WO2023100719A1 - FULLERENE DERIVATIVE, n-TYPE SEMICONDUCTOR MATERIAL, ORGANIC POWER GENERATION LAYER AND PHOTOELECTRIC CONVERSION ELEMENT - Google Patents

FULLERENE DERIVATIVE, n-TYPE SEMICONDUCTOR MATERIAL, ORGANIC POWER GENERATION LAYER AND PHOTOELECTRIC CONVERSION ELEMENT Download PDF

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WO2023100719A1
WO2023100719A1 PCT/JP2022/043184 JP2022043184W WO2023100719A1 WO 2023100719 A1 WO2023100719 A1 WO 2023100719A1 JP 2022043184 W JP2022043184 W JP 2022043184W WO 2023100719 A1 WO2023100719 A1 WO 2023100719A1
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group
substituents
alkyl group
substituent
fullerene derivative
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PCT/JP2022/043184
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French (fr)
Japanese (ja)
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隆文 永井
啓人 大瀧
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株式会社ハーベス
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to fullerene derivatives, n-type semiconductor materials, organic power generation layers, and photoelectric conversion elements.
  • An organic thin-film solar cell uses an organic compound as a photoelectric conversion material and is generally formed by a coating method from a solution.
  • Organic thin-film solar cells are inexpensive to fabricate, easy to scale up, flexible compared to inorganic materials such as silicon and can be used in a wider range of locations, and are less likely to deplete resources. It has various advantages such as. Therefore, in recent years, the development of organic thin-film solar cells has been promoted.
  • Patent Document 1 describes an organic photoelectric conversion element having a transparent electrode, a counter electrode, and a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are mixed, wherein the n-type organic semiconductor material of the bulk heterojunction layer is a crystal.
  • Patent Document 2 discloses an aryl group which has a pyrrolidine ring and may be substituted with one or more substituents, an alkyl group which may be substituted with one or more substituents, or 1 Inventions relating to fullerene derivatives characterized by having an alkyl ether optionally substituted with one or more substituents have been disclosed.
  • a photoelectric conversion device provided with an organic power generation layer using a conventional fullerene derivative as an n-type semiconductor material cannot obtain high conversion efficiency. Furthermore, a conventional photoelectric conversion device provided with an organic power generation layer using a fullerene derivative as an n-type semiconductor material cannot maintain high conversion efficiency for a long period of time, and there is room for improvement in durability. There was also limited information on compounds that could improve durability. Furthermore, generally, a photoelectric conversion element is produced by applying a solution composed of a p-type semiconductor material and an n-type semiconductor material. For this reason, the solubility of the semiconductor material used here in the organic solvent used for device fabrication is important. PCBM, which has been widely used as an n-type semiconductor material, has a solubility of about 1% by mass in toluene, and PCBM with a much lower solubility than this poses a problem in device fabrication by solution coating.
  • the present invention has been made in view of such circumstances, and in a photoelectric conversion device provided with an organic power generation layer using a fullerene derivative as an n-type semiconductor material, the device can be easily manufactured by solution coating, and high conversion efficiency can be achieved.
  • R 1 represents an aryl group optionally having one or more substituents
  • R 2 represents an organic group
  • R 3 represents an organic group, at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents
  • Ring A represents a fullerene ring
  • Formula (1) satisfies at least one of the following two conditions. i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents; )
  • a photoelectric conversion element having an organic power generation layer using a fullerene derivative having a structure represented by a specific formula (1) as an n-type semiconductor material achieves high conversion efficiency. Furthermore, the photoelectric conversion element can maintain a high conversion efficiency for a long period of time, leading to the completion of the present invention.
  • an n-type semiconductor material comprising the above-described fullerene derivative, and according to another aspect of the present invention, the above-described n-type semiconductor material and p-type semiconductor material Provided is an organic power-generating layer containing According to another aspect of the present invention, there is provided a photoelectric conversion device comprising the organic power generation layer described above.
  • R 1 represents an aryl group optionally having one or more substituents
  • R 2 represents an organic group
  • R 3 represents an organic group
  • R 2 and At least one of R 3 represents an aryl group optionally having one or more substituents
  • Ring A represents a fullerene ring
  • formula (1) satisfies at least satisfy any one of i)
  • R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and R 1 , R 2 and R 3 at least one of is an aryl group having a substituent.
  • R2 and/or R3 are aryl groups with fluorine-containing substituents; ) [2]
  • R 1 is an unsubstituted aryl group or an aryl group with one or more substituents, and R 1 is an aryl group with one or more substituents
  • the first substituent is an alkyl group optionally having one or more substituents
  • the fullerene derivative according to [1] comprising at least one selected from the group consisting of aralkyl groups optionally having one or more substituents.
  • At least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position, and/or R 2 and R 3 at least one of which is an aryl group having an electron-withdrawing group at the ortho-position and/or para-position, the fullerene derivative according to [1] or [2].
  • at least one of R 1 , R 2 , and R 3 contains an alkyl group optionally having one or more substituents, and the alkyl group has a carbon number
  • R 2 and R 3 contains any one of a fluorine atom and a fluorinated alkyl group having 2 or less carbon atoms, [1] to [4 ] The fullerene derivative according to any one of the above.
  • the fullerene derivative according to any one of [1] to [5] which has a LUMO level value of less than ⁇ 3.67 eV and a toluene solubility of 0.5% or more.
  • An n-type semiconductor material comprising the fullerene derivative according to any one of [1] to [6].
  • An organic power generating layer containing the n-type semiconductor material of [7] and a p-type semiconductor material.
  • a photoelectric conversion device comprising the organic power generation layer according to [8].
  • the photoelectric conversion device according to [9] which is an organic thin film solar cell.
  • the photoelectric conversion device according to [9] wherein the decrease in energy conversion efficiency after heating at 85°C for 2 hours relative to the initial energy conversion efficiency is within 5%.
  • a photoelectric conversion device having an organic power generation layer using the fullerene derivative as an n-type semiconductor material can obtain high conversion efficiency. A high conversion efficiency can be maintained.
  • R 1 represents an aryl group optionally having one or more substituents
  • R 2 represents an organic group
  • R 3 represents an organic group, at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents
  • Ring A represents a fullerene ring
  • Formula (1) satisfies at least one of the following two conditions. i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents;
  • the fullerene derivative according to the present invention has a structure represented by the above formula (1), so that a photoelectric conversion element having an organic power generation layer using the fullerene derivative as an n-type semiconductor material can obtain high conversion efficiency. Furthermore, the photoelectric conversion element can maintain high conversion efficiency for a long period of time. Although the reason why a photoelectric conversion device having high conversion efficiency and high durability can be obtained by using the fullerene derivative according to the present invention is not clear, the fullerene derivative according to the present invention can be used to improve the conversion efficiency and durability.
  • the fullerene derivative according to the present invention has a structure represented by formula (1), so that it is sufficiently soluble in an organic solvent such as toluene, and the organic power generation layer forming solution can be easily prepared.
  • a thin film can be easily formed on a substrate by adopting the thin film forming method of (1).
  • R 1 , R 2 , R 3 and ring A each have a specific structure, and formula (1) satisfies conditions i) and ii). It is characterized by satisfying at least one of them.
  • Common preferred embodiments for cases i) and ii) Particularly preferred embodiments for i) Especially preferred embodiments for ii) The embodiments of the present invention will be described in this order.
  • R 1 represents an aryl group optionally having one or more substituents.
  • R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, and the aryl group is preferably a phenyl group.
  • R 1 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 1 is referred to as a first substituent.
  • R 1 can consist of the first substituent and an aryl group.
  • the first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two.
  • the first substituent further preferably contains at least one selected from the group consisting of alkyl groups optionally having one or more substituents, and may contain one or more of these, It can contain one or two.
  • the first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
  • alkyl group optionally having one or more substituents that the first substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups.
  • the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
  • R2 represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 2 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group that has a low molecular weight is preferred.
  • R 2 is an alkyl group optionally having one or more substituents
  • R 2 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 2 When R 2 represents an aryl group optionally having one or more substituents, R 2 can be an unsubstituted aryl group or an aryl group having one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, and the aryl group is preferably a phenyl group.
  • R 2 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 2 is referred to as a second substituent.
  • R2 can consist of a second substituent and an aryl group.
  • the second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen.
  • R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, or a pentafluoroethyl group.
  • a trifluoromethyl group and a pentafluoroethyl group are more preferred, and a trifluoromethyl group is even more preferred.
  • alkyl group optionally having one or more substituents that the second substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R3 represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 3 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group that has a low molecular weight is preferred.
  • R 3 is an alkyl group optionally having one or more substituents
  • R 3 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 3 is an aryl group optionally having one or more substituents
  • the substituent of the aryl group contained in R 3 is referred to as the third substituent.
  • R3 can consist of a third substituent and an aryl group.
  • the third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen.
  • R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • the alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents.
  • Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R 2 and R 3 represents an aryl group optionally having one or more substituents.
  • one of R 2 and R 3 is an alkyl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents group, the other is preferably an aryl group in which the second (or third) substituent is a fluorine-containing group.
  • R 1 , R 2 and R 3 in formula (1), at least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position, and/or R 2 and/or R 3 can be an aryl group having an electron-withdrawing group at the ortho and/or para position.
  • R 1 , R 2 and R 3 in formula (1), only one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position.
  • two of R 1 , R 2 and R 3 may be aryl groups having an electron donating group at the meta position, or R 1 , R 2 and R 3 may have an electron donating group at the meta position.
  • R 2 or R 3 may be an aryl group having an electron withdrawing group at the ortho and/or para position, or R 2 and R 3 may have an electron withdrawing group at the ortho and/or para position.
  • R 2 and R 3 may have an electron withdrawing group at the ortho and/or para position.
  • Examples of the electron-donating group that at least one of R 1 , R 2 , and R 3 may have at the meta position include alkyl groups optionally having one or more substituents, and aralkyl groups. is preferably an alkyl group optionally having one or more substituents. Examples of the alkyl group optionally having one or more substituents include linear or branched alkyl groups optionally having one or more substituents. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. As the alkyl group, specific examples of the alkyl group listed as the first substituent can be given.
  • Examples of the electron-withdrawing group that at least one of R 2 and R 3 may have at the ortho-position and/or para-position include a fluorine atom and a fluorinated alkyl group.
  • a fluorinated alkyl group can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • At least one of R 1 , R 2 and R 3 may contain an alkyl group optionally having one or more substituents.
  • the alkyl group that at least one of R 1 , R 2 , and R 3 may contain may be a linear or branched alkyl group having 4 or more and 12 or less carbon atoms.
  • R 1 , R 2 and R 3 contains an alkyl group optionally having one or more substituents
  • R 1 , R 2 or , R 3 is an aryl group optionally having one or more substituents
  • R 1 , R 2 or R 3 is the first, second or third substituent, This includes cases where an alkyl group optionally having one or more substituents is included.
  • alkyl group that at least one of R 1 , R 2 and R 3 may contain does not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group that at least one of R 1 , R 2 and R 3 may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • At least one of R 2 and R 3 may contain any one of a fluorine atom and a fluorinated alkyl group having 1 or 2 carbon atoms.
  • "at least one of R 2 and R 3 contains any one of a fluorine atom and a fluorinated alkyl group having 1 or 2 carbon atoms” means, for example, R 2 and/or R 3 is an aryl group optionally having one or more substituents, wherein R 2 and/or R 3 are, as the second or third substituents, a fluorine atom and 1 or 2 carbon atoms It includes the case of containing any one of fluorinated alkyl groups.
  • the fluorinated alkyl group that at least one of R 2 and R 3 may have can be a fluoroalkyl group in which the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms. Specific examples of the fluorinated alkyl group include the fluorinated alkyl groups listed as the fluorinated alkyl groups that the second substituent and the third substituent may contain.
  • Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
  • the fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture.
  • the content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
  • the fullerene derivative represented by Formula (1) according to the present invention satisfies at least one of the following two conditions. i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents;
  • the fullerene derivative represented by formula (1) according to the present invention satisfies at least one of the above conditions i) and ii), and more preferably satisfies the above conditions i) and ii). An embodiment that is particularly preferred when condition i) is satisfied will be described in detail below.
  • R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is Especially preferred embodiment when the aryl group has a substituent>
  • R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and , R 1 , R 2 , and R 3 can be a substituted aryl group. That is, in this case, all of R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and R 1 , R 2 and R 3 At least one of them can be an aryl group having a substituent.
  • R 1 , R 2 and R 3 can be substituted aryl groups.
  • R 1 , R 2 and R 3 are preferably substituted aryl groups.
  • at least R 1 is preferably an aryl group having a substituent.
  • R 1 represents an aryl group optionally having one or more substituents. That is, R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 1 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 1 is referred to as a first substituent.
  • R 1 can consist of the first substituent and an aryl group.
  • the first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two.
  • the first substituent can be an alkyl group optionally having one or more substituents.
  • the first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
  • alkyl group optionally having one or more substituents that the first substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups.
  • the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
  • R 1 is preferably a substituted aryl group, more preferably a substituted phenyl group.
  • R 1 preferably has, as the first substituent, an alkyl group optionally substituted with one or more substituents. Preferred forms of alkyl groups optionally substituted with one or more substituents are as described above.
  • R 1 preferably has an alkyl group optionally substituted with one or more substituents at the meta position.
  • R2 represents an aryl group optionally having one or more substituents.
  • R 2 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 2 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 2 is referred to as a second substituent.
  • R2 can consist of a second substituent and an aryl group.
  • the second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen.
  • R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • alkyl group optionally having one or more substituents that the second substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R 3 in formula (1) represents an aryl group optionally having one or more substituents. That is, R 3 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • R3 is an aryl group having one or more substituents
  • the substituent of the aryl group contained in R3 is referred to as the third substituent.
  • R3 can consist of a third substituent and an aryl group.
  • the third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen.
  • R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • the alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents.
  • Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • At least one of R 2 and R 3 is preferably a substituted aryl group, more preferably a substituted phenyl group.
  • Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
  • the fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture.
  • the content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
  • condition ii) is satisfied
  • R 2 and/or R 3 is an aryl group having a fluorine-containing substituent>
  • at least one of R 2 and R 3 can be an aryl group having a fluorine-containing substituent.
  • R 2 and R 3 may be aryl groups having fluorine-containing substituents, or R 2 and R 3 may be aryl groups having fluorine-containing substituents.
  • R 2 or R 3 is preferably an aryl group having a fluorine-containing substituent.
  • R 1 represents an aryl group optionally having one or more substituents. That is, R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 1 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 1 is referred to as a first substituent.
  • R 1 can consist of the first substituent and an aryl group.
  • the first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two.
  • the first substituent can be an alkyl group optionally having one or more substituents.
  • the first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
  • alkyl group optionally having one or more substituents that the first substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups.
  • the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
  • R 1 is preferably an unsubstituted aryl group, preferably a phenyl group.
  • R 1 is preferably an aryl group having an alkyl group optionally substituted with one or more substituents as the first substituent, and one or more substituents as the first substituent A phenyl group having an optionally substituted alkyl group is more preferred. Preferred forms of alkyl groups optionally substituted with one or more substituents are as described above.
  • R 1 preferably has an alkyl group optionally substituted with one or more substituents at the meta position.
  • R2 represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 2 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents
  • An aryl group optionally having one or more substituents is preferable, and an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents is more preferable.
  • R 2 is an alkyl group optionally having one or more substituents
  • R 2 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 2 When R 2 represents an aryl group optionally having one or more substituents, R 2 can be an unsubstituted aryl group or an aryl group having one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 2 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 2 is referred to as a second substituent.
  • R2 can consist of a second substituent and an aryl group.
  • the second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen.
  • R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • alkyl group optionally having one or more substituents that the second substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R 3 in formula (1) represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 3 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents
  • An aryl group optionally having one or more substituents is preferred, and an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents is more preferred.
