JP2010241778A - Fullerene derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fullerene derivative excellent in solubility to an organic solvent. <P>SOLUTION: This fullerene derivative is expressed by formula (1) [wherein, ring A is the fullerene ring; Ar is an arylene group or divalent heterocyclic group; R is alkyl, and the hydrogen atom in the alkyl group may be substituted by alkoxy, aryl, a halogen atom, a monovalent heterocyclic group or a group having an ester structure; (n) is an integer of ≥1; and in the case that there are a plurality of the Ars, they may be the same or different]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a fullerene derivative.

  Organic semiconductor materials with charge (electron, hole) transport properties are expected to be applied to organic photoelectric conversion elements (organic solar cells, optical sensors, etc.). Among them, organic solar cells using fullerene derivatives are considered. Has been. When manufacturing an organic solar cell containing a fullerene derivative, a solution in which the fullerene derivative is dissolved in an organic solvent is prepared, and a thin film is prepared from the solution by a coating method, and can be used for the organic solar cell. As a fullerene derivative, for example, [6,6] -phenyl C61-butyric acid methyl ester soluble in 1,2-dichlorobenzene (hereinafter sometimes referred to as [60] -PCBM) is known (non-non-volatile). Patent Document 1).

Advanced Functional Materials Vol.13 (2003) 85p

  However, [60] -PCBM has a problem that its solubility in hydrocarbon solvents is not always sufficient.

  Then, an object of this invention is to provide the fullerene derivative excellent in the solubility with respect to a hydrocarbon type solvent.

（１）
[式中、Ａ環はフラーレン環を、Ａｒはアリーレン基又は２価の複素環基を、Ｒはアルキル基を表す。アルキル基中の水素原子は、アルコキシ基、アリール基、ハロゲン原子、１価の複素環基又はエステル構造を有する基で置換されていてもよい。ｎは１以上の整数を表す。Ａｒが複数個ある場合、それらは同一でも相異なってもよい。] That is, the present invention first provides a fullerene derivative represented by the formula (1).

(1)
[Wherein, A ring represents a fullerene ring, Ar represents an arylene group or a divalent heterocyclic group, and R represents an alkyl group. The hydrogen atom in the alkyl group may be substituted with an alkoxy group, an aryl group, a halogen atom, a monovalent heterocyclic group or a group having an ester structure. n represents an integer of 1 or more. When there are a plurality of Ar, they may be the same or different. ]

  The present invention secondly provides a composition comprising the fullerene derivative and an electron donating compound.

  Thirdly, the present invention provides an organic photoelectric conversion device having a pair of electrodes, at least one of which is transparent or translucent, and a layer containing the fullerene derivative between the electrodes.

  The fullerene derivative of the present invention is excellent in solubility in hydrocarbon solvents and is suitably used for organic photoelectric conversion elements.

  Hereinafter, the present invention will be described in detail.

<Fullerene derivative>
The fullerene derivative of the present invention is represented by the formula (1). In formula (1), A ring represents a fullerene ring, Ar represents an arylene group or a divalent heterocyclic group, and R represents an alkyl group. The hydrogen atom in the alkyl group may be substituted with an alkoxy group, an aryl group, a halogen atom, a monovalent heterocyclic group or a group having an ester structure. Two A rings are the same, and two R are the same. n represents an integer of 1 or more. When there are a plurality of Ar, they may be the same or different.

The arylene group represented by Ar usually has about 6 to 60 carbon atoms. Specific examples thereof include a phenylene group, a biphenylene group, a terphenyldiyl group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, and a pentarange. Yl group, indenediyl group, hepterenediyl group, indacenediyl group, binaphthyldiyl group, phenylnaphthalenediyl group, stilbenediyl group, fluorenediyl group and the like.
The divalent heterocyclic group usually has about 3 to 60 carbon atoms constituting the heterocyclic ring. Specific examples thereof include a pyridinediyl group, a diazaphenylene group, a quinolinediyl group, a quinoxalinediyl group, and an acridine. Examples thereof include a diyl group, a bipyridinediyl group, a phenanthroline diyl group, and a thiophenediyl group. Of the divalent heterocyclic groups, divalent aromatic heterocyclic groups are preferred.

