.56-7.54 (m, 1H), 7.49-7.43 (m, 2H), 4.26 (t, J = 4.8 Hz, 2H), 3.71 (t, J = 4.8 Hz, 2H), 3.64-3.62 (m, 2H), 3.55-3.53 (m, 2H), 3.37 (s, 3H), 3.07 (t, J = 7.2 Hz, 2H), 2.48 (t, J = 7.2 Hz, 2H), 2.10-2.06 (m, 2H)

2- (2- Methoxyethoxy Ethyl 5- (2- Tosylhydrazone ) -5- Phenylpentanoate   2- (2- methoxyethoxy ) ethyl  Synthesis of 5- (2-tosylhydrazono) -5-phenylpentanoate

2- (2-methoxyethoxy) ethyl 5-oxo-5-phenyl-pentanoate 2.58 g (8.77 mmol), p - Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 2.45 g ( 13.15 mmol) of 2- (2-methoxyethoxy) ethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (3.52 g, in the same manner as in Preparation Example 1 except that the solvent was dissolved in methanol (15 ml) 86%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 9.22 (s, 1H), 7.91 (d, J = 8.1 Hz, 2H), 7.67-7.63 (m, 2H), 7.35-7.28 (m, 5H), 4.40 ( t, J = 4.5 Hz, 2H), 3.78 (t, J = 4.5 Hz, 2H), 3.69 (t, J = 4.5 Hz, 2H), 3.54 (t, J = 4.5 Hz, 2H), 3.31 (s, 3H), 2.64 (t, J = 8.1 Hz, 2H), 2.41 (s, 3H), 2.36 (t, J = 6 Hz, 2H). 1.71-1.61 (m, 2H)

{6} -l- (3- (2 '-(2'- Methoxyethoxyethyl ) Carbonyl) propyl)-{5} -l- Phenyl [5.6]- C61  ({6} -l- (3- (2 '-(2'- methoxyethoxy ) ethylcarbonyl ) propyl )-{5} -l- phenyl [5.6]- C61 ) Synthesis

10 ml of 2- (2-methoxyethoxy) ethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (0.5 g, 1.08 mmol) was added to a 100 mL three-necked round bottom flask with nitrogen substitution. (6) -l- (3- (2 '-(2'-methoxyethoxyethyl) carbonyl) propyl as a brown solid in the same manner as in Preparation Example 1, except that the mixture was dissolved in the dried pyridine and stirred. -{5} -l-phenyl- [5.6] -C61 (140 mg, 25%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.97 (d, J = 6.9 Hz, 2H), 7.59-7.28 (m, 3H), 4.18 (t, J = 4.8 Hz, 2H), 3.71-3.60 (m, 4H), 3.56-3.52 (m, 2H), 3.38 (s, 3H), 2.16 (t, J = 7.5 Hz, 2H), 1.67-1.61 (m, 2H), 1.54-1.47 (m, 2H)

{6} -l- (3- (2 '-(2'- Methoxyethoxyethyl ) Carbonyl) propyl)-{5} -l- Phenyl [6.6]- C61  ({6} -l- (3- (2 '-(2'- methoxyethoxy ) ethylcarbonyl ) propyl )-{5} -l- phenyl [6.6]- C61 ) (Compound PC ₆₀ BE - II  [6,6] -isomers)

140 mg of {6} -l- (3- (2 '-(2'-methoxyethoxyethyl) carbonyl) propyl)-{5} -l-phenyl in a 100 mL two-neck round bottom flask under nitrogen atmosphere A dark purple solution of [6.6] -C61 in 1,2-dichlorobenzene solvent (15 ml) was refluxed for 24 hours to convert the [5,6] isomer to the [6,6] isomer through isomerization. . After the temperature was lowered to room temperature, the solvent was concentrated to about 5 ml under reduced pressure, 150 ml of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 ml of 1,2-dichlorobenzene, 100 ml of methanol was injected and precipitated again. Centrifugation gave pure {6} -l- (3- (2 '-(2'-methoxyethoxy). Ethyl) carbonyl) propyl)-{5} -l-phenyl [6.6] -C61 (Compound PC ₆₀ BE-II [6,6] -isomer) was obtained (yield: 91%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.93 (d, J = 6.9 Hz, 2H), 7.57-7.47 (m, 3H), 4.25 (t, J = 4.8 Hz, 2H), 3.71-3.62 (m, 4H), 3.57-3.53 (m, 2H), 3.38 (s, 3H), 2.94-2.88 (m, 2H), 2.56 (t, J = 7.5 Hz, 2H), 2.21-2.16 (m, 2H)