  • R 3 is an alkyl group optionally having one or more substituents
  • R 3 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 3 When R 3 is an aryl group optionally having one or more substituents, R 3 can be an unsubstituted aryl group or an aryl group having one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R3 is an aryl group having one or more substituents
  • the substituent of the aryl group contained in R3 is referred to as the third substituent.
  • R3 can consist of a third substituent and an aryl group.
  • the third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen.
  • R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • the alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents.
  • Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • At least one of R 2 and R 3 is preferably an aryl group having a fluorine-containing substituent, and at least one is preferably a phenyl group having a fluorine-containing substituent.
  • R 2 or R 3 is an alkyl group optionally having one or more substituents
  • the other is an aryl having a fluorine-containing substituent
  • the fluorine-containing group is fluorine or perfluoro It can contain an alkyl group.
  • Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
  • the fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture.
  • the content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
  • R 1 is a phenyl group or a phenyl group having an alkyl group
  • R 2 is a phenyl group having a fluorine atom or a fluorinated alkyl group
  • R 3 is a phenyl group
  • R 1 is a phenyl group or a phenyl group having an alkyl group
  • R 2 is a phenyl group having an alkyl group
  • R 3 is a phenyl group
  • R 1 is a phenyl group or a phenyl group having an alkyl group
  • R 2 is a phenyl group having a fluorine atom or a fluorinated alkyl group
  • R 3 is an alkyl group
  • the fullerene derivative according to one embodiment of the present invention preferably has a LUMO level value of less than -3.67 eV.
  • the values of the LUMO levels are, for example, ⁇ 3.75, ⁇ 3.74, ⁇ 3.73, ⁇ 3.72, ⁇ 3.71, ⁇ 3.7, ⁇ 3.69, ⁇ 3.68 eV. , within a range between any two of the numerical values exemplified herein.
  • a fullerene derivative according to one embodiment of the present invention has a structure represented by formula (1), and R 1 , R 2 , and/or R 3 have specific substituents, so that the LUMO level can be adjusted lower, which is considered to contribute to the improvement of conversion efficiency.
  • the LUMO level can be measured by the method described in Karakawa et al., Journal of Materials Chemistry A, 2014, 2, 20889 pages.
  • the fullerene derivative according to one embodiment of the present invention preferably has a toluene solubility of 0.5% by mass or more at room temperature, more preferably 1.0% by mass or more.
  • the toluene solubility may be, for example, about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0% by mass, or between any two of the numerical values exemplified here. may be within the range.
  • the toluene solubility means the mass of a fullerene derivative soluble in 100 g of toluene.
  • a fullerene derivative according to an embodiment of the present invention has a structure represented by formula (1), and R 1 , R 2 and/or R 3 have specific substituents such as toluene. It is presumed to have moderate solubility in an organic solvent, so that the organic power generation layer forming solution can be easily prepared, and the organic power generation layer can be easily formed.
  • the solubility in toluene at room temperature can be determined from the absorbance using the Beer-Lambert law.
  • a molar extinction coefficient is obtained using a toluene solution of a fullerene derivative with a known concentration.
  • a certain amount of the supernatant solution of the supersaturated toluene solution of the fullerene derivative is weighed, and the absorbance thereof is measured.
  • the concentration can be calculated according to the following formula.
  • C A/ ⁇ d [In the formula, C: concentration, A: absorbance, ⁇ : molar extinction coefficient, d: cell length for absorbance measurement (1 cm)]
  • the method for producing the fullerene derivative according to the present invention is not particularly limited, and it can be produced by a known method for producing a fullerene derivative or a method analogous thereto.
  • a fullerene derivative according to one embodiment of the present invention can be synthesized by the following scheme known as the plateau reaction.
  • the amount ratio of the aldehyde compound, the amino acid compound, and the fullerene is not particularly limited, but from the viewpoint of increasing the yield, for example, 0.1 to 10 mol each of the aldehyde compound and the amino acid compound can be used per 1 mol of the fullerene. can be used, preferably in an amount of 0.5 to 2 mol.
  • the reaction can be carried out in the absence of solvent or in a solvent.
  • solvents include carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like. Among these, chloroform, toluene, xylene, chlorobenzene, and the like are preferable. These solvents may be mixed in an appropriate ratio and used.
  • the reaction temperature can be, for example, room temperature to 150°C, preferably 80 to 120°C. In this specification, room temperature is 15 to 30°C.
  • the reaction time is, for example, 1 hour to 4 days, preferably 10 to 48 hours.
  • the obtained compound can be purified by a known purification method, if necessary.
  • the obtained compound is purified by silica gel column chromatography (developing solvent is preferably hexane-chloroform, hexane-toluene, or hexane-carbon disulfide), and then further HPLC (preparative GPC ) (preferable developing solvent is, for example, chloroform or toluene).
  • Aldehyde compounds, amino acid compounds, and fullerenes used in the reaction may be synthesized by known methods or methods based thereon, or may be commercially available.
  • an aldehyde compound and an amino acid compound can be synthesized, for example, by the method of Examples.
  • the n-type semiconductor material according to one embodiment of the present invention can contain the fullerene derivative.
  • the n-type semiconductor material according to one embodiment of the present invention can also be made of the above fullerene derivative.
  • An organic power generation layer according to an embodiment of the present invention can contain the n-type semiconductor material and the p-type semiconductor material.
  • An organic power generation layer according to an embodiment of the present invention can be made of the n-type semiconductor material of the present invention and the organic p-type semiconductor.
  • Examples of p-type semiconductor materials include poly-p-phenylene vinylene, poly-alkoxy-p-phenylene vinylene, poly-9,9-dialkylfluorene, poly-p-phenylene vinylene, and the like.
  • a donor-acceptor type ⁇ -conjugated polymer can be used that enables absorption of long-wavelength light by narrowing the bandgap (low bandgap).
  • a donor-acceptor type ⁇ -conjugated polymer has a structure in which donor units and acceptor units are alternately arranged.
  • Donor units include benzodithiophene, dithienosilol, and N-alkylcarbazole, and acceptor units include benzothiadiazole, thienothiophene, thiophenepyrroledione, and the like.
  • poly(thieno[3,4-b]thiophene-co-benzo[1,2-b:4,5-b′]thiophene) (PTBx series)
  • poly( Dithieno[1,2-b:4,5-b′][3,2-b:2′,3′-d]silole-alt-(2,1,3-benzothiadiazole)s can be mentioned.
  • Examples include PTB7, PBDTTPD, PSBTBT, PBDTTT-CF, PDTP-DFBT, and the like.
  • the n-type semiconductor material containing the fullerene derivative according to the present invention mixes with good affinity even with a long-wavelength absorption p-type semiconductor material, which has relatively poor affinity with conventional n-type semiconductor materials, Since a bulk heterojunction structure having a large interface area and high stability can be constructed, a photoelectric conversion element having high conversion efficiency and high durability can be obtained.
  • the fullerene derivative according to the present invention can also be suitably used as an n-type semiconductor material for an organic power generation layer using a long wavelength absorption p-type semiconductor material.
  • the long-wave absorption p-type semiconductor material can be specifically a p-type semiconductor material having a maximum absorption wavelength of 700 nm or more.
  • PDTP-DFBT, PTB7-Th, PCDTBT, PCPDTBT, NT812, etc. can be mentioned as long-wavelength absorption p-type semiconductor materials.
  • the n-type semiconductor material containing the fullerene derivative according to the present invention and the p-type semiconductor material form a bulk heterojunction structure.
  • the organic power generation layer according to one embodiment of the present invention can be produced, for example, by a production method including an organic power generation layer forming solution preparation step and an organic power generation layer formation step.
  • the organic power generation layer forming solution preparation step the n-type semiconductor material and p-type semiconductor material containing the fullerene derivative according to the present invention can be dissolved in an organic solvent to obtain an organic power generation layer forming solution.
  • the obtained organic power generation layer forming solution is applied to a substrate by employing a known thin film forming method such as a spin coating method, a casting method, a dipping method, an ink jet method, and a screen printing method.
  • a known thin film forming method such as a spin coating method, a casting method, a dipping method, an ink jet method, and a screen printing method.
  • a thin film can be formed thereon.
  • a photoelectric conversion device can be provided with the organic power generation layer described above.
  • a photoelectric conversion element according to an embodiment of the present invention can be used as a photosensor.
  • the photoelectric conversion element which concerns on one Embodiment of this invention can be made into an organic thin-film solar cell.
  • An organic thin-film solar cell according to an embodiment of the present invention includes, for example, a transparent electrode (cathode), a cathode-side charge transport layer, an organic power-generating layer, an anode-side charge transport layer, and a counter electrode (anode) which are sequentially laminated on a substrate.
  • a solar cell having a structure can be obtained.
  • the organic power generation layer can be a semiconductor thin film layer (that is, a photoelectric conversion layer) in which an n-type semiconductor material containing the fullerene derivative according to the present invention and a p-type semiconductor material form a bulk heterojunction structure.
  • Electrode materials include aluminum, gold, silver, copper, and indium oxide (ITO).
  • Materials for the charge transport layer include, for example, PFN (poly[9,9-bis(3′-(N,N-dimethylamino)propyl-2,7-fluorene)-alt-2,7-(9,9 -dioctylfluorene)]) and MoO 3 (molybdenum oxide).
  • a photoelectric conversion device and an organic thin film solar cell according to an embodiment of the present invention have an initial energy conversion efficiency of 7.0% or more when PTB7 or PDTP-DFBT is used as the p-type semiconductor material. Furthermore, the energy conversion efficiency after heating the photoelectric conversion element and the organic thin film solar cell at 85° C. for 2 hours can maintain 95% or more of the initial energy conversion efficiency. That is, the decrease in energy conversion efficiency after heating at 85° C. for 2 hours with respect to the initial energy conversion efficiency is within 5%.
  • a photoelectric conversion device and an organic thin film solar cell provided with an organic power generation layer containing an n-type semiconductor material containing a fullerene derivative according to the present invention according to the present invention are such that an n-type semiconductor material and a p-type semiconductor material are mixed with good affinity, Since a bulk heterojunction structure having a large interface area and high stability can be constructed, a photoelectric conversion element and an organic thin-film solar cell having high conversion efficiency and high durability can be obtained.
  • reaction vessel was immersed in an oil bath (bath temperature 100° C.) and heated with stirring for 48 hours. The reaction was followed by GLC and the reaction endpoint was determined by the disappearance of starting material. After cooling, the reaction liquid was subjected to extraction separation using ethyl acetate and water. The organic phase was concentrated by an evaporator to obtain intermediate 21 (oct-1-yn-1-yl)nitrobenzene).
  • reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene 100:1 to 50:1) and preparative HPLC (column: Buckyprep 28 mm x 250 mm, eluent: toluene, 10 mL/min, detector: RI) to obtain compound 4 (fullerene derivative (HPdFNP)) (32% yield).
  • the reactant obtained here was dissolved in 30 mL of 1,3-bis(trifluoromethyl)benzene, and NBS (N-bromosuccinimide) (1.78 g, 10.0 mmol), AIBN (azobisisobutyro nitrile) (200 mg) was added, and the mixture was heated and stirred at 90°C for 15 hours.
  • the reaction solution was diluted with heptane, washed with water and concentrated by evaporation. Aniline (1 mL), triethylamine (4 mL), and methanol (2 mL) were added to the obtained reaction product, and the mixture was stirred at room temperature for 18 hours.
  • the reaction solution was diluted with ethyl acetate, washed with water, and concentrated by evaporation.
  • Sodium hydroxide (1.8 g), 40 mL of methanol and 20 mL of water were added to the above ester, and the mixture was stirred at room temperature for 24 hours.
  • reaction solution was acidified to pH 3 with dilute hydrochloric acid and extracted with ethyl acetate. Concentration by evaporation gave 2.1 g of 2-(phenylamino)-2-[4-(trifluoromethyl)phenyl]acetic acid (93%).
  • test solar cells were prepared and their conversion efficiencies were evaluated.
  • PDTP-DFBT see the chemical formula below
  • charge transport layer material PFN (poly[9,9-bis(3′-(N,N-dimethylamino)propyl-2,7- fluorene)-alt-2,7-(9,9-dioctylfluorene)]) and MoO3 (molybdenum oxide), and ITO (indium tin oxide) (cathode) and aluminum (anode) as electrodes, respectively.
  • the solubility of the 1,2,5-triphenylpyrrolidine derivative is insufficient, and there is a problem in producing a coating-type photoelectric conversion element, but introduction of a long-chain alkyl group to the phenyl group here, or one carbon is sufficient. has improved solubility due to the introduction of CF3 groups with fluorine.
  • the LUMO level of a fullerene derivative in which R 1 , R 2 and R 3 are all phenyl groups is ⁇ 3.67 eV.
  • fullerene derivatives of compounds 2 to 6 having an electron donating group at the meta position or an electron withdrawing group at the ortho and/or para positions have a LUMO level of less than -3.67 eV.

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Abstract

The present invention provides a fullerene derivative that enables a photoelectric conversion element, which comprises an organic power generation layer that uses this fullerene derivative as an n-type semiconductor material, to achieve a high conversion efficiency, while enabling the photoelectric conversion element to maintain the high conversion efficiency for a long period of time. The present invention provides a fullerene derivative which is represented by formula (1).

Description

フラーレン誘導体、ｎ型半導体材料、有機発電層、及び光電変換素子fullerene derivative, n-type semiconductor material, organic power generation layer, and photoelectric conversion device
本発明は、フラーレン誘導体、ｎ型半導体材料、有機発電層、及び光電変換素子に関する。 The present invention relates to fullerene derivatives, n-type semiconductor materials, organic power generation layers, and photoelectric conversion elements.
有機薄膜太陽電池は、光電変換材料として有機化合物を用い、一般に、溶液からの塗布法によって形成される。有機薄膜太陽電池は、デバイス作製時のコストが低いこと、大面積化が容易であること、シリコン等の無機材料と比較してフレキシブルであり使用できる場所が広がること、資源枯渇の心配が少ないこと等の各種の利点を有する。このため、近年、有機薄膜太陽電池の開発が進められている。 An organic thin-film solar cell uses an organic compound as a photoelectric conversion material and is generally formed by a coating method from a solution. Organic thin-film solar cells are inexpensive to fabricate, easy to scale up, flexible compared to inorganic materials such as silicon and can be used in a wider range of locations, and are less likely to deplete resources. It has various advantages such as. Therefore, in recent years, the development of organic thin-film solar cells has been promoted.
特許文献１には、透明電極、対電極、及びｐ型半導体材料とｎ型半導体材料が混合されたバルクヘテロジャンクション層を有する有機光電変換素子において、前記バルクヘテロジャンクション層のｎ型有機半導体材料が、結晶性のフラーレン誘導体と、非晶性のフラーレン誘導体とを、１：９９～９９：１の比率で混合した組成物であることを特徴とする有機光電変換素子が開示されている。
また、特許文献２には、ピロリジン環を有し、１個以上の置換基で置換されていてもよいアリール基、及び、１個以上の置換基で置換されていてもよいアルキル基、または１個以上の置換基で置換されていてもよいアルキルエーテルを有すること等を特徴とするフラーレン誘導体に係る発明が開示されている。 Patent Document 1 describes an organic photoelectric conversion element having a transparent electrode, a counter electrode, and a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are mixed, wherein the n-type organic semiconductor material of the bulk heterojunction layer is a crystal. discloses an organic photoelectric conversion device characterized by a composition in which a crystalline fullerene derivative and an amorphous fullerene derivative are mixed at a ratio of 1:99 to 99:1.
Further, Patent Document 2 discloses an aryl group which has a pyrrolidine ring and may be substituted with one or more substituents, an alkyl group which may be substituted with one or more substituents, or 1 Inventions relating to fullerene derivatives characterized by having an alkyl ether optionally substituted with one or more substituents have been disclosed.