  In formula (1), n represents an integer of 1 or more. From the viewpoint of solubility of the fullerene derivative in the hydrocarbon solvent, n is preferably 1 or more and 10 or less. When there are a plurality of Ar, they may be the same or different. The hydrogen atom contained in Ar may be substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a monovalent heterocyclic group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The alkyl group usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyl group. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, s-butyl group, 3-methylbutyl group, n -Pentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group and the like. The hydrogen atom in the alkyl group may be substituted with a halogen atom, and examples thereof include a monohalomethyl group, a dihalomethyl group, a trihalomethyl group, and a pentahaloethyl group. Of the halogen atoms, it is preferably substituted with a fluorine atom. Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  The alkoxy group usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyloxy group. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, and n-pentyloxy. Group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, n -Lauryloxy group etc. are mentioned. A hydrogen atom in the alkoxy group may be substituted with a halogen atom. Of the halogen atoms, it is preferably substituted with a fluorine atom. Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

The aryl group usually has 6 to 60 carbon atoms and may have a substituent. Examples of the substituent that the aryl group has include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms. Or an alkoxy group containing a cycloalkyl group having 1 to 20 carbon atoms in its structure. Specific examples of the aryl group include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms, and the same applies to the following), C ₁ to C. ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl and the like, preferably an aryl group having 6 to 20 carbon atoms, C ₁ -C ₁₂ alkoxyphenyl group, more preferably C ₁ -C ₁₂ alkylphenyl group . A hydrogen atom in the aryl group may be substituted with a halogen atom. Of the halogen atoms, it is preferably substituted with a fluorine atom.

  As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable. Specific examples include a chenyl group, a pyridyl group, a furyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, and a pyrrolyl group.

  In formula (1), R represents an alkyl group. The hydrogen atom in the alkyl group may be substituted with an alkoxy group, an aryl group, a halogen atom, a monovalent heterocyclic group or a group having an ester structure. Specific examples of the alkyl group, alkoxy group, aryl group, halogen atom and monovalent heterocyclic group are the same as described above.

  Specific examples of the group having an ester structure include a group having butyric acid methyl ester, a group having butyric acid n-butyl ester, a group having butyric acid isopropyl ester, and a group having butyric acid 3-ethylthiophene ester.

The fullerene ring represented by the A ring is preferably a C ₆₀ fullerene ring or a C ₇₀ fullerene ring from the viewpoint of easy availability of raw materials.

  Specific examples of the fullerene derivative represented by the formula (1) include compounds represented by the following formula.

The fullerene derivative represented by the formula (1) is excellent in solubility in a hydrocarbon solvent, and since it is a fullerene dimer, it has a large molecular weight and excellent thermal stability. Moreover, the solar cell which has a sensitivity with respect to the light of a long wavelength can be created by giving light absorbency to the part of-(Ar) _n- in Formula (1).

Specifically, the fullerene derivative represented by the formula (1) can be synthesized by the following method.
By reacting the diketone Ar (—CO—R) ₂ (Ar and R have the same meaning as described above) represented by the formula (2) with the hydrazide represented by the formula (3), the formula (4 ) Is produced. By reacting the bishydrazone body with a base, a carbene intermediate represented by the formula (5) is generated. A fullerene derivative represented by the formula (1) can be synthesized by reacting the carbene intermediate with a fullerene molecule.

In formula (3), examples of Ar ² include a phenyl group and a tolyl group. The solvent used in the synthesis of the bishydrazone body (4) may be any solvent that does not react with the hydrazide (3) and dissolves the diketone body (2). For example, alcohols such as methanol, ethanol, isopropyl alcohol, Organic bases such as pyridine and triethylamine, aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene, halogenated unsaturated hydrocarbon solvents such as chlorobenzene and dichlorobenzene, halogens such as chloroform, dichloromethane and carbon tetrachloride And saturated ethers such as diethyl ether, methyl tertiary butyl ether, and diphenyl ether. These solvents may be used alone, or two or more kinds of solvents may be mixed and used.