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.04, 145.83, 145.17, 145.05, 144.77, 144.65, 144.48, 144.40, 143.98, 143.74, 143.01, 142.97, 142.91, 142.21, 142.15, 142.11. 128.42, 128.23, 79.85, 71.86, 70.48, 69.13, 63.60, 59.09, 51.86, 33.96, 30.92, 22.33

FABMS m / z : 998 (M ⁺ H): calcd. (C ₁₆ H ₂₄ O ₄ ), 999

[ Production Example  3] compound PC ₇₀ BE Synthesis of -I [6,6] -isomer

2- Methoxyethyl  5-oxo-5- Phenylpentanoate  (2- methoxyethyl  5- oxo -5- phenylpentanoate ) Synthesis

In a three-neck 100 ml round bottom flask, 2.00 g (10.41 mmol) of 4-benzoylbutyryl acid, 0.95 g (12.49 mmol) of ethylene glycol monomethyl ether and 0.25 g (2.50 mmol) of concentrated sulfuric acid were used. In the same manner, 2-methoxyethyl 5-oxo-5-phenylpentanoate (2.29 g, 87%) was obtained.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.98-7.95 (m, 2H), 7.56-7.53 (m, 1H), 7.48-7.43 (m, 2H), 4.25 (t, J = 4.8 Hz, 2H) , 3.59 (t, J = 4.8 Hz, 2H), 3.38 (s, 3H), 3.07 (t, J = 7.2 Hz, 2H), 2.49 (t, J = 7.2 Hz, 2H), 2.13-2.06 (m, 2H)

2- Methoxyethyl  5- (2- Tosylhydrazone ) -5- Phenylpentanoate  (2- methoxyethyl  5- (2- tosylhydrazono ) -5-phenylpentanoate)

2-methoxyethyl 5-oxo-5-phenyl-pentanoate 2.26 g (9.03 mmol), p - Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 2.52 g ( 13.55 mmol) in methanol (15 ml) Except for the dissolution, 2-methoxyethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (3.28 g, 86%) was obtained in the same manner as in Preparation Example 1.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 9.21 (s, 1H), 7.91 (d, J = 8.1 Hz, 2H), 7.66-7.63 (m, 2H), 7.35-7.28 (m, 5H), 4.39 (t, J = 4.5 Hz, 2H), 3.66 (t, J = 4.5 Hz, 2H), 3.41 (s, 3H), 2.63 (t, J = 8.1 Hz, 2H), 2.41 (s, 3H), 2.38 -2.35 (m, 2H), 1.74-1.69 (m, 2H)

{6} -l- (3- (2’- Methoxyethyloxycarbonyl ) Propyl)-{5} -l- Phenyl [5.6] -C71 ({6} -l- (3- (2'- methoxyethyloxycarbonyl ) propyl )-{5} -l- phenyl  [5.6]- C71 ) Synthesis

A 2-methoxyethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (0.4 g, 0.96 mmol) was dissolved in 10 ml of dried pyridine in a nitrogen-substituted 100 mL three necked round bottom flask. [6] -l- (3- (2'-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl- [5.6] as a brown solid in the same manner as in Preparation Example 1 except that the mixture was stirred. -C71 (105 mg, 20%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 8.48 (d, J = 6.9 Hz, 1H), 7.81-7.76 (m, 2H), 7.60-7.52 (m, 2H), 4.21-4.18 (m, 2H), 3.57-3.54 (m, 2H), 3.38 (s, 3H), 2.52-2.17 (m, 4H), 1.93-1.70 (m, 2H)