特開２０１２－１５４３４号公報JP 2012-15434 A 国際公開２０１７／０６１５４３号WO2017/061543
しかしながら、従来のフラーレン誘導体をｎ型半導体材料として用いた有機発電層を備える光電変換素子は、高い変換効率を得ることができない場合があった。さらに、従来のフラーレン誘導体をｎ型半導体材料として用いた有機発電層を備える光電変換素子は、長期間高い変換効率を維持することができず、耐久性に改善の余地があった。また耐久性を改善できる化合物に関する情報も限られていた。
またさらには、一般に、光電変換素子はp型半導体材料とｎ型半導体材料とからなる溶液を塗布することにより作製される。この為、ここで用いられる半導体材料の素子作成に用いられる有機溶媒への溶解度は重要である。これまでｎ型半導体材料として広く用いられてきたＰＣＢＭのトルエンへの溶解度は１質量％程度であり、これより大きく溶解度が落ちるものは溶液塗布による素子作製上課題となる。 However, in some cases, a photoelectric conversion device provided with an organic power generation layer using a conventional fullerene derivative as an n-type semiconductor material cannot obtain high conversion efficiency. Furthermore, a conventional photoelectric conversion device provided with an organic power generation layer using a fullerene derivative as an n-type semiconductor material cannot maintain high conversion efficiency for a long period of time, and there is room for improvement in durability. There was also limited information on compounds that could improve durability.
Furthermore, generally, a photoelectric conversion element is produced by applying a solution composed of a p-type semiconductor material and an n-type semiconductor material. For this reason, the solubility of the semiconductor material used here in the organic solvent used for device fabrication is important. PCBM, which has been widely used as an n-type semiconductor material, has a solubility of about 1% by mass in toluene, and PCBM with a much lower solubility than this poses a problem in device fabrication by solution coating.
本発明は、このような事情に鑑みてなされたものであり、フラーレン誘導体をｎ型半導体材料として用いた有機発電層を備える光電変換素子において、溶液塗布による素子作製が容易で、高い変換効率を得ることができ、さらに、長期間高い変換効率を維持することができるフラーレン誘導体を提供するものである。 The present invention has been made in view of such circumstances, and in a photoelectric conversion device provided with an organic power generation layer using a fullerene derivative as an n-type semiconductor material, the device can be easily manufactured by solution coating, and high conversion efficiency can be achieved. A fullerene derivative that can be obtained and that can maintain high conversion efficiency for a long period of time.
本発明によれば、下記式（１）で表されるフラーレン誘導体が提供される。 According to the present invention, a fullerene derivative represented by the following formula (1) is provided.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
式（１）中、
　Ｒ１は、１個以上の置換基を有していてもよいアリール基を表し、
　Ｒ２は、有機基を表し、
　Ｒ３は、有機基を表し、
　Ｒ２及びＲ３のうち少なくとも一方が、１個以上の置換基を有していてもよいアリール基を表し、
　環Ａは、フラーレン環を表し、
　式（１）は、下記の２つの条件のうち、少なくともいずれか１つを満たす。
　ｉ）Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基である。
　ｉｉ）Ｒ２及び／又はＲ３がフッ素含有置換基を有するアリール基である。） In formula (1),
R 1 represents an aryl group optionally having one or more substituents,
R 2 represents an organic group,
R 3 represents an organic group,
at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents;
Ring A represents a fullerene ring,
Formula (1) satisfies at least one of the following two conditions.
i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group.
ii) R2 and/or R3 are aryl groups with fluorine-containing substituents; )
本発明者は、鋭意検討を行ったところ、特定の式（１）で表される構造を有するフラーレン誘導体をｎ型半導体材料として用いた有機発電層を備える光電変換素子において、高い変換効率を得ることができ、さらに、該光電変換素子は、長期間高い変換効率を維持することができることを見出し、本発明の完成に至った。 As a result of intensive studies, the present inventors have found that a photoelectric conversion element having an organic power generation layer using a fullerene derivative having a structure represented by a specific formula (1) as an n-type semiconductor material achieves high conversion efficiency. Furthermore, the photoelectric conversion element can maintain a high conversion efficiency for a long period of time, leading to the completion of the present invention.
本発明の別の観点によれば、前記記載のフラーレン誘導体を含む、ｎ型半導体材料が提また、本発明の別の観点によれば、前記記載のｎ型半導体材料、及び、ｐ型半導体材料を含有する有機発電層が提供される。
本発明の別の観点によれば、前記記載の有機発電層を備える光電変換素子が提供される。 According to another aspect of the present invention, there is provided an n-type semiconductor material comprising the above-described fullerene derivative, and according to another aspect of the present invention, the above-described n-type semiconductor material and p-type semiconductor material Provided is an organic power-generating layer containing
According to another aspect of the present invention, there is provided a photoelectric conversion device comprising the organic power generation layer described above.
以下、本発明の種々の実施形態を例示する。以下に示す実施形態は互いに組み合わせ可能である。
［１］下記式（１）で表されるフラーレン誘導体。 Various embodiments of the present invention are illustrated below. The embodiments shown below can be combined with each other.
[1] A fullerene derivative represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
 （式（１）中、Ｒ１は、１個以上の置換基を有していてもよいアリール基を表し、Ｒ２は、有機基を表し、Ｒ３は、有機基を表し、Ｒ２及びＲ３のうち少なくとも一方が、１個以上の置換基を有していてもよいアリール基を表し、環Ａは、フラーレン環を表し、式（１）は、下記の２つの条件のうち、少なくともいずれか１つを満たす。ｉ）Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基である。ｉｉ）Ｒ２及び／又はＲ３がフッ素含有置換基を有するアリール基である。）
［２］式（１）において、Ｒ１が置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基であって、Ｒ１が１個以上の置換基を有するアリール基である場合に、Ｒ１に含まれるアリール基が有する置換基を第１の置換基とすると、前記第１の置換基が、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含む、［１］に記載のフラーレン誘導体。
［３］式（１）において、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくともいずれ一つが、メタ位に電子供与基を有するアリール基であり、及び／又は、Ｒ２、及び、Ｒ３のうち少なくともいずれ一つが、オルト位及び／又はパラ位に電子求引基を有するアリール基である、［１］又は［２］に記載のフラーレン誘導体。
［４］式（１）において、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、１個以上の置換基を有していてもよいアルキル基を含み、前記アルキル基が、炭素数４以上１２以下の、直鎖又は分岐アルキル基である、［１］～［３］のいずれか１項に記載のフラーレン誘導体。
［５］式（１）において、Ｒ２、及び、Ｒ３のうち少なくとも１つが、フッ素原子及び炭素数が２以下のフッ化アルキル基のうちいずれか１つを含む、［１］～［４］のいずれか１項に記載のフラーレン誘導体。
［６］ＬＵＭＯ準位の値が－３．６７ｅＶ未満であり、トルエン溶解度が０．５％以上である、［１］～［５］のいずれか１項に記載のフラーレン誘導体。
［７］［１］～［６］のいずれか１項に記載のフラーレン誘導体を含む、ｎ型半導体材料。
［８］［７］に記載のｎ型半導体材料、及び、ｐ型半導体材料を含有する有機発電層。
［９］［８］に記載の有機発電層を備える光電変換素子。
［１０］有機薄膜太陽電池である、［９］に記載の光電変換素子。
［１１］光センサーである、［９］に記載の光電変換素子。
［１２］初期エネルギー変換効率に対する８５℃で２時間加熱後のエネルギー変換効率の低下が５％以内である、［９］に記載の光電変換素子。
Figure JPOXMLDOC01-appb-C000003
 (In formula (1), R 1 represents an aryl group optionally having one or more substituents, R 2 represents an organic group, R 3 represents an organic group, R 2 and At least one of R 3 represents an aryl group optionally having one or more substituents, Ring A represents a fullerene ring, and formula (1) satisfies at least satisfy any one of i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and R 1 , R 2 and R 3 at least one of is an aryl group having a substituent. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents; )
[2] In formula (1), R 1 is an unsubstituted aryl group or an aryl group with one or more substituents, and R 1 is an aryl group with one or more substituents In some cases, when the substituent of the aryl group contained in R 1 is the first substituent, the first substituent is an alkyl group optionally having one or more substituents, and The fullerene derivative according to [1], comprising at least one selected from the group consisting of aralkyl groups optionally having one or more substituents.
[3] In formula (1), at least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position, and/or R 2 and R 3 at least one of which is an aryl group having an electron-withdrawing group at the ortho-position and/or para-position, the fullerene derivative according to [1] or [2].
[4] In formula (1), at least one of R 1 , R 2 , and R 3 contains an alkyl group optionally having one or more substituents, and the alkyl group has a carbon number The fullerene derivative according to any one of [1] to [3], which is a linear or branched alkyl group of 4 or more and 12 or less.
[5] In formula (1), at least one of R 2 and R 3 contains any one of a fluorine atom and a fluorinated alkyl group having 2 or less carbon atoms, [1] to [4 ] The fullerene derivative according to any one of the above.
[6] The fullerene derivative according to any one of [1] to [5], which has a LUMO level value of less than −3.67 eV and a toluene solubility of 0.5% or more.
[7] An n-type semiconductor material comprising the fullerene derivative according to any one of [1] to [6].
[8] An organic power generating layer containing the n-type semiconductor material of [7] and a p-type semiconductor material.
[9] A photoelectric conversion device comprising the organic power generation layer according to [8].
[10] The photoelectric conversion device according to [9], which is an organic thin film solar cell.
[11] The photoelectric conversion element according to [9], which is an optical sensor.
[12] The photoelectric conversion device according to [9], wherein the decrease in energy conversion efficiency after heating at 85°C for 2 hours relative to the initial energy conversion efficiency is within 5%.
本発明に係るフラーレン誘導体によれば、該フラーレン誘導体をｎ型半導体材料として用いた有機発電層を備える光電変換素子において、高い変換効率を得ることができ、さらに、該光電変換素子は、長期間高い変換効率を維持することができる。 According to the fullerene derivative according to the present invention, a photoelectric conversion device having an organic power generation layer using the fullerene derivative as an n-type semiconductor material can obtain high conversion efficiency. A high conversion efficiency can be maintained.
以下、本発明の実施形態を例示して本発明について詳細な説明をする。本発明は、これらの記載によりなんら限定されるものではない。以下に示す本発明の実施形態の各種特徴事項は、互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, the present invention will be described in detail by exemplifying embodiments of the present invention. The present invention is not limited in any way by these descriptions. Various features of embodiments of the invention described below can be combined with each other. In addition, the invention is established independently for each characteristic item.
１．フラーレン誘導体
１．１　フラーレン誘導体の構造
本発明に係るフラーレン誘導体は下記式（１）で表される。 1. 1.1 Structure of Fullerene Derivative The fullerene derivative according to the present invention is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
式（１）中、
　Ｒ１は、１個以上の置換基を有していてもよいアリール基を表し、
　Ｒ２は、有機基を表し、
　Ｒ３は、有機基を表し、
　Ｒ２及びＲ３のうち少なくとも一方が、１個以上の置換基を有していてもよいアリール基を表し、
　環Ａは、フラーレン環を表し、
　式（１）は、下記の２つの条件のうち、少なくともいずれか１つを満たす。
　ｉ）Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基である。
　ｉｉ）Ｒ２及び／又はＲ３がフッ素含有置換基を有するアリール基である。 In formula (1),
R 1 represents an aryl group optionally having one or more substituents,
R 2 represents an organic group,
R 3 represents an organic group,
at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents;
Ring A represents a fullerene ring,
Formula (1) satisfies at least one of the following two conditions.
i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group.
ii) R2 and/or R3 are aryl groups with fluorine-containing substituents;
本発明に係るフラーレン誘導体は、上記式（１）で表される構造を有することにより、該フラーレン誘導体をｎ型半導体材料として用いた有機発電層を備える光電変換素子において、高い変換効率を得ることができ、さらに、該光電変換素子は、長期間高い変換効率を維持することができる。
本発明に係るフラーレン誘導体を用いることで、高い変換効率かつ高い耐久性を有する光電変換素子を得ることができる理由は明らかではないが、変換効率及び耐久性の向上には、本発明に係るフラーレン誘導体のＬＵＭＯ準位が適度に調整されること、及び、本発明に係るフラーレン誘導体をｎ型半導体材料として用いた際の、ｎ型半導体材料とｐ型半導体との優れた親和性が関与し、さらには本発明のフラーレン誘導体に導入された置換基数およびその構造によるものと推測される。 The fullerene derivative according to the present invention has a structure represented by the above formula (1), so that a photoelectric conversion element having an organic power generation layer using the fullerene derivative as an n-type semiconductor material can obtain high conversion efficiency. Furthermore, the photoelectric conversion element can maintain high conversion efficiency for a long period of time.
Although the reason why a photoelectric conversion device having high conversion efficiency and high durability can be obtained by using the fullerene derivative according to the present invention is not clear, the fullerene derivative according to the present invention can be used to improve the conversion efficiency and durability. Appropriate adjustment of the LUMO level of the derivative and excellent affinity between the n-type semiconductor material and the p-type semiconductor when the fullerene derivative according to the present invention is used as the n-type semiconductor material are involved, Furthermore, it is presumed that it depends on the number of substituents introduced into the fullerene derivative of the present invention and its structure.
さらに、本発明に係るフラーレン誘導体は、式（１）で表される構造を有することにより、トルエン等の有機溶剤に十分に溶解し、有機発電層形成用溶液を容易に調整可能であり、公知の薄膜形成方法を採用して、基板上に容易に薄膜を形成することができる。 Furthermore, the fullerene derivative according to the present invention has a structure represented by formula (1), so that it is sufficiently soluble in an organic solvent such as toluene, and the organic power generation layer forming solution can be easily prepared. A thin film can be easily formed on a substrate by adopting the thin film forming method of (1).
以下、本発明に係る式（１）で表される構造を有するフラーレン誘導体について詳説する。なお、本発明に係るフラーレン誘導体は、式（１）において、Ｒ１、Ｒ２、Ｒ３、環Ａがそれぞれ特定の構造であり、かつ、式（１）が、条件ｉ）及びｉｉ）のうち、少なくともいずれか１つを満たすことを特徴とする。以下、
・ｉ）及びｉｉ）の場合での共通の好ましい実施形態
・ｉ）の場合に特に好ましい実施形態
・ｉｉ）の場合に特に好ましい実施形態
の順に本発明の実施形態について説明する。 The fullerene derivative having the structure represented by formula (1) according to the present invention will be described in detail below. In the fullerene derivative according to the present invention, in formula (1), R 1 , R 2 , R 3 and ring A each have a specific structure, and formula (1) satisfies conditions i) and ii). It is characterized by satisfying at least one of them. the following,
Common preferred embodiments for cases i) and ii) Particularly preferred embodiments for i) Especially preferred embodiments for ii) The embodiments of the present invention will be described in this order.
まず、ｉ）及びｉｉ）の場合で共通の好ましい実施形態について説明する。
式（１）において、Ｒ１は、１個以上の置換基を有していてもよいアリール基を表す。Ｒ１は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。
アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、アリール基は、フェニル基であることが好ましい。 First, preferred embodiments common to cases i) and ii) will be described.
In formula (1), R 1 represents an aryl group optionally having one or more substituents. R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, and the aryl group is preferably a phenyl group.
Ｒ１が１個以上の置換基を有するアリール基である場合、Ｒ１に含まれるアリール基が有する置換基を第１の置換基と称する。Ｒ１は、第１の置換基とアリール基からなるものとできる。 When R 1 is an aryl group having one or more substituents, the substituent of the aryl group included in R 1 is referred to as a first substituent. R 1 can consist of the first substituent and an aryl group.