  Examples of the base used for the formation of the carbene intermediate (5) and the reaction of the carbene intermediate with the fullerene molecule include sodium methoxide, sodium hydride, potassium hydride, t-butoxy potassium, t-butoxy sodium and the like. Can be mentioned. The solvent used for the production of the carbene intermediate and the reaction between the carbene intermediate and the fullerene molecule may be any solvent as long as it does not react with the above-mentioned base. For example, organic bases such as pyridine and triethylamine, diethyl ether, t-butyl Examples thereof include ethers such as methyl ether and diphenyl ether, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and halogenated unsaturated hydrocarbon solvents such as mesitylene, chlorobenzene and dichlorobenzene.

<Organic photoelectric conversion element>
The organic photoelectric conversion element using the fullerene derivative of the present invention has a pair of electrodes, at least one of which is transparent or translucent, and a layer containing the fullerene derivative of the present invention between the electrodes. The fullerene derivative of the present invention can be used as an electron accepting compound or an electron donating compound, but is preferably used as an electron accepting compound.

  Next, the operation mechanism of the organic photoelectric conversion element will be described. Light energy incident from a transparent or translucent electrode is absorbed by the electron-accepting compound and / or the electron-donating compound to generate excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface. Electric charges (electrons and holes) that can move are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

As a specific example of the organic photoelectric conversion element using the fullerene derivative of the present invention,
1. A pair of electrodes, at least one of which is transparent or translucent, a first organic layer provided between the electrodes and containing the fullerene derivative of the present invention as an electron-accepting compound, and adjacent to the first organic layer An organic photoelectric conversion element having a second organic layer containing an electron donating compound provided;
2. An organic photoelectric conversion device having a pair of electrodes, at least one of which is transparent or translucent, and at least one organic layer provided between the electrodes and containing the fullerene derivative of the present invention and an electron-donating compound as an electron-accepting compound Characterized by that,
Either of these is preferable.

  As the organic photoelectric conversion element of the present invention, the above-mentioned 2. Is preferred. In the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the organic layer in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons.

  As a material used for the additional layer, an alkali metal such as lithium fluoride, a halide of an alkaline earth metal, an oxide, or the like can be used. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

  In addition, 2. In the organic photoelectric conversion element, the ratio of the fullerene derivative in the organic layer containing the fullerene derivative and the electron donating compound of the present invention is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the electron donating compound. 50 to 500 parts by weight is more preferable.

  The organic layer containing the fullerene derivative of the present invention preferably includes an organic thin film containing the fullerene derivative. The thickness of the organic thin film is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

  The electron donating compound may be a low molecular compound or a high molecular compound. Examples of the low molecular weight compound include phthalocyanine, metal phthalocyanine, porphyrin, metal porphyrin, oligothiophene, tetracene, pentacene, and rubrene. Examples of the polymer compound include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and Examples thereof include polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like. From the viewpoint of applicability, a polymer compound is preferable.

（６） （７）
[式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、同一又は相異なり、水素原子、アルキル基、アルコキシ基又はアリール基を表す。] From the viewpoint of the conversion efficiency of the organic photoelectric conversion element, the electron donating compound used in the organic photoelectric conversion element is a polymer compound having a repeating unit selected from the group consisting of the following formula (6) and the following formula (7). The polymer compound having a repeating unit represented by the following formula (6) is more preferable.

(6) (7)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, an alkyl group, an alkoxy group or an aryl Represents a group. ]

In the above formula (6), specific examples in the case where R ¹ and R ² are alkyl groups include the same alkyl groups as those exemplified above. Specific examples in the case where R ¹ and R ² are alkoxy groups include the same alkoxy groups as those exemplified above. Specific examples of the case where R ¹ and R ² are aryl groups include the same aryl groups as those exemplified above for the aryl group.