{6} -l- (3- (2’- Methoxyethyloxycarbonyl ) Propyl)-{5} -l- Phenyl [6.6]- C71  ({6} -l- (3- (2'-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl [6.6]- C71 ) (Compound PC ₇₀ BE -I [6,6] -isomer)

105 mg of {6} -l- (3- (2'-methoxyethyloxycarbonyl) propyl)-{5} -l-phenyl- [5.6] -C71 in a 100 ml two-neck round bottom flask under nitrogen atmosphere The dark purple solution dissolved in 1,2-dichlorobenzene solvent (15 ml) was refluxed for 24 hours to convert the [5,6] isomer into the [6,6] isomer through the isomerization reaction. After the temperature was lowered to room temperature, the solvent was concentrated to about 5 ml under reduced pressure, 150 ml of methanol solvent was poured out to precipitate, and centrifuged. The solid thus separated was dissolved in 10 ml of 1,2-dichlorobenzene, 100 ml of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (2'-methoxyethyloxycarbonyl) propyl. )-{5} -l-phenyl- [6.6] -C71 (Compound PC ₇₀ BE-I [6,6] -isomer) was obtained (yield: 74%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.91 (d, J = 6 Hz, 2H), 7.55-7.41 (m, 3H), 4.23 (t. J = 4.8 Hz, 2H), 3.58 (t, J = 4.8 Hz, 2H), 3.38 (s, 3H), 2.55-2.42 (m, 4H), 2.23-2.05 (m, 2H)

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.00, 150.51, 149.41, 149.17, 148.50, 148.29, 148.00, 147.55, 147.41, 145.80, 145.63, 143.22, 142.62, 137.26, 131.58, 130.74, 128.52. 75.89, 71.88, 70.41, 69.79, 63.57, 61.76, 59.03, 35.88, 34.06, 30.92, 21.66

FABMS m / z : 1074 (M ⁺ H): calcd. (C ₁₄ H ₂₀ O ₃ ), 1076

[ Production Example  4] compound PC ₇₀ BE - II  Synthesis of [6,6] -isomers

2- (2- Methoxyethoxy Ethyl 5-oxo-5- Phenylpentanoate  (2- (2- methoxyethoxy ) ethyl  5- oxo -5-phenylpentanoate)

In a three-neck 100 ml round bottom flask, 2.0 g (10.41 mmol) of 4-benzoylbutyryl acid, 1.5 g (12.49 mmol) of diethylene glycol methyl ether, and 0.25 g (2.50 mmol) of concentrated sulfuric acid were used in the same manner as in Preparation Example 1. 2- (2-methoxyethoxy) ethyl 5-oxo-5-phenylpentanoate (2.62 g, 85%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.98-7.95 (m, 2H), 7.56-7.54 (m, 1H), 7.49-7.43 (m, 2H), 4.26 (t, J = 4.8 Hz, 2H), 3.71 (t, J = 4.8 Hz, 2H), 3.64-3.62 (m, 2H), 3.55-3.53 (m, 2H), 3.37 (s, 3H), 3.07 (t, J = 7.2 Hz, 2H), 2.48 (t, J = 7.2 Hz, 2H), 2.10-2.06 (m, 2H)

2- (2- Methoxyethoxy Ethyl 5- (2- Tosylhydrazone ) -5- Phenylpentanoate  [2- (2- methoxyethoxy ) ethyl  Synthesis of 5- (2-tosylhydrazono) -5-phenylpentanoate]