第１の置換基は、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第１の置換基は、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第１の置換基は、酸素、硫黄、窒素などのヘテロ元素を含まない炭化水素基で構築されることが好ましい。即ち、Ｒ１は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ１がエーテル結合及びエステル結合を含まないことが好ましい。 The first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two. The first substituent further preferably contains at least one selected from the group consisting of alkyl groups optionally having one or more substituents, and may contain one or more of these, It can contain one or two. The first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
第１の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、イソブチル基、ｓｅｃ－ブチル基、イソペンチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１－エチルブチル基、２－エチルブチル基、１－メチルヘキシル基、２－メチルヘキシル基、３－メチルヘキシル基、４－メチルヘキシル基、５－メチルヘキシル基、１－エチルペンチル基、２－エチルペンチル基、３－エチルペンチル基、１－プロピルブチル基、１－（１－メチルエチル）ブチル基、１－（１－メチルエチル）－２－メチルプロピル基、１－メチルヘプチル基、２－メチルヘプチル基、３－メチルヘプチル基、４－メチルヘプチル基、５－メチルヘプチル基、６－メチルヘプチル基、１－エチルヘキシル基、２－エチルヘキシル基、３－エチルヘキシル基、４－エチルヘキシル基、１－ｎ－プロピルペンチル基、２－プロピルペンチル基、１－（１－メチルエチル）ペンチル基、１－ブチルブチル基、１－ブチル－２－メチルブチル基、１－ブチル－３－メチルブチル基、１－（１，１－ジメチルエチル）ブチルブチル基、ｔｅｒｔ－ブチル基、１，１－ジメチルプロピル基、１，１－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、２，３－ジメチルブチル基、１－エチル－２－メチルプロピル基、１，１－ジメチルペンチル基、１，２－ジメチルペンチル基、１，３－ジメチルペンチル基、１，４－ジメチルペンチル基、２，２－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３，３－ジメチルペンチル基、３，４－ジメチルペンチル基、１－エチル－１－メチルブチル基、１－エチル－２－メチルブチル基、１－エチル－３－メチルブチル基、２－エチル－１－メチルブチル基、２－エチル－３－メチルブチル基、１，１－ジメチルヘキシル基、１，２－ジメチルヘキシル基、１，３－ジメチルヘキシル基、１，４－ジメチルヘキシル基、１，５－ジメチルヘキシル基、２，２－ジメチルヘキシル基、２，３－ジメチルヘキシル基、２，４－ジメチルヘキシル基、２，５－ジメチルヘキシル基、３，３－ジメチルヘキシル基、３，４－ジメチルヘキシル基、３，５－ジメチルヘキシル基、４，４－ジメチルヘキシル基、４，５－ジメチルヘキシル基、１－エチル－２－メチルペンチル基、１－エチル－３－メチルペンチル基、１－エチル－４－メチルペンチル基、２－エチル－１－メチルペンチル基、２－エチル－２－メチルペンチル基、２－エチル－３－メチルペンチル基、２－エチル－４－メチルペンチル基、３－エチル－１－メチルペンチル基、３－エチル－２－メチルペンチル基、３－エチル－３－メチルペンチル基、３－エチル－４－メチルペンチル基、１－プロピル－１－メチルブチル基、１－プロピル－２－メチルブチル基、１－プロピル－３－メチルブチル基、１－（１－メチルエチル）－１－メチルブチル基、１－（１－メチルエチル）－２－メチルブチル基、１－（１－メチルエチル）－３－メチルブチル基、１，１－ジエチルブチル基、１，２－ジエチルブチル基）等を挙げることができる。 As the alkyl group optionally having one or more substituents that the first substituent may contain, a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups. , 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methyl hexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 1-(1-methylethyl)butyl group, 1-(1-methylethyl)-2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group , 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1-(1-methylethyl)pentyl group, 1-butylbutyl group , 1-butyl-2-methylbutyl group, 1-butyl-3-methylbutyl group, 1-(1,1-dimethylethyl)butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethyl butyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethyl pentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group , 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3 -methylbutyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl- 1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl- 2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1-propyl-3- methylbutyl group, 1-(1-methylethyl)-1-methylbutyl group, 1-(1-methylethyl)-2-methylbutyl group, 1-(1-methylethyl)-3-methylbutyl group, 1,1-diethyl butyl group, 1,2-diethylbutyl group) and the like.
第１の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、３－フェニルプロピル基、４－フェニルブチル基、５－フェニルペンチル基等を挙げることができる。 In the aralkyl group optionally having one or more substituents that can be contained in the first substituent, the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
式（１）において、Ｒ２は、有機基を表す。
本明細書において、有機基とは、１個以上の炭素原子を含有する基（又は有機化合物から１個の水素原子を除去して形成される基）を意味する。有機基は、１個以上の置換基を有していてもよい炭化水素基とすることができる。炭化水素基としては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、シクロアルカジエニル基、アリール基、及びアラルキル基、並びにこれらの２個以上が連結している基を挙げることができる。Ｒ２としては、１個以上の置換基を有していてもよいアルキル基、１個以上の置換基を有していてもよいアラルキル基、又は、１個以上の置換基を有していてもよいアリール基、が好ましい。 In formula (1), R2 represents an organic group.
As used herein, an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound). The organic group can be a hydrocarbon group optionally having one or more substituents. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to. R 2 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group that has a low molecular weight is preferred.
Ｒ２が１個以上の置換基を有していてもよいアルキル基である場合、Ｒ２は、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基とすることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 When R 2 is an alkyl group optionally having one or more substituents, R 2 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
Ｒ２が１個以上の置換基を有していてもよいアラルキル基である場合、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 When R 2 is an aralkyl group optionally having one or more substituents, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
Ｒ２が、１個以上の置換基を有していてもよいアリール基を表す場合、Ｒ２は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。
アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、アリール基は、フェニル基であることが好ましい。 When R 2 represents an aryl group optionally having one or more substituents, R 2 can be an unsubstituted aryl group or an aryl group having one or more substituents.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, and the aryl group is preferably a phenyl group.
Ｒ２が１個以上の置換基を有するアリール基である場合、Ｒ２に含まれるアリール基が有する置換基を第２の置換基と称する。Ｒ２は、第２の置換基とアリール基からなるものとできる。 When R 2 is an aryl group having one or more substituents, the substituent of the aryl group included in R 2 is referred to as a second substituent. R2 can consist of a second substituent and an aryl group.
第２の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第２の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第２の置換基は、フッ素を含む場合があるものの、これ以外に、酸素、硫黄、窒素などのヘテロ元素を含まない置換基であることが好ましい。Ｒ２は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ２がエーテル結合及びエステル結合を含まないことが好ましい。 The second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included. The second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included. The second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen. R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
第２の置換基が含み得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 A fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, or a pentafluoroethyl group. A trifluoromethyl group and a pentafluoroethyl group are more preferred, and a trifluoromethyl group is even more preferred.
第２の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第２の置換基が含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 As the alkyl group optionally having one or more substituents that the second substituent may contain, a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
第２の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第２の置換基が含み得るアラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 In the aralkyl group optionally having one or more substituents that the second substituent may contain, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
式（１）において、Ｒ３は、有機基を表す。
本明細書において、有機基とは、１個以上の炭素原子を含有する基（又は有機化合物から１個の水素原子を除去して形成される基）を意味する。有機基は、１個以上の置換基を有していてもよい炭化水素基とすることができる。炭化水素基としては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、シクロアルカジエニル基、アリール基、及びアラルキル基、並びにこれらの２個以上が連結している基を挙げることができる。Ｒ３としては、１個以上の置換基を有していてもよいアルキル基、１個以上の置換基を有していてもよいアラルキル基、又は、１個以上の置換基を有していてもよいアリール基、が好ましい。 In formula (1), R3 represents an organic group.
As used herein, an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound). The organic group can be a hydrocarbon group optionally having one or more substituents. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to. R 3 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group that has a low molecular weight is preferred.
Ｒ３が１個以上の置換基を有していてもよいアルキル基である場合、Ｒ３は、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基とすることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 When R 3 is an alkyl group optionally having one or more substituents, R 3 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
Ｒ３が１個以上の置換基を有していてもよいアラルキル基である場合、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 When R 3 is an aralkyl group optionally having one or more substituents, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
Ｒ３が１個以上の置換基を有していてもよいアリール基である場合、Ｒ３に含まれるアリール基が有する置換基を第３の置換基と称する。Ｒ３は、第３の置換基とアリール基からなるものとできる。 When R 3 is an aryl group optionally having one or more substituents, the substituent of the aryl group contained in R 3 is referred to as the third substituent. R3 can consist of a third substituent and an aryl group.
第３の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第３の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第３の置換基は、フッ素を含む場合があるものの、これ以外に、酸素、硫黄、窒素などのヘテロ元素を含まない置換基であることが好ましい。Ｒ３は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ３がエーテル結合及びエステル結合を含まないことが好ましい。 The third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included. The third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included. Although the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen. For example, R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
第３の置換基が含み得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基、であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 A fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
第３の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基は置換基を有しないものとすることもできる。
第３の置換基が含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 The alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents. Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups can also be unsubstituted.
Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
第３の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第３の置換基が含み得るアラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 In the aralkyl group optionally having one or more substituents which may be included in the third substituent, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
式（１）において、Ｒ２及びＲ３のうち少なくとも一方が、１個以上の置換基を有していてもよいアリール基を表す。また、式（１）において、Ｒ２及びＲ３のうちの一方が、１個以上の置換基を有していてもよいアルキル基、又は１個以上の置換基を有していてもよいアラルキル基である場合、他方は、第２（又は第３）の置換基がフッ素含有基であるアリール基であることが好ましい。 In formula (1), at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents. In formula (1), one of R 2 and R 3 is an alkyl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents group, the other is preferably an aryl group in which the second (or third) substituent is a fluorine-containing group.
本発明の一実施形態に係るフラーレン誘導体は、式（１）において、Ｒ１、Ｒ２、及びＲ３のうち少なくともいずれか１つが、メタ位に電子供与基を有するアリール基であり、
及び／又は、
Ｒ２、及び／又はＲ３が、オルト位及び／又はパラ位に電子求引基を有するアリール基
であるものとできる。
本発明の一実施形態に係るフラーレン誘導体は、式（１）において、Ｒ１、Ｒ２、及びＲ３のうちいずれか１つのみが、メタ位に電子供与基を有するアリール基であってもよいし、Ｒ１、Ｒ２、及びＲ３のうち２つがメタ位に電子供与基を有するアリール基であってもよいし、Ｒ１、Ｒ２、及びＲ３がメタ位に電子供与基を有するアリール基であってもよい。
Ｒ２又はＲ３が、オルト位及び／又はパラ位に電子求引基を有するアリール基であってもよいし、Ｒ２及びＲ３が、オルト位及び／又はパラ位に電子求引基を有するアリール基であってもよい。 In the fullerene derivative according to one embodiment of the present invention, in formula (1), at least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position,
and/or
R 2 and/or R 3 can be an aryl group having an electron-withdrawing group at the ortho and/or para position.
In the fullerene derivative according to one embodiment of the present invention, in formula (1), only one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position. Alternatively, two of R 1 , R 2 and R 3 may be aryl groups having an electron donating group at the meta position, or R 1 , R 2 and R 3 may have an electron donating group at the meta position. may be an aryl group having
R 2 or R 3 may be an aryl group having an electron withdrawing group at the ortho and/or para position, or R 2 and R 3 may have an electron withdrawing group at the ortho and/or para position. may be an aryl group having
Ｒ１、Ｒ２、及びＲ３のうち少なくともいずれか１つがメタ位に有し得る電子供与基としては、１個以上の置換基を有していてもよいアルキル基、及びアラルキル基を挙げることができ、１個以上の置換基を有していてもよいアルキル基であることが好ましい。
１個以上の置換基を有していてもよいアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基は置換基を有しないものとすることもできる。アルキル基としては、第１の置換基として列挙したアルキル基の具体例を挙げることができる。 Examples of the electron-donating group that at least one of R 1 , R 2 , and R 3 may have at the meta position include alkyl groups optionally having one or more substituents, and aralkyl groups. is preferably an alkyl group optionally having one or more substituents.
Examples of the alkyl group optionally having one or more substituents include linear or branched alkyl groups optionally having one or more substituents. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups can also be unsubstituted. As the alkyl group, specific examples of the alkyl group listed as the first substituent can be given.
Ｒ２及びＲ３の少なくともいずれ一方がオルト位及び／又はパラ位に有し得る電子求引基としては、フッ素原子、及びフッ化アルキル基を挙げることができる。フッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基、であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 Examples of the electron-withdrawing group that at least one of R 2 and R 3 may have at the ortho-position and/or para-position include a fluorine atom and a fluorinated alkyl group. A fluorinated alkyl group can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
本発明の一実施形態に係るフラーレン誘導体は、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、１個以上の置換基を有していてもよいアルキル基を含むものとできる。また、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが含み得るアルキル基は、炭素数４以上１２以下の、直鎖又は分岐アルキル基とすることができる。ここで、「Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、１個以上の置換基を有していてもよいアルキル基を含む」とは、例えば、Ｒ１、Ｒ２、又は、Ｒ３が、１個以上の置換基を有していてもよいアリール基であって、Ｒ１、Ｒ２、又は、Ｒ３が、第１、第２，又は第３の置換基として、１個以上の置換基を有していてもよいアルキル基を含む場合を包含する。 In the fullerene derivative according to one embodiment of the present invention, at least one of R 1 , R 2 and R 3 may contain an alkyl group optionally having one or more substituents. Also, the alkyl group that at least one of R 1 , R 2 , and R 3 may contain may be a linear or branched alkyl group having 4 or more and 12 or less carbon atoms. Here, "at least one of R 1 , R 2 and R 3 contains an alkyl group optionally having one or more substituents" means, for example, R 1 , R 2 or , R 3 is an aryl group optionally having one or more substituents, and R 1 , R 2 or R 3 is the first, second or third substituent, This includes cases where an alkyl group optionally having one or more substituents is included.
「Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが含み得るアルキル基」は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 The “alkyl group that at least one of R 1 , R 2 and R 3 may contain” does not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group that at least one of R 1 , R 2 and R 3 may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
本発明の一実施形態に係るフラーレン誘導体は、Ｒ２及びＲ３のうち少なくとも１つが、フッ素原子及び炭素数が１又は２のフッ化アルキル基のうちいずれか１つを含むものとできる。ここで、「Ｒ２及びＲ３のうち少なくとも１つが、フッ素原子及び炭素数が１又は２のフッ化アルキル基のうちいずれか１つを含む」とは、例えば、Ｒ２及び／又はＲ３が、１個以上の置換基を有していてもよいアリール基であって、Ｒ２及び／又はＲ３が、第２又は第３の置換基として、フッ素原子及び炭素数が１又は２のフッ化アルキル基のうちいずれか１つを含む場合を包含する。 In the fullerene derivative according to one embodiment of the present invention, at least one of R 2 and R 3 may contain any one of a fluorine atom and a fluorinated alkyl group having 1 or 2 carbon atoms. Here, "at least one of R 2 and R 3 contains any one of a fluorine atom and a fluorinated alkyl group having 1 or 2 carbon atoms" means, for example, R 2 and/or R 3 is an aryl group optionally having one or more substituents, wherein R 2 and/or R 3 are, as the second or third substituents, a fluorine atom and 1 or 2 carbon atoms It includes the case of containing any one of fluorinated alkyl groups.
Ｒ２及びＲ３のうち少なくとも１つが有し得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基の具体例としては、第２の置換基及び第３の置換基が含み得るフッ化アルキル基として列挙したフッ化アルキル基を挙げることができる。 The fluorinated alkyl group that at least one of R 2 and R 3 may have can be a fluoroalkyl group in which the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. Specific examples of the fluorinated alkyl group include the fluorinated alkyl groups listed as the fluorinated alkyl groups that the second substituent and the third substituent may contain.