In the formula (6), from the viewpoint of the conversion efficiency of the organic photoelectric conversion element, at least one of R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl having 4 to 8 carbon atoms. More preferably, it is a group.

In the above formula (7), specific examples in the case where R ^{3 to} R ¹⁰ are alkyl groups include the same alkyl groups as those exemplified above. Specific examples of the case where R ^{3 to} R ¹⁰ are alkoxy groups include the same alkoxy groups as those exemplified above. Specific examples of the case where R ^{3 to} R ¹⁰ are aryl groups include the same aryl groups as those exemplified above for the aryl group.

In the formula (7), R ^{5 to} R ¹⁰ are preferably hydrogen atoms from the viewpoint of ease of monomer synthesis. From the viewpoint of the conversion efficiency of the organic photoelectric conversion element, R ³ and R ⁴ are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 5 to 8 carbon atoms. It is more preferably a group or an aryl group having 6 to 15 carbon atoms.

  The organic photoelectric conversion element of the present invention is usually formed on a substrate. This substrate may be any substrate that does not change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

  Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film thereof (NESA) manufactured using a conductive material made of indium / tin / oxide (ITO), indium / zinc / oxide, or the like. Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material. Furthermore, as the electrode material, a metal, a conductive polymer, or the like can be used. Preferably, the material of one of the pair of electrodes is preferably a material having a low work function. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and two of them One or more alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or a graphite intercalation compound are used. It is done. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like.

<Method for producing organic thin film>
The method for producing the organic thin film is not particularly limited, and examples thereof include a method by film formation from a solution containing the fullerene derivative of the present invention.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve the fullerene derivative of the present invention. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and t-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane. Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, And ether solvents such as tetrahydrofuran and tetrahydropyran. The fullerene derivative can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

  The solution may further contain a polymer compound. Specific examples of the solvent used in the solution include the above-mentioned solvents. From the viewpoint of the solubility of the polymer compound, a hydrocarbon solvent is preferable, an aromatic hydrocarbon solvent is more preferable, toluene, Xylene and mesitylene are more preferable. Since the fullerene derivative of the present invention has excellent solubility in a hydrocarbon solvent, a layer included in a photoelectric conversion element is formed using a polymer compound, a solution containing the fullerene of the present invention and a hydrocarbon solvent. Can do.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

  By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

As reagents and solvents used in the synthesis, commercially available products were used as they were or products obtained by distillation purification in the presence of a desiccant were used. C ₆₀ fullerene used was made by Frontier Carbon.

窒素雰囲気下、50mlナスフラスコにクロロホルム100ｍｌ、化合物 1 2.40g（4.11mmol）、酸クロリド2 0.76g（4.62mmol）、塩化アルミニウム（ＩＩＩ） 0.66g（4.94mmol）を順次加え10時間加熱還流した。反応液を冷却後、水100mｌ中に反応液を加え、酢酸エチル100mｌを用い、有機相を２回抽出した後、有機相を無水硫酸ナトリウムを用いて乾燥し、減圧濃縮することで粗ビスケトエステル体を得た。これをシリカゲルカラムクロマトグラフィー（WakosilC-300、展開液：トルエン／酢酸エチル＝３：１（容積比））にて精製することでビスケトエステル体３を0.48g（収率13.9%）得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ ０．９１（ｔ、６Ｈ）、１．２５−１．７０（ｍ、１６Ｈ）、２．０９（quint、４Ｈ）、２．４６（ｔ、４Ｈ）、２．７３（ｍ、４Ｈ）、２．９７（ｔ、４Ｈ）、３．６９（ｓ、６Ｈ）、７．０８（ｄ、２Ｈ）、７．１６（ｄ、２Ｈ）、７．２５（ｄ、２Ｈ）、７．６３（ｄ、２Ｈ） Example 1
(Synthesis of bisketoester 3 )