2- (2-methoxyethoxy) ethyl 5-oxo-5-phenyl-pentanoate 2.58 g (8.77 mmol), p - Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 2.45 g ( 13.15 mmol) of 2- (2-methoxyethoxy) ethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (3.52 g, in the same manner as in Preparation Example 1 except that the solvent was dissolved in methanol (15 ml) 86%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 9.22 (s, 1H), 7.91 (d, J = 8.1 Hz, 2H), 7.67-7.63 (m, 2H), 7.35-7.28 (m, 5H), 4.40 ( t, J = 4.5 Hz, 2H), 3.78 (t, J = 4.5 Hz, 2H), 3.69 (t, J = 4.5 Hz, 2H), 3.54 (t, J = 4.5 Hz, 2H), 3.31 (s, 3H), 2.64 (t, J = 8.1 Hz, 2H), 2.41 (s, 3H), 2.36 (t, J = 6 Hz, 2H). 1.71-1.61 (m, 2H)

{6} -l- (3- (2 '-(2'- Methoxyethoxyethyl ) Carbonyl) propyl)-{5} -l- Phenyl [5.6]- C71  ({6} -l- (3- (2 '-(2'- methoxyethoxy ) ethylcarbonyl ) propyl )-{5} -l-  phenyl [5.6]- C71 ) Synthesis

10 ml of 2- (2-methoxyethoxy) ethyl 5- (2-tosylhydrazone) -5-phenylpentanoate (0.4 g, 0.86 mmol) was added to a nitrogen-substituted 100 mL three necked round bottom flask. {6} -l- (3- (2 '-(2'-methoxyethoxyethyl) carbonyl) propyl) as a brown solid in the same manner as in Preparation Example 1 except that the mixture was dissolved in dried pyridine and stirred. -{5} -l-phenyl- [5.6] -C61 (180 mg, 37%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 8.48 (d, J = 6.9 Hz, 1H), 7.88-7.72 (m, 2H), 7.62-7.48 (m, 2H), 4.26-4.19 (m, 2H), 3.71-3.40 (m, 6H), 3.38 (s, 3H), 2.59-2.39 (m, 2H), 2.38-2.26 (m, 2H), 1.95-1.84 (m, 2H)

{6} -l- (3- (2 '-(2'- Methoxyethoxyethyl ) Carbonyl) propyl)-{5} -l- Phenyl [6.6]- C71  ({6} -l- (3- (2 '-(2'- methoxyethoxy ) ethylcarbonyl ) propyl )-{5} -l- phenyl [6.6]- C71 ) Synthesis

180 mg of {6} -l- (3- (2 '-(2'-methoxyethoxyethyl) carbonyl) propyl)-{5} -l-phenyl in a 100 mL two-neck round bottom flask under nitrogen atmosphere -A dark purple solution of [5.6] -C71 in 1,2-dichlorobenzene solvent (20 mL) was refluxed for 24 hours to convert the [5,6] isomer to the [6,6] isomer through isomerization. I was. After the temperature was lowered to room temperature, the solvent was concentrated to about 15 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to pure {6} -l- (3- (2 '-(2'-methoxy). Methoxyethyl) carbonyl) propyl)-{5} -l-phenyl- [6.6] -C71 (Compound PC ₇₀ BE-II [6,6] -isomer) was obtained (yield: 74%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.91 (d, J = 6 Hz, 2H), 7.55-7.41 (m, 3H), 4.26 (t, J = 4.8 Hz, 2H), 3.71-3.41 (m, 6H), 3.38 (s, 3H), 2.54-2.42 (m, 4H), 2.20-2.07 (m, 2H)

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 172.97, 150.51, 149.16, 149.11, 148.49, 148.29, 148.00, 147.94, 147.50, 146.27, 145.79, 144.49, 141.71, 141.39, 140.13, 131.58, 130.74 128.19, 76.07, 71.87, 70.48, 69.79, 69.14, 63.61, 59.10, 53.41, 35.89, 34.07, 31.57, 22.63, 21.65, 14.10

FABMS m / z : 1118 (M ⁺ H): calcd. (C ₁₆ H ₂₄ O ₄ ), 1120

[ Example  1] according to the present invention Metanofullerene  Optical and Electrochemical Properties of Compounds

Optical characteristics of the meta-no fullerene compound (PC ₆₀ BE-I, PC ₆₀ BE-II, PC ₇₀ BE-I and PC ₇₀ BE-II) containing the ethyleneoxy group prepared in Preparation Examples 1 to 4 of the present invention UV absorption spectra and PL spectra are shown in FIGS. 2 and 3 using a UV / Vis spectrometer (UV-2550, Shimadzu) and a PL spectrometer (Fluoromax 2, Jovin-Yvon) for observation.