環Ａは、好ましくは、Ｃ６０フラーレン、又はＣ７０フラーレンであり、より好ましくはＣ６０フラーレンである。
式（１）のフラーレン誘導体は、環ＡがＣ６０フラーレンであるフラーレン誘導体（以下、Ｃ６０フラーレン誘導体ともいう。）、及び環ＡがＣ７０フラーレンであるフラーレン誘導体（以下、Ｃ７０フラーレン誘導体ともいう。）の混合物であってもよい。混合物における、Ｃ６０フラーレン誘導体の含有量は、例えば、０．００１、０．０１、０．１、１、１０、２０、３０、４０、５０、６０、７０、８０、９０、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
The fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture. The content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
本発明に係る式（１）で表されるフラーレン誘導体は、下記の２つの条件のうち、少なくともいずれか１つを満たす。
　ｉ）Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基である。
　ｉｉ）Ｒ２及び／又はＲ３がフッ素含有置換基を有するアリール基である。
本発明に係る式（１）で表されるフラーレン誘導体は、上記条件ｉ）及びｉｉ）のうち少なくともいずれか１つを満たし、上記条件ｉ）及びｉｉ）を満たすことがより好ましい。
以下、条件ｉ）を満たす場合に特に好ましい実施形態について詳説する。 The fullerene derivative represented by Formula (1) according to the present invention satisfies at least one of the following two conditions.
i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group.
ii) R2 and/or R3 are aryl groups with fluorine-containing substituents;
The fullerene derivative represented by formula (1) according to the present invention satisfies at least one of the above conditions i) and ii), and more preferably satisfies the above conditions i) and ii).
An embodiment that is particularly preferred when condition i) is satisfied will be described in detail below.
＜ｉ）Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基である場合に、特に好ましい実施形態＞
本発明の一実施形態に係る式（１）で表されるフラーレン誘導体は、Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基とできる。すなわち、この場合、Ｒ１、Ｒ２、及び、Ｒ３のすべてが、１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基とできる。 <i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is Especially preferred embodiment when the aryl group has a substituent>
In the fullerene derivative represented by formula (1) according to one embodiment of the present invention, R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and , R 1 , R 2 , and R 3 can be a substituted aryl group. That is, in this case, all of R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and R 1 , R 2 and R 3 At least one of them can be an aryl group having a substituent.
本発明の一実施形態に係る式（１）で表されるフラーレン誘導体は、Ｒ１、Ｒ２、及び、Ｒ３のうち１つ、又は２つ、又は全てが置換基を有するアリール基とでき、Ｒ１、Ｒ２、及び、Ｒ３のうち２つが置換基を有するアリール基であることが好ましい。また、本発明の一実施形態に係る式（１）で表されるフラーレン誘導体は、少なくともＲ１が、置換基を有するアリール基であることが好ましい。 In the fullerene derivative represented by formula (1) according to one embodiment of the present invention, one, two or all of R 1 , R 2 and R 3 can be substituted aryl groups. , R 1 , R 2 and R 3 are preferably substituted aryl groups. Further, in the fullerene derivative represented by formula (1) according to one embodiment of the present invention, at least R 1 is preferably an aryl group having a substituent.
式（１）において、Ｒ１は、１個以上の置換基を有していてもよいアリール基を表す。すなわち、Ｒ１は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。
アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、フェニル基であることが好ましい。 In formula (1), R 1 represents an aryl group optionally having one or more substituents. That is, R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
Ｒ１が１個以上の置換基を有するアリール基である場合、Ｒ１に含まれるアリール基が有する置換基を第１の置換基と称する。Ｒ１は、第１の置換基とアリール基からなるものとできる。 When R 1 is an aryl group having one or more substituents, the substituent of the aryl group included in R 1 is referred to as a first substituent. R 1 can consist of the first substituent and an aryl group.
第１の置換基は、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第１の置換基は、１個以上の置換基を有していてもよいアルキル基とできる。第１の置換基は、酸素、硫黄、窒素などのヘテロ元素を含まない炭化水素基で構築されることが好ましい。即ち、Ｒ１は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ１がエーテル結合及びエステル結合を含まないことが好ましい。 The first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two. The first substituent can be an alkyl group optionally having one or more substituents. The first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
第１の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、イソブチル基、ｓｅｃ－ブチル基、イソペンチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１－エチルブチル基、２－エチルブチル基、１－メチルヘキシル基、２－メチルヘキシル基、３－メチルヘキシル基、４－メチルヘキシル基、５－メチルヘキシル基、１－エチルペンチル基、２－エチルペンチル基、３－エチルペンチル基、１－プロピルブチル基、１－（１－メチルエチル）ブチル基、１－（１－メチルエチル）－２－メチルプロピル基、１－メチルヘプチル基、２－メチルヘプチル基、３－メチルヘプチル基、４－メチルヘプチル基、５－メチルヘプチル基、６－メチルヘプチル基、１－エチルヘキシル基、２－エチルヘキシル基、３－エチルヘキシル基、４－エチルヘキシル基、１－ｎ－プロピルペンチル基、２－プロピルペンチル基、１－（１－メチルエチル）ペンチル基、１－ブチルブチル基、１－ブチル－２－メチルブチル基、１－ブチル－３－メチルブチル基、１－（１，１－ジメチルエチル）ブチルブチル基、ｔｅｒｔ－ブチル基、１，１－ジメチルプロピル基、１，１－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、２，３－ジメチルブチル基、１－エチル－２－メチルプロピル基、１，１－ジメチルペンチル基、１，２－ジメチルペンチル基、１，３－ジメチルペンチル基、１，４－ジメチルペンチル基、２，２－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３，３－ジメチルペンチル基、３，４－ジメチルペンチル基、１－エチル－１－メチルブチル基、１－エチル－２－メチルブチル基、１－エチル－３－メチルブチル基、２－エチル－１－メチルブチル基、２－エチル－３－メチルブチル基、１，１－ジメチルヘキシル基、１，２－ジメチルヘキシル基、１，３－ジメチルヘキシル基、１，４－ジメチルヘキシル基、１，５－ジメチルヘキシル基、２，２－ジメチルヘキシル基、２，３－ジメチルヘキシル基、２，４－ジメチルヘキシル基、２，５－ジメチルヘキシル基、３，３－ジメチルヘキシル基、３，４－ジメチルヘキシル基、３，５－ジメチルヘキシル基、４，４－ジメチルヘキシル基、４，５－ジメチルヘキシル基、１－エチル－２－メチルペンチル基、１－エチル－３－メチルペンチル基、１－エチル－４－メチルペンチル基、２－エチル－１－メチルペンチル基、２－エチル－２－メチルペンチル基、２－エチル－３－メチルペンチル基、２－エチル－４－メチルペンチル基、３－エチル－１－メチルペンチル基、３－エチル－２－メチルペンチル基、３－エチル－３－メチルペンチル基、３－エチル－４－メチルペンチル基、１－プロピル－１－メチルブチル基、１－プロピル－２－メチルブチル基、１－プロピル－３－メチルブチル基、１－（１－メチルエチル）－１－メチルブチル基、１－（１－メチルエチル）－２－メチルブチル基、１－（１－メチルエチル）－３－メチルブチル基、１，１－ジエチルブチル基、１，２－ジエチルブチル基）等を挙げることができる。 As the alkyl group optionally having one or more substituents that the first substituent may contain, a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups. , 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methyl hexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 1-(1-methylethyl)butyl group, 1-(1-methylethyl)-2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group , 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1-(1-methylethyl)pentyl group, 1-butylbutyl group , 1-butyl-2-methylbutyl group, 1-butyl-3-methylbutyl group, 1-(1,1-dimethylethyl)butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethyl butyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethyl pentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group , 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3 -methylbutyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl- 1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl- 2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1-propyl-3- methylbutyl group, 1-(1-methylethyl)-1-methylbutyl group, 1-(1-methylethyl)-2-methylbutyl group, 1-(1-methylethyl)-3-methylbutyl group, 1,1-diethyl butyl group, 1,2-diethylbutyl group) and the like.
第１の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、３－フェニルプロピル基、４－フェニルブチル基、５－フェニルペンチル基等を挙げることができる。 In the aralkyl group optionally having one or more substituents that can be contained in the first substituent, the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
条件ｉ）において、上記の中でも、Ｒ１は、置換基を有するアリール基であることが好ましく、置換基を有するフェニル基であることがより好ましい。
Ｒ１は、第１の置換基として、１個以上の置換基で置換されていてもよいアルキル基を有することが好ましい。１個以上の置換基で置換されていてもよいアルキル基の好ましい形態は上記した通りである。
Ｒ１は、１個以上の置換基で置換されていてもよいアルキル基をメタ位に有することが好ましい。 In condition i), among the above, R 1 is preferably a substituted aryl group, more preferably a substituted phenyl group.
R 1 preferably has, as the first substituent, an alkyl group optionally substituted with one or more substituents. Preferred forms of alkyl groups optionally substituted with one or more substituents are as described above.
R 1 preferably has an alkyl group optionally substituted with one or more substituents at the meta position.
式（１）において、Ｒ２は、１個以上の置換基を有していてもよいアリール基を表す。Ｒ２は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。
アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、フェニル基であることが好ましい。 In formula (1), R2 represents an aryl group optionally having one or more substituents. R 2 can be an unsubstituted aryl group or an aryl group with one or more substituents.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
Ｒ２が１個以上の置換基を有するアリール基である場合、Ｒ２に含まれるアリール基が有する置換基を第２の置換基と称する。Ｒ２は、第２の置換基とアリール基からなるものとできる。 When R 2 is an aryl group having one or more substituents, the substituent of the aryl group included in R 2 is referred to as a second substituent. R2 can consist of a second substituent and an aryl group.
第２の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第２の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第２の置換基は、フッ素を含む場合があるものの、これ以外に、酸素、硫黄、窒素などのヘテロ元素を含まない置換基であることが好ましい。Ｒ２は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ２がエーテル結合及びエステル結合を含まないことが好ましい。 The second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included. The second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included. The second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen. R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
第２の置換基が含み得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基、であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 A fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
第２の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第２の置換基が含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 As the alkyl group optionally having one or more substituents that the second substituent may contain, a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
第２の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第２の置換基が含み得るアラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 In the aralkyl group optionally having one or more substituents that the second substituent may contain, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
条件ｉ）において、式（１）のＲ３は、１個以上の置換基を有していてもよいアリール基を表す。すなわち、Ｒ３は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。Ｒ３が１個以上の置換基を有するアリール基である場合、Ｒ３に含まれるアリール基が有する置換基を第３の置換基と称する。Ｒ３は、第３の置換基とアリール基からなるものとできる。 In condition i), R 3 in formula (1) represents an aryl group optionally having one or more substituents. That is, R 3 can be an unsubstituted aryl group or an aryl group with one or more substituents. When R3 is an aryl group having one or more substituents, the substituent of the aryl group contained in R3 is referred to as the third substituent. R3 can consist of a third substituent and an aryl group.
第３の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第３の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第３の置換基は、フッ素を含む場合があるものの、これ以外に、酸素、硫黄、窒素などのヘテロ元素を含まない置換基であることが好ましい。Ｒ３は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ３がエーテル結合及びエステル結合を含まないことが好ましい。 The third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included. The third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included. Although the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen. For example, R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
第３の置換基が含み得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基、であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 A fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
第３の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基は置換基を有しないものとすることもできる。
第３の置換基が含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 The alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents. Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups can also be unsubstituted.
Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
第３の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第３の置換基が含み得るアラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 In the aralkyl group optionally having one or more substituents which may be included in the third substituent, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
条件ｉ）において、上記の中でも、Ｒ２又はＲ３は、少なくとも一方が、置換基を有するアリール基であることが好ましく、少なくとも一方が置換基を有するフェニル基であることがより好ましい。 In condition i), among the above, at least one of R 2 and R 3 is preferably a substituted aryl group, more preferably a substituted phenyl group.
環Ａは、好ましくは、Ｃ６０フラーレン、又はＣ７０フラーレン、より好ましくはＣ６０フラーレンである。
式（１）のフラーレン誘導体は、環ＡがＣ６０フラーレンであるフラーレン誘導体（以下、Ｃ６０フラーレン誘導体ともいう。）、及び環ＡがＣ７０フラーレンであるフラーレン誘導体（以下、Ｃ７０フラーレン誘導体ともいう。）の混合物であってもよい。混合物における、Ｃ６０フラーレン誘導体の含有量は、例えば、０．００１、０．０１、０．１、１、１０、２０、３０、４０、５０、６０、７０、８０、９０、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
The fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture. The content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
以下、条件ｉｉ）を満たす場合に特に好ましい実施形態について詳説する。 A particularly preferred embodiment when condition ii) is satisfied will be described in detail below.
＜ｉｉ）Ｒ2及び／又はＲ3がフッ素含有置換基を有するアリール基である場合に特に好ましい実施形態＞
本発明の一実施形態に係る式（１）で表されるフラーレン誘導体は、Ｒ２及びＲ３の少なくともいずれか一方がフッ素含有置換基を有するアリール基とできる。この場合、Ｒ２及びＲ３がフッ素含有置換基を有するアリール基であってもよいし、Ｒ２及びＲ３がフッ素含有置換基を有するアリール基であってもよい。本発明の一実施形態に係る式（１）で表されるフラーレン誘導体は、Ｒ２又はＲ３がフッ素含有置換基を有するアリール基であることが好ましい。 <ii) A particularly preferred embodiment when R 2 and/or R 3 is an aryl group having a fluorine-containing substituent>
In the fullerene derivative represented by formula (1) according to one embodiment of the present invention, at least one of R 2 and R 3 can be an aryl group having a fluorine-containing substituent. In this case, R 2 and R 3 may be aryl groups having fluorine-containing substituents, or R 2 and R 3 may be aryl groups having fluorine-containing substituents. In the fullerene derivative represented by formula (1) according to one embodiment of the present invention, R 2 or R 3 is preferably an aryl group having a fluorine-containing substituent.
式（１）において、Ｒ１は、１個以上の置換基を有していてもよいアリール基を表す。すなわち、Ｒ１は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。
アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、フェニル基であることが好ましい。 In formula (1), R 1 represents an aryl group optionally having one or more substituents. That is, R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
Ｒ１が１個以上の置換基を有するアリール基である場合、Ｒ１に含まれるアリール基が有する置換基を第１の置換基と称する。Ｒ１は、第１の置換基とアリール基からなるものとできる。 When R 1 is an aryl group having one or more substituents, the substituent of the aryl group included in R 1 is referred to as a first substituent. R 1 can consist of the first substituent and an aryl group.