Under a nitrogen atmosphere, 50 ml eggplant type flask in chloroform 100 ml, Compound 1 2.40g (4.11mmol), the acid chloride 2 0.76g (4.62mmol), was added sequentially heated under reflux for 10 hours aluminum chloride (III) 0.66g (4.94mmol). After cooling the reaction solution, the reaction solution is added to 100 ml of water, the organic phase is extracted twice with 100 ml of ethyl acetate, the organic phase is dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude bisketo ester. Got the body. This was purified by silica gel column chromatography (Wakosil C-300, developing solution: toluene / ethyl acetate = 3: 1 (volume ratio)) to obtain 0.48 g (yield 13.9%) of bisketo ester 3 .
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.25-1.70 (m, 16H), 2.09 (quint, 4H), 2.46 (t, 4H), 2.73 (m, 4H), 2.97 (t, 4H), 3.69 (s, 6H), 7.08 (d, 2H), 7.16 (d, 2H), 7.25 (d, 2H), 7.63 (d) 2H)

ビスケトエステル体３ 0.48gをクロロホルム50ｍｌに溶解し、ｐ−トルエンスルホニルヒドラジド0.24g（1.29mmol）を加え、20時間加熱還流した。
反応液を放冷後、エバポレータを用いて濃縮乾固させ、残渣をメタノール100mlを用いてリパルプ洗浄し、得られた固形分を減圧乾燥することでビスヒドラゾン体４を0.30g（収率４４．５％）得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ ０．９２（ｔ、６Ｈ）、１．２５−１．８０（ｍ、２０Ｈ）、２．３３（ｍ、４Ｈ）、２．４１（ｓ、６Ｈ）、２．５９（ｔ、４Ｈ）、２．７３（ｍ、４Ｈ）、３．８０（ｓ、６Ｈ）、７．００−７．１０（ｍ、６Ｈ）、７．１８（ｄ、２Ｈ）、７．３１（ｄ、４Ｈ）、７．９２（ｄ、４Ｈ）、９．０３（ｓ、２Ｈ） (Synthesis of bishydrazone body 4 )

Bisketoester 3 0.48g was dissolved in chloroform 50ml, p-toluenesulfonyl hydrazide 0.24g (1.29mmol) was added, and it heated and refluxed for 20 hours.
The reaction solution is allowed to cool and then concentrated to dryness using an evaporator. The residue is washed with repulp using 100 ml of methanol, and the resulting solid is dried under reduced pressure to obtain 0.30 g of bishydrazone body 4 (yield 44.%). 5%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.92 (t, 6H), 1.25-1.80 (m, 20H), 2.33 (m, 4H), 2.41 (s, 6H), 2.59 (t, 4H), 2.73 (m, 4H), 3.80 (s, 6H), 7.00-7.10 (m, 6H), 7.18 (d, 2H), 7.31 (d, 4H), 7 .92 (d, 4H), 9.03 (s, 2H)

窒素雰囲気下、50mlナスフラスコにビスヒドラゾン体４ 0.30ｇ（0.26mmol）と乾燥ピリジン10ml、ナトリウムメトキシド0.03g（0.64mmol）を加え15分間室温で撹拌した。ピリジン溶液中に、クロロベンゼン20mｌに溶解したC60フラーレン 0.18g（0.26mmol）を一度に加え、窒素気流下７0℃にて24時間加熱撹拌した。反応液を室温まで冷却した後、エバポレータを用いて反応液を減圧濃縮し、その後、得られた残渣をシリカゲルクロマトグラフィー（WakosilC-300）にて精製した。シリカゲルクロマトグラフィーによる精製は、グラジエントをかけながらトルエンと酢酸エチルとの混合溶媒をトルエン／酢酸エチル＝１００／０から９０／１０（容積比）の条件で流し、その後、クロロホルムと酢酸エチルとの混合溶媒をクロロホルム／酢酸エチル＝９０／１０（容積比）の条件で流した。分画した溶液のうち、フラーレン誘導体が含まれる溶液を濃縮し、得られた残渣にトルエン10ｍl加えて撹拌溶解させ、トルエン溶液をメタノール50ml中に加え、目的物であるフラーレン誘導体を再沈殿させた。固形物をろ取後、減圧乾燥することで目的物であるフラーレン誘導体５を85mg（収率12.7 %）得た。これをフラーレン誘導体Ａと呼ぶ。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ ０．９２（ｍ、６Ｈ）、１．２０−１．７０（ｍ、１６Ｈ）、２．２０−２．５０（ｍ、４Ｈ）、２．６１（ｍ、４Ｈ）、２．７２（ｍ、４Ｈ）、２．９７（ｍ、４Ｈ）、３．７０（ｓ、６H）、７．００−７．４０（ｍ、８Ｈ） (Synthesis of fullerene derivative A)