In addition, the electrochemical properties of the meta-no fullerene compound (PC ₆₀ BE-I, PC ₆₀ BE-II, PC ₇₀ BE-I and PC ₇₀ BE-II) containing the ethyleneoxy group prepared in Preparation Examples 1 to 4 For observation, oxidation / reduction characteristics were observed using a cyclovoltameter. CV equipment was used BAS 100 cyclovoltametry, 0.1M Bu ₄ NBF ₄ was used as acetonitrile solvent, the sample was dissolved in 1,2, -dichlorobenzene at a concentration of 10 ^-3 M. Measured at a scanning speed of 100 mW / s under Ar at room temperature, using a glass carbon electrode (0.3 mm diameter) as a working electrode, using a Pt and Ag / AgCl electrode as a counter electrode and a reference electrode and the results are shown in Figure 4 Shown in

In the UV absorption spectrum of FIG. 2, the metanofullerene derivatives including the ethyleneoxy group of the present invention showed almost the same absorption characteristics as the conventional PCBM ([6,6] phenyl-C61-butyric acid methyl ester), a kind of methanofullerene). In the PL spectrum of FIG. 3, light emission characteristics were observed at almost the same wavelength, but the light emission efficiency was relatively low. Through the above results, it was confirmed that the metanofullerene compound according to the present invention has a possibility of transferring light or electric energy absorbed more easily than the PCBM toward the electrode.

In addition, the meta-no fullerene compounds according to the present invention from Figure 4 showed three quasireversible reduction levels similar to PCBM in the interval of 0V to -2.0V, showed a somewhat positive value compared to the PCBM. These results are due to the electron withdrawing characteristics of the introduced ethyleneoxy group, it has been confirmed that the excellent n-type organic semiconductor material through the excellent electron affinity, the characteristics that can receive electrons through this. In addition, it is expected that the electron transfer characteristics can be improved.

[ Example  2] according to the present invention Metanofullerene  Fabrication of Organic Solar Cell Device Containing Compound and Measurement of Energy Conversion Efficiency

After spin coating PEDOT-PSS (Bayer Baytron P, Al 4083) by 40 nm on the washed ITO glass substrate, poly (3-hexylthiophene) [Poly-3- (hexylthiophene)] and the present invention prepared 1,2-dichlorobenzene or chlorobenzene, by selecting one of the metaoprene compounds containing ethyleneoxy group (PC ₆₀ BE-I, PC ₆₀ BE-II, PC ₇₀ BE-I and PC ₇₀ BE-II) Chloroform was dissolved alone or in a mixed solvent thereof to form an organic thin film by spin coating or the like. LiF / Al was deposited on the organic film thus formed under vacuum with an electrode, and then sealed with a glass cap with a moisture absorbent.

In general, the power conversion efficiency (PCE) of the solar cell can be obtained through the following equation.

[Wherein,

Voc is an open circuit voltage (V) and represents a voltage in a state in which no current flows;

Jsc is short circuit current density (mA / cm ² ), indicating current density at 0 V;

FF is the fill factor, the maximum power divided by the product of Voc and Jsc ;

Pinc represents the light intensity (mW / cm ² ) split.]

[Table 1] Comparison of characteristics of organic solar cell devices manufactured by mixing with P3HT.

As shown in Table 1, in the case of the device using the meta-no fullerene compound containing the ethyleneoxy group of the present invention, it was confirmed that shows a higher efficiency than the conventional PCBM in the state without a separate annealing. In particular, when the electron accepting materials of Preparation Examples 1 and 3 were used, high efficiencies of 2.54% and 3.24% were obtained, respectively.