第１の置換基は、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第１の置換基は、１個以上の置換基を有していてもよいアルキル基とできる。第１の置換基は、酸素、硫黄、窒素などのヘテロ元素を含まない炭化水素基で構築されることが好ましい。即ち、Ｒ１は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ１がエーテル結合及びエステル結合を含まないことが好ましい。 The first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two. The first substituent can be an alkyl group optionally having one or more substituents. The first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
第１の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、イソブチル基、ｓｅｃ－ブチル基、イソペンチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１－エチルブチル基、２－エチルブチル基、１－メチルヘキシル基、２－メチルヘキシル基、３－メチルヘキシル基、４－メチルヘキシル基、５－メチルヘキシル基、１－エチルペンチル基、２－エチルペンチル基、３－エチルペンチル基、１－プロピルブチル基、１－（１－メチルエチル）ブチル基、１－（１－メチルエチル）－２－メチルプロピル基、１－メチルヘプチル基、２－メチルヘプチル基、３－メチルヘプチル基、４－メチルヘプチル基、５－メチルヘプチル基、６－メチルヘプチル基、１－エチルヘキシル基、２－エチルヘキシル基、３－エチルヘキシル基、４－エチルヘキシル基、１－ｎ－プロピルペンチル基、２－プロピルペンチル基、１－（１－メチルエチル）ペンチル基、１－ブチルブチル基、１－ブチル－２－メチルブチル基、１－ブチル－３－メチルブチル基、１－（１，１－ジメチルエチル）ブチルブチル基、ｔｅｒｔ－ブチル基、１，１－ジメチルプロピル基、１，１－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、２，３－ジメチルブチル基、１－エチル－２－メチルプロピル基、１，１－ジメチルペンチル基、１，２－ジメチルペンチル基、１，３－ジメチルペンチル基、１，４－ジメチルペンチル基、２，２－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３，３－ジメチルペンチル基、３，４－ジメチルペンチル基、１－エチル－１－メチルブチル基、１－エチル－２－メチルブチル基、１－エチル－３－メチルブチル基、２－エチル－１－メチルブチル基、２－エチル－３－メチルブチル基、１，１－ジメチルヘキシル基、１，２－ジメチルヘキシル基、１，３－ジメチルヘキシル基、１，４－ジメチルヘキシル基、１，５－ジメチルヘキシル基、２，２－ジメチルヘキシル基、２，３－ジメチルヘキシル基、２，４－ジメチルヘキシル基、２，５－ジメチルヘキシル基、３，３－ジメチルヘキシル基、３，４－ジメチルヘキシル基、３，５－ジメチルヘキシル基、４，４－ジメチルヘキシル基、４，５－ジメチルヘキシル基、１－エチル－２－メチルペンチル基、１－エチル－３－メチルペンチル基、１－エチル－４－メチルペンチル基、２－エチル－１－メチルペンチル基、２－エチル－２－メチルペンチル基、２－エチル－３－メチルペンチル基、２－エチル－４－メチルペンチル基、３－エチル－１－メチルペンチル基、３－エチル－２－メチルペンチル基、３－エチル－３－メチルペンチル基、３－エチル－４－メチルペンチル基、１－プロピル－１－メチルブチル基、１－プロピル－２－メチルブチル基、１－プロピル－３－メチルブチル基、１－（１－メチルエチル）－１－メチルブチル基、１－（１－メチルエチル）－２－メチルブチル基、１－（１－メチルエチル）－３－メチルブチル基、１，１－ジエチルブチル基、１，２－ジエチルブチル基）等を挙げることができる。 As the alkyl group optionally having one or more substituents that the first substituent may contain, a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups. , 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methyl hexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 1-(1-methylethyl)butyl group, 1-(1-methylethyl)-2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group , 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1-(1-methylethyl)pentyl group, 1-butylbutyl group , 1-butyl-2-methylbutyl group, 1-butyl-3-methylbutyl group, 1-(1,1-dimethylethyl)butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethyl butyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethyl pentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group , 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3 -methylbutyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl- 1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl- 2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1-propyl-3- methylbutyl group, 1-(1-methylethyl)-1-methylbutyl group, 1-(1-methylethyl)-2-methylbutyl group, 1-(1-methylethyl)-3-methylbutyl group, 1,1-diethyl butyl group, 1,2-diethylbutyl group) and the like.
第１の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、３－フェニルプロピル基、４－フェニルブチル基、５－フェニルペンチル基等を挙げることができる。 In the aralkyl group optionally having one or more substituents that can be contained in the first substituent, the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
条件ｉｉ）において、上記の中でも、Ｒ１は、置換基を有しないアリール基であることが好ましく、フェニル基であることが好ましい。
または、Ｒ１は、第１の置換基として１個以上の置換基で置換されていてもよいアルキル基、を有するアリール基であることが好ましく、第１の置換基として１個以上の置換基で置換されていてもよいアルキル基を有するフェニル基であることがより好ましい。
１個以上の置換基で置換されていてもよいアルキル基の好ましい形態は上記した通りである。Ｒ１は、１個以上の置換基で置換されていてもよいアルキル基をメタ位に有することが好ましい。 In condition ii), among the above, R 1 is preferably an unsubstituted aryl group, preferably a phenyl group.
Alternatively, R 1 is preferably an aryl group having an alkyl group optionally substituted with one or more substituents as the first substituent, and one or more substituents as the first substituent A phenyl group having an optionally substituted alkyl group is more preferred.
Preferred forms of alkyl groups optionally substituted with one or more substituents are as described above. R 1 preferably has an alkyl group optionally substituted with one or more substituents at the meta position.
式（１）において、Ｒ２は、有機基を表す。
本明細書において、有機基とは、１個以上の炭素原子を含有する基（又は有機化合物から１個の水素原子を除去して形成される基）を意味する。有機基は、１個以上の置換基を有していてもよい炭化水素基とすることができる。炭化水素基としては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、シクロアルカジエニル基、アリール基、及びアラルキル基、並びにこれらの２個以上が連結している基を挙げることができる。Ｒ２としては、１個以上の置換基を有していてもよいアルキル基、１個以上の置換基を有していてもよいアラルキル基、又は、１個以上の置換基を有していてもよいアリール基が好ましく、１個以上の置換基を有していてもよいアルキル基、又は１個以上の置換基を有していてもよいアリール基であることがより好ましい。 In formula (1), R2 represents an organic group.
As used herein, an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound). The organic group can be a hydrocarbon group optionally having one or more substituents. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to. R 2 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group optionally having one or more substituents is preferable, and an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents is more preferable.
Ｒ２が１個以上の置換基を有していてもよいアルキル基である場合、Ｒ２は、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基とすることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 When R 2 is an alkyl group optionally having one or more substituents, R 2 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
Ｒ２が１個以上の置換基を有していてもよいアラルキル基である場合、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 When R 2 is an aralkyl group optionally having one or more substituents, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
Ｒ２が、１個以上の置換基を有していてもよいアリール基を表す場合、Ｒ２は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。
アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、フェニル基であることが好ましい。 When R 2 represents an aryl group optionally having one or more substituents, R 2 can be an unsubstituted aryl group or an aryl group having one or more substituents.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
Ｒ２が１個以上の置換基を有するアリール基である場合、Ｒ２に含まれるアリール基が有する置換基を第２の置換基と称する。Ｒ２は、第２の置換基とアリール基からなるものとできる。 When R 2 is an aryl group having one or more substituents, the substituent of the aryl group included in R 2 is referred to as a second substituent. R2 can consist of a second substituent and an aryl group.
第２の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第２の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第２の置換基は、フッ素を含む場合があるものの、これ以外に酸素、硫黄、窒素などのヘテロ元素を含まない置換基であることが好ましい。Ｒ２は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ２がエーテル結合及びエステル結合を含まないことが好ましい。 The second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included. The second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included. The second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen. R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
第２の置換基が含み得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基、であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 A fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
第２の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第２の置換基が含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 As the alkyl group optionally having one or more substituents that the second substituent may contain, a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
第２の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第２の置換基が含み得るアラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 In the aralkyl group optionally having one or more substituents that the second substituent may contain, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
条件ｉｉ）において、式（１）のＲ３は、有機基を表す。
本明細書において、有機基とは、１個以上の炭素原子を含有する基（又は有機化合物から１個の水素原子を除去して形成される基）を意味する。有機基は、１個以上の置換基を有していてもよい炭化水素基とすることができる。炭化水素基としては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、シクロアルカジエニル基、アリール基、及びアラルキル基、並びにこれらの２個以上が連結している基を挙げることができる。Ｒ３としては、１個以上の置換基を有していてもよいアルキル基、１個以上の置換基を有していてもよいアラルキル基、又は、１個以上の置換基を有していてもよいアリール基、が好ましく、１個以上の置換基を有していてもよいアルキル基、又は１個以上の置換基を有していてもよいアリール基であることがより好ましい。 In condition ii), R 3 in formula (1) represents an organic group.
As used herein, an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound). The organic group can be a hydrocarbon group optionally having one or more substituents. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to. R 3 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group optionally having one or more substituents is preferred, and an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents is more preferred.
Ｒ３が１個以上の置換基を有していてもよいアルキル基である場合、Ｒ３は、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基とすることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基は置換基を有しないものとすることもできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 When R 3 is an alkyl group optionally having one or more substituents, R 3 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
Ｒ３が１個以上の置換基を有していてもよいアラルキル基である場合、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 When R 3 is an aralkyl group optionally having one or more substituents, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
Ｒ３が１個以上の置換基を有していてもよいアリール基である場合、Ｒ３は、置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基とできる。アリール基としては、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、又は２－アンスリル基を挙げることができ、フェニル基であることが好ましい。 When R 3 is an aryl group optionally having one or more substituents, R 3 can be an unsubstituted aryl group or an aryl group having one or more substituents. Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
Ｒ３が１個以上の置換基を有するアリール基である場合、Ｒ３に含まれるアリール基が有する置換基を第３の置換基と称する。Ｒ３は、第３の置換基とアリール基からなるものとできる。 When R3 is an aryl group having one or more substituents, the substituent of the aryl group contained in R3 is referred to as the third substituent. R3 can consist of a third substituent and an aryl group.
第３の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含むことが好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第３の置換基は、フッ素原子、フッ化アルキル基、１個以上の置換基を有していてもよいアルキル基からなる群から選択される少なくとも１つを含むことが更により好ましく、これらを１つ以上含むことができ、１つ又は２つ含むものとできる。第３の置換基は、フッ素を含む場合があるものの、これ以外に、酸素、硫黄、窒素などのヘテロ元素を含まない置換基であることが好ましい。Ｒ３は、例えば、アリール基と任意の置換基との間の結合部分にエーテル結合及びエステル結合を含まないことが好ましく、Ｒ３がエーテル結合及びエステル結合を含まないことが好ましい。 The third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included. The third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included. Although the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen. For example, R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
第３の置換基が含み得るフッ化アルキル基は、アルキル基が１個以上のフッ素原子で置換されている、フルオロアルキル基とできる。フッ化アルキル基はフッ素原子以外の置換基を有していても良い。フッ化アルキル基は、フッ素原子以外の置換基を有しないアルキル基とすることもできる。フッ化アルキル基は、アルキル基中の全ての水素原子がフッ素原子で置換された、パーフルオロアルキル基であることが好ましい。
フッ化アルキル基の炭素数は、１又は２であることが好ましい。フッ化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペンタフルオロエチル基、であることが好ましく、トリフルオロメチル基、ペンタフルオロエチル基であることがより好ましく、トリフルオロメチル基が更により好ましい。 A fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms. The fluorinated alkyl group may have a substituent other than a fluorine atom. The fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms. The fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
The fluorinated alkyl group preferably has 1 or 2 carbon atoms. The fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
第３の置換基が含み得る１個以上の置換基を有していても良いアルキル基としては、１個以上の置換基を有していてもよい、直鎖状、又は分枝鎖状のアルキル基を挙げることができる。なお、１個以上の置換基を有していても良いアルキル基は、フッ化アルキル基を含まないものとできる。アルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。アルキル基は置換基を有しないものとすることもできる。
第３の置換基が含み得るアルキル基としては、第１の置換基が含み得るアルキル基として列挙したアルキル基を挙げることができる。 The alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents. Alkyl groups may be mentioned. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Alkyl groups can also be unsubstituted.
Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
第３の置換基が含み得る１個以上の置換基を有していてもよいアラルキル基において、アラルキル基の炭素数は、４～１２とすることができ、４～１０であることが好ましい。アラルキル基の炭素数は、例えば、４、５、６、７、８、９、１０、１１、１２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
第３の置換基が含み得るアラルキル基としては、第１の置換基が含み得るアラルキル基として列挙したアラルキル基を挙げることができる。 In the aralkyl group optionally having one or more substituents which may be included in the third substituent, the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms. The number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
条件ｉｉ）において、Ｒ２及びＲ３は、少なくとも一方がフッ素含有置換基を有するアリール基であり、少なくとも一方が、フッ素含有置換基を有するフェニル基であることが好ましい。Ｒ２又はＲ３の一方が、１個以上の置換基を有していてもよいアルキル基である場合、他方は、フッ素含有置換基を有するアリールであり、フッ素含有基は、フッ素又はパーフルオロアルキル基を含むものとできる。 In condition ii), at least one of R 2 and R 3 is preferably an aryl group having a fluorine-containing substituent, and at least one is preferably a phenyl group having a fluorine-containing substituent. When one of R 2 or R 3 is an alkyl group optionally having one or more substituents, the other is an aryl having a fluorine-containing substituent, and the fluorine-containing group is fluorine or perfluoro It can contain an alkyl group.
環Ａは、好ましくは、Ｃ６０フラーレン、又はＣ７０フラーレン、より好ましくはＣ６０フラーレンである。
式（１）のフラーレン誘導体は、環ＡがＣ６０フラーレンであるフラーレン誘導体（以下、Ｃ６０フラーレン誘導体ともいう。）、及び環ＡがＣ７０フラーレンであるフラーレン誘導体（以下、Ｃ７０フラーレン誘導体ともいう。）の混合物であってもよい。混合物における、Ｃ６０フラーレン誘導体の含有量は、例えば、０．００１、０．０１、０．１、１、１０、２０、３０、４０、５０、６０、７０、８０、９０、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
The fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture. The content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
本発明の一実施形態に係る式（１）で表されるフラーレン誘導体が、条件ｉ）及びｉｉ）を満たす場合の具体例としては、
Ｒ１が、フェニル基、又は、アルキル基を有するフェニル基であって、
Ｒ２が、フッ素原子又はフッ化アルキル基を有する、フェニル基であって、
Ｒ３が、フェニル基である場合、
を挙げることができる。 As a specific example of the case where the fullerene derivative represented by formula (1) according to one embodiment of the present invention satisfies the conditions i) and ii),
R 1 is a phenyl group or a phenyl group having an alkyl group,
R 2 is a phenyl group having a fluorine atom or a fluorinated alkyl group,
When R 3 is a phenyl group,
can be mentioned.
本発明の一実施形態に係る式（１）で表されるフラーレン誘導体が、条件ｉ）を満たし、条件ｉｉ）を満たさない場合の具体例としては、
Ｒ１が、フェニル基、又は、アルキル基を有するフェニル基であって、
Ｒ２が、アルキル基を有するフェニル基であって、
Ｒ３が、フェニル基である場合、
を挙げることができる。 As a specific example of the case where the fullerene derivative represented by formula (1) according to one embodiment of the present invention satisfies condition i) but does not satisfy condition ii),
R 1 is a phenyl group or a phenyl group having an alkyl group,
R 2 is a phenyl group having an alkyl group,
When R 3 is a phenyl group,
can be mentioned.
本発明の一実施形態に係る式（１）で表されるフラーレン誘導体が、条件ｉｉ）を満たし、条件ｉ）を満たさない場合の具体例としては、
Ｒ１が、フェニル基、又は、アルキル基を有するフェニル基であって、
Ｒ２が、フッ素原子又はフッ化アルキル基を有する、フェニル基であって、
Ｒ３が、アルキル基である場合、
を挙げることができる。 As a specific example of the case where the fullerene derivative represented by formula (1) according to one embodiment of the present invention satisfies condition ii) but does not satisfy condition i),
R 1 is a phenyl group or a phenyl group having an alkyl group,
R 2 is a phenyl group having a fluorine atom or a fluorinated alkyl group,
When R 3 is an alkyl group,
can be mentioned.
１．２　フラーレン誘導体の特性
以下、本発明に係る式（１）で表される構造を有するフラーレン誘導体の特性について説明する。
なお、以下のフラーレン誘導体の特性に係る実施形態は、ｉ）及びｉｉ）の場合で共通の好ましい実施形態である。 1.2 Properties of Fullerene Derivative Properties of the fullerene derivative having the structure represented by formula (1) according to the present invention are described below.
The following embodiment relating to the properties of the fullerene derivative is a preferred embodiment common to cases i) and ii).
本発明の一実施形態に係るフラーレン誘導体は、ＬＵＭＯ準位の値が－３．６７ｅＶ未満であることが好ましい。
ＬＵＭＯ準位の値は、例えば、－３．７５、－３．７４、－３．７３、－３．７２、－３．７１、－３．７、－３．６９、－３．６８ｅＶであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
本発明の一実施形態に係るフラーレン誘導体は、式（１）で表される構造を有し、Ｒ１、Ｒ２、及び／又は、Ｒ３が特定の置換基を有することにより、ＬＵＭＯ準位を低めに調整することができ、変換効率の向上に寄与すると考えられる。
なお、ＬＵＭＯ準位は、Ｋａｒａｋａｗａら、Ｊｏｕｒｎａｌ　ｏｆ　Ｍ　ａｔｅｒｉａｌｓ　Ｃｈｅｍｉｓｔｒｙ　Ａ，２０１４年，２巻，２０８８９頁に記載の方法によって測定することができる。 The fullerene derivative according to one embodiment of the present invention preferably has a LUMO level value of less than -3.67 eV.