Under a nitrogen atmosphere, 0.30 g (0.26 mmol) of bishydrazone compound 4, 10 ml of dry pyridine and 0.03 g (0.64 mmol) of sodium methoxide were added to a 50 ml eggplant flask and stirred at room temperature for 15 minutes. To the pyridine solution, 0.18 g (0.26 mmol) of C60 fullerene dissolved in 20 ml of chlorobenzene was added at once, and the mixture was heated and stirred at 70 ° C. for 24 hours under a nitrogen stream. After cooling the reaction solution to room temperature, the reaction solution was concentrated under reduced pressure using an evaporator, and then the obtained residue was purified by silica gel chromatography (Wakosil C-300). For purification by silica gel chromatography, a mixed solvent of toluene and ethyl acetate is allowed to flow under conditions of toluene / ethyl acetate = 100/0 to 90/10 (volume ratio) while applying a gradient, and then mixed with chloroform and ethyl acetate. The solvent was passed under conditions of chloroform / ethyl acetate = 90/10 (volume ratio). Of the fractionated solution, the solution containing the fullerene derivative was concentrated, 10 ml of toluene was added to the resulting residue and dissolved by stirring, and the toluene solution was added into 50 ml of methanol to reprecipitate the fullerene derivative as the target product. . The solid was collected by filtration and dried under reduced pressure to obtain 85 mg (yield: 12.7%) of the target fullerene derivative 5 . This is called fullerene derivative A.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.92 (m, 6H), 1.20-1.70 (m, 16H), 2.20-2.50 (m, 4H), 2.61 (m, 4H), 2.72 (m 4H), 2.97 (m, 4H), 3.70 (s, 6H), 7.00-7.40 (m, 8H)

Evaluation Example 1
(Evaluation of solubility in xylene)
A xylene solvent was added to the fullerene derivative A to a concentration of 1 wt%, and the mixture was stirred for 10 minutes with a magnetic stirrer. The subsequent solubility in xylene solvent was visually observed. The results are shown in Table 1.

Evaluation example 2
(Evaluation of solubility in xylene)
The solubility in a xylene solvent was evaluated in the same manner as in Evaluation Example 1 except that [60] PCBM (manufactured by Frontier Carbon, trade name nanom spectra E100, lot number: 8B059-A) was used instead of the fullerene derivative A. The results are shown in Table 1.

Claims (5)

A fullerene derivative represented by the formula (1):

(1)
[Wherein, A ring represents a fullerene ring, Ar represents an arylene group or a divalent heterocyclic group, and R represents an alkyl group. The hydrogen atom in the alkyl group may be substituted with an alkoxy group, an aryl group, a halogen atom, a monovalent heterocyclic group or a group having an ester structure. n represents an integer of 1 or more. When there are a plurality of Ar, they may be the same or different. ]   A composition comprising the fullerene derivative according to claim 1 and an electron donating compound.   The composition according to claim 2, wherein the electron donating compound is a polymer compound.   An organic photoelectric conversion device comprising a pair of electrodes, at least one of which is transparent or translucent, and a layer containing the fullerene derivative according to claim 1 between the electrodes.   An organic photoelectric conversion device comprising a pair of electrodes, at least one of which is transparent or translucent, and a layer containing the composition according to claim 2 or 3 between the electrodes.