Figure 1-Schematic diagram that can improve the aggregation between the electron acceptor material through the introduction of ethyleneoxy group

FIG. 2-UV Absorption Spectrum of Metanofullerene Derivatives Having Ethyleneoxy Group Prepared in Synthesis Examples 1 to 4

3-Electrochemical properties through CV of metanofullerene derivatives having ethyleneoxy groups prepared in Synthesis Examples 1 to 4

FIG. 4-Current-voltage curves of organic solar cell devices fabricated using ethyleneoxy group-based metanofullerene derivatives or PCBMs prepared in Synthesis Examples 1 to 4 as electron acceptors and P3HT as electron donors

Claims (6)

The metano fullerene compound represented by following formula (1). [Formula 1]

[Wherein A is a fullerene derivative, C60, C72, C76, C78 or C84; R ¹ is (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, wherein the aryl or heteroaryl of R ¹ is (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) 3- to 7-membered saturated or unsaturated containing ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen or sulfur in the heterocycle Heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, Phenoxy, cyano, nitro or

May be further substituted with one or more substituents selected from the rotor; R ² is

Is; R ₁₁ and R ₁₂ independently of one another are (C ₁ -C ₃₀ ) alkyl, (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, alkyl, aryl or hetero of R ₁₁ and R ₁₂ Aryl is (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C _1- C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, 3- to 7-membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, containing oxygen, nitrogen or sulfur in the heterocycle, (C _1- One or more selected from C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano or nit; L ₁ is a chemical bond, (C ₂ -C ₃₀ ) alkylene, (C ₂ -C ₃₀ ) alkenylene, (C ₂ -C ₃₀ ) alkynylene, (C ₆ -C ₃₀ ) arylene or (C ₄ -C ₃₀₎ and heteroarylene, alkylene, alkenylene, arylene, heterocyclic arylene wherein L ₁ is (C ₁ -C ₃₀₎ alkyl, (C ₁ -C ₃₀₎ alkoxy, (C ₆ -C ₃₀ ) Aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀₎ alkoxy, (C ₄ -C ₃₀₎ heteroaryl, (C ₃ -C ₃₀₎ cycloalkyl, saturation of the oxygen, nitrogen or sulfur-containing 3-to 7-membered in the heterocyclic or unsaturated heterocycloalkyl, hydroxy , Carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano, One or more selected from nitro or halogen may be further substituted; a and b are each independently an integer from 1 to 100; n is an integer of 1 to 7.] The method of claim 1, R ₁ is selected from the following structures:

[Wherein X, Y and Z are independently of each other hydrogen, (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) 3- to 7-membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (including heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen or sulfur in the heterocycle) C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano, nitro or

ego; R ₁₁ is (C ₁ -C ₃₀ ) alkyl, (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, wherein the alkyl, aryl or heteroaryl of R ₁₁ is (C ₁ -C ₃₀ ) Alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, (C ₃ -C ₃₀ ) cycloalkyl, oxygen, nitrogen or sulfur in the heterocycle 3- to 7-membered saturated or unsaturated heterocycloalkyl, hydroxy, carboxylic acid, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀₎ alkoxycarbonyl, and the at least one selected from benzoyl, phenoxy, cyano, or knitted may be further substituted; a is an integer from 1 to 100; x is an integer from 1 to 5; y is an integer from 1 to 3; p is an integer from 1 to 4; q is an integer from 1 to 3; r is an integer of 1 or 2; s is an integer of 1 to 3.] The method of claim 1, A metano fullerene compound, characterized in that it is selected from the following compounds.

The method of claim 1, A metano fullerene compound, characterized in that it is selected from the following compounds.

An organic electronic device comprising the metano fullerene compound according to any one of claims 1 to 4. The method of claim 5, The organic electronic device is an organic electronic device, characterized in that selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic memory and an organic transistor.

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