The values of the LUMO levels are, for example, −3.75, −3.74, −3.73, −3.72, −3.71, −3.7, −3.69, −3.68 eV. , within a range between any two of the numerical values exemplified herein.
A fullerene derivative according to one embodiment of the present invention has a structure represented by formula (1), and R 1 , R 2 , and/or R 3 have specific substituents, so that the LUMO level can be adjusted lower, which is considered to contribute to the improvement of conversion efficiency.
The LUMO level can be measured by the method described in Karakawa et al., Journal of Materials Chemistry A, 2014, 2, 20889 pages.
本発明の一実施形態に係るフラーレン誘導体は、室温におけるトルエン溶解度が０．５質量％以上であることが好ましく、１．０質量％以上であることがより好ましい。
トルエン溶解度は、例えば、０．５、１．０、１．５、２．０、２．５、３．０質量％程度であれは良く、またここで例示した数値の何れか２つの間の範囲内であってもよい。なお、トルエン溶解度とは、１００gのトルエンに可溶なフラーレン誘導体の質量を意味する。
本発明の一実施形態に係るフラーレン誘導体は、式（１）で表される構造を有し、Ｒ１、Ｒ２、及び／又は、Ｒ３が特定の置換基を有することにより、トルエン等の有機溶剤に対して適度な溶解性を有するものと推測され、有機発電層形成用溶液を容易に調整可能であり、有機発電層を容易に形成可能である。 The fullerene derivative according to one embodiment of the present invention preferably has a toluene solubility of 0.5% by mass or more at room temperature, more preferably 1.0% by mass or more.
The toluene solubility may be, for example, about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0% by mass, or between any two of the numerical values exemplified here. may be within the range. The toluene solubility means the mass of a fullerene derivative soluble in 100 g of toluene.
A fullerene derivative according to an embodiment of the present invention has a structure represented by formula (1), and R 1 , R 2 and/or R 3 have specific substituents such as toluene. It is presumed to have moderate solubility in an organic solvent, so that the organic power generation layer forming solution can be easily prepared, and the organic power generation layer can be easily formed.
なお、室温におけるトルエンへの溶解度は、ランベルト・ベールの法則を用いて、吸光度から求めることができる。まず、濃度既知のフラーレン誘導体のトルエン溶液を用いてモル吸光係数を求める。次に、フラーレン誘導体の過飽和トルエン溶液の上澄み溶液を一定量秤量し、これの吸光度を測定する。以下の式に従い、濃度を算出できる。
　　Ｃ＝Ａ／εｄ
［式中、Ｃ：濃度、Ａ：吸光度、ε：モル吸光係数、ｄ：吸光度測定用セル長（１ｃｍ）］ The solubility in toluene at room temperature can be determined from the absorbance using the Beer-Lambert law. First, a molar extinction coefficient is obtained using a toluene solution of a fullerene derivative with a known concentration. Next, a certain amount of the supernatant solution of the supersaturated toluene solution of the fullerene derivative is weighed, and the absorbance thereof is measured. The concentration can be calculated according to the following formula.
C=A/εd
[In the formula, C: concentration, A: absorbance, ε: molar extinction coefficient, d: cell length for absorbance measurement (1 cm)]
１．３　フラーレン誘導体の製造方法
本発明に係るフラーレン誘導体の製造方法は、特に制限されず、公知のフラーレン誘導体の製造方法、又はこれに準じた方法によって製造することができる。
一例として、本発明の一実施形態に係るフラーレン誘導体は、プラトー反応として知られる下記スキームで合成することとができる。 1.3 Method for Producing Fullerene Derivative The method for producing the fullerene derivative according to the present invention is not particularly limited, and it can be produced by a known method for producing a fullerene derivative or a method analogous thereto.
As an example, a fullerene derivative according to one embodiment of the present invention can be synthesized by the following scheme known as the plateau reaction.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
上記スキームでは、Ｒ１、Ｒ３を含むアミノ酸化合物と、Ｒ２を含むアルデヒド化合物と、フラーレンとを反応させ、式（１）で表されるフラーレン誘導体を得ることができる。
なお、上記式（１－１）における、Ｒ１、Ｒ２、Ｒ３は、式（１）におけるＲ１、Ｒ２、Ｒ３に対応する。 In the above scheme, an amino acid compound containing R 1 and R 3 , an aldehyde compound containing R 2 and a fullerene are reacted to obtain a fullerene derivative represented by formula (1).
R 1 , R 2 and R 3 in formula (1-1) above correspond to R 1 , R 2 and R 3 in formula (1).
アルデヒド化合物、アミノ酸化合物、及びフラーレンの量比は特に限定されないが、収率を高くする観点から、例えば、フラーレン１モルに対して、アルデヒド化合物及びアミノ酸化合物をそれぞれ０．１～１０モル用いることができ、好ましくは０．５～２モルの量で用いる。 The amount ratio of the aldehyde compound, the amino acid compound, and the fullerene is not particularly limited, but from the viewpoint of increasing the yield, for example, 0.1 to 10 mol each of the aldehyde compound and the amino acid compound can be used per 1 mol of the fullerene. can be used, preferably in an amount of 0.5 to 2 mol.
反応は、無溶媒又は溶媒中で行うことができる。溶媒としては、例えば、二硫化炭素、クロロホルム、ジクロロエタン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン等を挙げることができる。このなかでも、クロロホルム、トルエン、キシレン、及びクロロベンゼン等が好ましい。これらの溶媒は、適当な割合で混合して用いてもよい。 The reaction can be carried out in the absence of solvent or in a solvent. Examples of solvents include carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like. Among these, chloroform, toluene, xylene, chlorobenzene, and the like are preferable. These solvents may be mixed in an appropriate ratio and used.
反応温度は、例えば、室温～１５０℃とすることができ、好ましくは８０～１２０℃である。なお、本明細書中、室温は、１５～３０℃である。 The reaction temperature can be, for example, room temperature to 150°C, preferably 80 to 120°C. In this specification, room temperature is 15 to 30°C.
反応時間は、例えば、１時間～４日間であり、好ましくは１０～４８時間である。 The reaction time is, for example, 1 hour to 4 days, preferably 10 to 48 hours.
得られた化合物は、必要に応じて公知の精製方法で精製できる。
例えば、得られた化合物を、シリカゲルカラムクロマトグラフィー（展開溶媒としては、例えば、ヘキサン－クロロホルム、ヘキサン－トルエン、又はヘキサン－二硫化炭素が好ましい。）で精製し、その後、更にＨＰＬＣ（分取ＧＰＣ）（展開溶媒としては、例えば、クロロホルム、又はトルエンが好ましい。）で精製することができる。 The obtained compound can be purified by a known purification method, if necessary.
For example, the obtained compound is purified by silica gel column chromatography (developing solvent is preferably hexane-chloroform, hexane-toluene, or hexane-carbon disulfide), and then further HPLC (preparative GPC ) (preferable developing solvent is, for example, chloroform or toluene).
反応で用いられる、アルデヒド化合物、アミノ酸化合物、及びフラーレンは、公知の方法、又はこれに準じた方法によって合成してもよく、商業的に入手してもよい。一例として、アルデヒド化合物、及び、アミノ酸化合物は、例えば、実施例の方法で合成することができる。 Aldehyde compounds, amino acid compounds, and fullerenes used in the reaction may be synthesized by known methods or methods based thereon, or may be commercially available. As an example, an aldehyde compound and an amino acid compound can be synthesized, for example, by the method of Examples.
２．ｎ型半導体材料、有機発電層、及び光電変換素子
本発明の一実施形態に係るｎ型半導体材料は、上記フラーレン誘導体を含むものとできる。本発明の一実施形態に係るｎ型半導体材料は、上記フラーレン誘導体からなるものとすることもできる。 2. N-Type Semiconductor Material, Organic Power Generation Layer, and Photoelectric Conversion Device The n-type semiconductor material according to one embodiment of the present invention can contain the fullerene derivative. The n-type semiconductor material according to one embodiment of the present invention can also be made of the above fullerene derivative.
本発明の一実施形態に係る有機発電層は、上記ｎ型半導体材料と、ｐ型半導体材料を含有するものとできる。本発明の一実施形態に係る有機発電層は、本発明のｎ型半導体材料及び前記有機ｐ型半導体からなるものとできる。 An organic power generation layer according to an embodiment of the present invention can contain the n-type semiconductor material and the p-type semiconductor material. An organic power generation layer according to an embodiment of the present invention can be made of the n-type semiconductor material of the present invention and the organic p-type semiconductor.
ｐ型半導体材料としては、ポリ－ｐ－フェニレンビニレン、ポリ－アルコキシ－ｐ－フェニレンビニレン、ポリ－９，９－ジアルキルフルオレン、ポリ－ｐ－フェニレンビニレンなどを挙げることができる。
また、より高い変換効率を得るために、バンドギャップを狭くすることで（ローバンドギャップ）長波長光の吸収を可能にした、ドナーアクセプター型π共役高分子を用いることができる。ドナーアクセプター型π共役高分子は、ドナーユニットとアクセプターユニットとを有し、これらが交互に配置された構造を有する。ドナーユニットとしては、ベンゾジチオフェン、ジチエノシロール、Ｎ－アルキルカルバゾールを挙げることができ、アクセプターユニットとしては、ベンゾチアジアゾール、チエノチオフェン、チオフェンピロールジオンなどを挙げることができる。 Examples of p-type semiconductor materials include poly-p-phenylene vinylene, poly-alkoxy-p-phenylene vinylene, poly-9,9-dialkylfluorene, poly-p-phenylene vinylene, and the like.
Also, in order to obtain higher conversion efficiency, a donor-acceptor type π-conjugated polymer can be used that enables absorption of long-wavelength light by narrowing the bandgap (low bandgap). A donor-acceptor type π-conjugated polymer has a structure in which donor units and acceptor units are alternately arranged. Donor units include benzodithiophene, dithienosilol, and N-alkylcarbazole, and acceptor units include benzothiadiazole, thienothiophene, thiophenepyrroledione, and the like.
具体的には、これらのユニットを組み合わせた、ポリ（チエノ［３，４－ｂ］チオフェン－ｃｏ－ベンゾ［１，２－ｂ：４，５－ｂ'］チオフェン）（ＰＴＢｘシリーズ）、ポリ（ジチエノ［１，２－ｂ：４，５－ｂ'］［３，２－ｂ：２'，３'－ｄ］シロール－ａｌｔ－（２，１，３－ベンゾチアジアゾール）類を挙げることができ、一例としては、ＰＴＢ７、ＰＢＤＴＴＰＤ、ＰＳＢＴＢＴ、ＰＢＤＴＴＴ－ＣＦ、ＰＤＴＰ－ＤＦＢＴ等を挙げることができる。 Specifically, poly(thieno[3,4-b]thiophene-co-benzo[1,2-b:4,5-b′]thiophene) (PTBx series), poly( Dithieno[1,2-b:4,5-b′][3,2-b:2′,3′-d]silole-alt-(2,1,3-benzothiadiazole)s can be mentioned. , Examples include PTB7, PBDTTPD, PSBTBT, PBDTTT-CF, PDTP-DFBT, and the like.
本発明に係る上記フラーレン誘導体を含むｎ型半導体材料は、従来のｎ型半導体材料とは比較的親和性が悪い、長波長吸収型のｐ型半導体材料とであっても、親和性良く混ざり、界面面積が大きく、安定性の高いバルクヘテロジャンクション構造を構築することができるため、高い変換効率かつ高い耐久性を有する光電変換素子を得ることができる。
本発明に係る上記フラーレン誘導体は、長波長吸収型のｐ型半導体材料を用いる有機発電層のｎ型半導体材料としても好適に用いることができる。長波長吸収型のｐ型半導体材料とは、具体的には、極大吸収波長が７００ｎｍ以上であるｐ型半導体材料とできる。また、長波長吸収型のｐ型半導体材料としては、ＰＤＴＰ－ＤＦＢＴ及びＰＴＢ７－Ｔｈ，ＰＣＤＴＢＴ，ＰＣＰＤＴＢＴ，ＮＴ８１２などを挙げることができる。 The n-type semiconductor material containing the fullerene derivative according to the present invention mixes with good affinity even with a long-wavelength absorption p-type semiconductor material, which has relatively poor affinity with conventional n-type semiconductor materials, Since a bulk heterojunction structure having a large interface area and high stability can be constructed, a photoelectric conversion element having high conversion efficiency and high durability can be obtained.
The fullerene derivative according to the present invention can also be suitably used as an n-type semiconductor material for an organic power generation layer using a long wavelength absorption p-type semiconductor material. The long-wave absorption p-type semiconductor material can be specifically a p-type semiconductor material having a maximum absorption wavelength of 700 nm or more. Further, PDTP-DFBT, PTB7-Th, PCDTBT, PCPDTBT, NT812, etc. can be mentioned as long-wavelength absorption p-type semiconductor materials.
本発明の一実施形態に係る有機発電層においては、本発明に係るフラーレン誘導体を含むｎ型半導体材料と、ｐ型半導体材料とがバルクヘテロジャンクション構造を形成していることが好ましい。本発明の一実施形態に係る有機発電層は、例えば、有機発電層形成用溶液調製工程、及び、有機発電層形成工程を含む製造方法により製造することができる。有機発電層形成用溶液調製工程では、本発明に係るフラーレン誘導体を含むｎ型半導体材料及びｐ型半導体材料を有機溶媒に溶解させて、有機発電層形成用溶液を得ることができる。また、有機発電層形成工程では、得られた有機発電層形成用溶液を、スピンコート法、キャスト法、ディッピング法、インクジェット法、及びスクリーン印刷法等の公知の薄膜形成方法を採用して、基板上に薄膜を形成することができる。 In the organic power generation layer according to one embodiment of the present invention, it is preferable that the n-type semiconductor material containing the fullerene derivative according to the present invention and the p-type semiconductor material form a bulk heterojunction structure. The organic power generation layer according to one embodiment of the present invention can be produced, for example, by a production method including an organic power generation layer forming solution preparation step and an organic power generation layer formation step. In the organic power generation layer forming solution preparation step, the n-type semiconductor material and p-type semiconductor material containing the fullerene derivative according to the present invention can be dissolved in an organic solvent to obtain an organic power generation layer forming solution. Further, in the organic power generation layer forming step, the obtained organic power generation layer forming solution is applied to a substrate by employing a known thin film forming method such as a spin coating method, a casting method, a dipping method, an ink jet method, and a screen printing method. A thin film can be formed thereon.
本発明の一実施形態に係る光電変換素子は、上記の有機発電層を備えるものとできる。本発明の一実施形態に係る光電変換素子は、光センサーとできる。また、本発明の一実施形態に係る光電変換素子は、有機薄膜太陽電池とできる。
本発明の一実施形態に係る有機薄膜太陽電池は、例えば、基板上に、透明電極（陰極）、陰極側電荷輸送層、有機発電層、陽極側電荷輸送層及び対極（陽極）が順次積層された構造の太陽電池とすることができる。有機発電層は、本発明に係るフラーレン誘導体を含むｎ型半導体材料と、ｐ型半導体材料とがバルクヘテロジャンクション構造を形成している半導体薄膜層（すなわち、光電変換層）とできる。 A photoelectric conversion device according to an embodiment of the present invention can be provided with the organic power generation layer described above. A photoelectric conversion element according to an embodiment of the present invention can be used as a photosensor. Moreover, the photoelectric conversion element which concerns on one Embodiment of this invention can be made into an organic thin-film solar cell.
An organic thin-film solar cell according to an embodiment of the present invention includes, for example, a transparent electrode (cathode), a cathode-side charge transport layer, an organic power-generating layer, an anode-side charge transport layer, and a counter electrode (anode) which are sequentially laminated on a substrate. A solar cell having a structure can be obtained. The organic power generation layer can be a semiconductor thin film layer (that is, a photoelectric conversion layer) in which an n-type semiconductor material containing the fullerene derivative according to the present invention and a p-type semiconductor material form a bulk heterojunction structure.
本発明の一実施形態に係る有機薄膜太陽電池において、有機発電層以外の各層の材料としては、公知の材料を適宜使用できる。具体的には、電極の材料としては、例えば、アルミニウム、金、銀、銅、及び酸化インジウム（ＩＴＯ）等が例示される。電荷輸送層の材料としては、例えば、ＰＦＮ（ポリ［９，９－ビス（３'－（Ｎ，Ｎ－ジメチルアミノ）プロピル－２，７－フルオレン）－ａｌｔ－２，７－（９，９－ジオクチルフルオレン）］）及びＭｏＯ３（酸化モリブデン）等が例示される。 In the organic thin-film solar cell according to one embodiment of the present invention, known materials can be appropriately used as materials for each layer other than the organic power generation layer. Specifically, examples of electrode materials include aluminum, gold, silver, copper, and indium oxide (ITO). Materials for the charge transport layer include, for example, PFN (poly[9,9-bis(3′-(N,N-dimethylamino)propyl-2,7-fluorene)-alt-2,7-(9,9 -dioctylfluorene)]) and MoO 3 (molybdenum oxide).
本発明の一実施形態に係る光電変換素子及び有機薄膜太陽電池は、ｐ型半導体材料としてＰＴＢ７或いはＰＤＴＰ－ＤＦＢＴを用いた際の初期エネルギー変換効率が７．０％以上である。さらには、光電変換素子及び有機薄膜太陽電池を８５℃で２時間加熱後のエネルギー変換効率が、初期エネルギー変換効率の９５％以上を保持できる。すなわち、初期エネルギー変換効率に対する８５℃で２時間加熱後のエネルギー変換効率の低下が５％以内である。
本発明に係る本発明に係るフラーレン誘導体を含むｎ型半導体材料を含む有機発電層を備える光電変換素子及び有機薄膜太陽電池は、ｎ型半導体材料とｐ型半導体材料とが親和性よく混合し、界面面積が大きく、安定性の高いバルクヘテロジャンクション構造を構築することができるため、高い変換効率かつ高い耐久性を有する光電変換素子及び有機薄膜太陽電池を得ることができる。 A photoelectric conversion device and an organic thin film solar cell according to an embodiment of the present invention have an initial energy conversion efficiency of 7.0% or more when PTB7 or PDTP-DFBT is used as the p-type semiconductor material. Furthermore, the energy conversion efficiency after heating the photoelectric conversion element and the organic thin film solar cell at 85° C. for 2 hours can maintain 95% or more of the initial energy conversion efficiency. That is, the decrease in energy conversion efficiency after heating at 85° C. for 2 hours with respect to the initial energy conversion efficiency is within 5%.
A photoelectric conversion device and an organic thin film solar cell provided with an organic power generation layer containing an n-type semiconductor material containing a fullerene derivative according to the present invention according to the present invention are such that an n-type semiconductor material and a p-type semiconductor material are mixed with good affinity, Since a bulk heterojunction structure having a large interface area and high stability can be constructed, a photoelectric conversion element and an organic thin-film solar cell having high conversion efficiency and high durability can be obtained.
以下、実施例に基づいて本発明を更に詳細に説明するが、本発明はこれらに限定して解釈されるものではない。 EXAMPLES The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited to these examples.
（化合物１）
［６，６］－フェニル－Ｃ６１－酪酸メチル（Ｓｉｇｍａ－Ａｌｄｒｉｃｈ、Ｎｏ．６８４４４９，９９．５％）を化合物１として用いた。 (Compound 1)
[6,6]-Phenyl-C61-methylbutyrate (Sigma-Aldrich, No. 684449, 99.5%) was used as compound 1.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（化合物２の合成）
（３－オクチルアニリンの合成）
（１－オクチンと3-ブロモニトロベンゼンのＳｏｎｏｇａｓｈｉｒａ反応）
撹拌子を入れた３口フラスコ（容量２００ｍＬ）中に、１－ブロモ－３－ニトロベンゼン（９．７ｇ，４８ｍｍｏｌ）、トリフェニルホスフィン（１．２６ｇ，４．８ｍｍｏｌ）、酢酸パラジウム（ＩＩ）（５４４ｍｇ，２．４ｍｍｏｌ）のトリエチルアミン溶液（９７ｍＬ）を入れ、窒素置換を行った後、１－オクチン（１０．６ｍＬ，７２ｍｍｏｌ）を加えた。反応容器をオイルバス（浴温１００℃）に浸け、撹拌下で４８時間加熱した。反応をＧＬＣで追跡し、原料の消失により反応終点を判定した。冷却後、反応液を酢酸エチルと水を用いて抽出分離を行った。有機相をエバポレーターにより濃縮し中間体２１（オクト－１－イン－１－イル）ニトロベンゼン）を得た。 (Synthesis of compound 2)
(Synthesis of 3-octylaniline)
(Sonogashira reaction of 1-octyne and 3-bromonitrobenzene)
1-bromo-3-nitrobenzene (9.7 g, 48 mmol), triphenylphosphine (1.26 g, 4.8 mmol), palladium(II) acetate (544 mg) were placed in a three-necked flask (capacity 200 mL) containing a stirrer. , 2.4 mmol) in triethylamine (97 mL) was added, and after nitrogen substitution, 1-octyne (10.6 mL, 72 mmol) was added. The reaction vessel was immersed in an oil bath (bath temperature 100° C.) and heated with stirring for 48 hours. The reaction was followed by GLC and the reaction endpoint was determined by the disappearance of starting material. After cooling, the reaction liquid was subjected to extraction separation using ethyl acetate and water. The organic phase was concentrated by an evaporator to obtain intermediate 21 (oct-1-yn-1-yl)nitrobenzene).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
得られた中間体２１の分析結果を以下に示す。
ＭＳ（ＥＩ）２３１（Ｍ＋）
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：０．９１（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），１．２５－１．４０（４Ｈ，ｍ），１．４０－１．５５（２Ｈ，ｍ），１．５８－１．７０（２Ｈ，ｍ），２．４３（２Ｈ，ｔ，Ｊ＝７．１Ｈｚ），７．４５（１Ｈ，ｄ－ｄ，Ｊ＝７．８，８．２Ｈｚ），７．６８（１Ｈ，ｄ－ｄ－ｄ，Ｊ＝７．８，２．０，１．０Ｈｚ），８．１５（１Ｈ，ｄ－ｄ－ｄ，Ｊ＝８．２，２．０，１．０Ｈｚ），８．２２（１Ｈ，ｄ－ｄ，Ｊ＝２．０，１．０Ｈｚ）． The analytical results of the obtained intermediate 21 are shown below.
MS(EI)231(M+)
H-NMR (500MHz, CDCl3 )
δ: 0.91 (3H, t, J = 7.0Hz), 1.25-1.40 (4H, m), 1.40-1.55 (2H, m), 1.58-1.70 (2H, m), 2.43 (2H, t, J = 7.1 Hz), 7.45 (1H, dd, J = 7.8, 8.2 Hz), 7.68 (1H, d- dd, J = 7.8, 2.0, 1.0 Hz), 8.15 (1H, dd, J = 8.2, 2.0, 1.0 Hz), 8.22 ( 1H, dd, J=2.0, 1.0 Hz).
（中間体２１（オクト－１－イン－１－イル）ニトロベンゼン）の還元反応）
得られた粗生成物をメタノール溶液（５００ｍＬ）とし、Ｐｄ／Ｃ０．５ｇを加えた。反応容器内を水素置換した後、水素圧力１気圧で室温下に撹拌した。反応をＧＬＣで追跡し、原料の消失により反応終点を判定した。反応液をセライト濾過し、エバポレーションにより濃縮した。濃縮した粗生成物を減圧蒸留により精製し、中間体２２（３－オクチルアニリン）を得た（収率：７５％（２工程））。 (Reduction reaction of intermediate 21 (oct-1-yn-1-yl)nitrobenzene))
The resulting crude product was made into a methanol solution (500 mL), and 0.5 g of Pd/C was added. After the inside of the reaction vessel was replaced with hydrogen, the mixture was stirred at room temperature under a hydrogen pressure of 1 atm. The reaction was followed by GLC and the reaction endpoint was determined by the disappearance of starting material. The reaction solution was filtered through celite and concentrated by evaporation. The concentrated crude product was purified by vacuum distillation to give intermediate 22 (3-octylaniline) (yield: 75% (2 steps)).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
得られた中間体２２の分析結果を以下に示す。
ＭＳ（ＥＩ）２０５（Ｍ＋）
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：０．８８（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．２０－１．４０（１０Ｈ，ｍ），１．５０－１．６５（２Ｈ，ｍ），２．５０（２Ｈ，ｔ，Ｊ＝７．８Ｈｚ），３．５７（２Ｈ，ｂｓ），６．４９（１Ｈ，ｄ，Ｊ＝７．６Ｈｚ），６．５０（１Ｈ，ｓ），６．５８（１Ｈ，ｄ，Ｊ＝７．６Ｈｚ），７．０５（１Ｈ，ｄ－ｄ，Ｊ＝７．６，７．６Ｈｚ）． The analytical results of the obtained intermediate 22 are shown below.
MS(EI)205(M+)
H-NMR (500MHz, CDCl3 )
δ: 0.88 (3H, t, J = 7.1Hz), 1.20-1.40 (10H, m), 1.50-1.65 (2H, m), 2.50 (2H, t , J = 7.8 Hz), 3.57 (2H, bs), 6.49 (1H, d, J = 7.6 Hz), 6.50 (1H, s), 6.58 (1H, d, J = 7.6 Hz), 7.05 (1H, dd, J = 7.6, 7.6 Hz).
（２－フェニル－Ｎ－（３－オクチルフェニル）グリシンの合成）
撹拌子を入れた二径フラスコ（容量５０ｍＬ）中に、３－オクチルアニリン（２．５ｇ，１２ｍｍｏｌ）、α－ブロモフェニル酢酸（３．８７ｇ，１８ｍｍｏｌ）、メタノール（５ｍＬ）、トリエチルアミン（５ｍＬ）を入れ、窒素雰囲気下、室温で４２時間攪拌した。反応の追跡はＴＬＣ（展開溶媒：クロロホルム：メタノール＝２０：１（ｖ／ｖ））により行った。反応溶液をエバポレーションにより濃縮後、希塩酸で液性をｐＨ３に調整して析出した結晶（中間体２３）をろ取した（収率６３％）。 (Synthesis of 2-phenyl-N-(3-octylphenyl)glycine)
3-octylaniline (2.5 g, 12 mmol), α-bromophenylacetic acid (3.87 g, 18 mmol), methanol (5 mL), and triethylamine (5 mL) were placed in a double diameter flask (capacity 50 mL) containing a stirrer. and stirred at room temperature for 42 hours under a nitrogen atmosphere. The reaction was tracked by TLC (developing solvent: chloroform:methanol=20:1 (v/v)). After concentrating the reaction solution by evaporation, the pH was adjusted to pH 3 with dilute hydrochloric acid, and the precipitated crystals (intermediate 23) were collected by filtration (yield 63%).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
得られた中間体２３の分析結果を以下に示す。
ＭＳ（ＥＩ）３４０（Ｍ＋）
Ｈ－ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ３）
δ：０．９１（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．２０－１．４０（１０Ｈ，ｍ），１．５０－１．６０（２Ｈ，ｍ），２．５０（２Ｈ，ｔ，Ｊ＝７．８Ｈｚ），５．１１（１Ｈ，ｓ），６．４１（１Ｈ，ｄ，Ｊ＝７．８Ｈｚ），６．４６（１Ｈ，ｓ），７．０７（１Ｈ，ｄ－ｄ，Ｊ＝７．６，７．８Ｈｚ），７．３５（１Ｈ，ｔ，Ｊ＝７．１Ｈｚ），７．３９（２Ｈ，ｄ－ｄ，Ｊ＝７．１，７．１Ｈｚ），７．５２（２Ｈ，ｄ，Ｊ＝７．１Ｈｚ）． The analytical results of the obtained intermediate 23 are shown below.
MS(EI)340(M+)
H-NMR (600MHz, CDCl3 )
δ: 0.91 (3H, t, J = 7.1Hz), 1.20-1.40 (10H, m), 1.50-1.60 (2H, m), 2.50 (2H, t , J = 7.8 Hz), 5.11 (1H, s), 6.41 (1H, d, J = 7.8 Hz), 6.46 (1H, s), 7.07 (1H, dd , J=7.6, 7.8 Hz), 7.35 (1H, t, J=7.1 Hz), 7.39 (2H, dd, J=7.1, 7.1 Hz), 7. 52 (2H,d,J=7.1Hz).
（フラーレン誘導体（ＰＰＴＦＮＰＯ）合成）
側管にガス導入管を装着した容量３Ｌセパラブルフラスコ中に、２－［（３－オクチルフェニル）アミノ］－２－フェニル酢酸（９．６５ｇ，２８ｍｍｏｌ）、４－トリフルオロメチルベンツアルデヒド（３７．６ｍＬ，２８０ｍｍｏｌ）、フラーレン（Ｃ６０、１１．２６ｇ、１５．６ｍｍｏｌ）を入れ、溶媒（ｏ－キシレン）２．５Ｌを加えた。上記溶液をガス導入管から窒素バブリング（２時間）を行い、系中から酸素を除去した。オイルバス中１５０℃（バス温）で７時間加熱撹拌した。溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン－トルエン　５０：１～３０：１）により、さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ２８ｍｍ×２５０ｍｍ、溶離液：トルエン、１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物２（フラーレン誘導体（ＰＰＴＦＮＰＯ））９．５６ｇを得た（収率５２％）。 (Fullerene derivative (PPTFNPO) synthesis)
2-[(3-octylphenyl)amino]-2-phenylacetic acid (9.65 g, 28 mmol), 4-trifluoromethylbenzaldehyde (37 .6 mL, 280 mmol), fullerene (C60, 11.26 g, 15.6 mmol) was added, and 2.5 L of solvent (o-xylene) was added. Nitrogen bubbling (2 hours) was performed on the above solution from the gas inlet tube to remove oxygen from the system. The mixture was heated and stirred in an oil bath at 150°C (bath temperature) for 7 hours. The solvent was concentrated by evaporation, and the obtained reaction product was subjected to silica gel column chromatography (eluent: n-heptane-toluene 50:1 to 30:1), followed by preparative HPLC (column: Buckyprep 28 mm × 250 mm, Eluent: toluene, 10 mL/min, detector: RI) to obtain 9.56 g of compound 2 (fullerene derivative (PPTFNPO)) (yield: 52%).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
得られた化合物２の分析結果を以下に示す。
Ｈ－ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ３）
δ：０．９３（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．１０－１．２２（２Ｈ，ｍ），１．２２－１．４５（１０Ｈ，ｍ），２．４１－２．５３（２Ｈ，ｍ），６．６５（１Ｈ，ｄ，Ｊ＝７．５Ｈｚ），６．９５（１Ｈ，ｄ，Ｊ＝７．５Ｈｚ），６．９５（１Ｈ，ｓ），７．０６（１Ｈ，ｄ－ｄ，Ｊ＝７．５，７．５Ｈｚ），７．１３（１Ｈ，ｓ），７．１９（１Ｈ，ｓ），７．２７（１Ｈ，ｔ，Ｊ＝７．６Ｈｚ），７．３４（２Ｈ，ｄ－ｄ，Ｊ＝７．６，７．３Ｈｚ），７．６４（２Ｈ，ｄ，Ｊ＝８．１Ｈｚ），７．８３（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ），７．９８（２Ｈ，ｄ，Ｊ＝８．１Ｈｚ）．
Ｆ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：－６２．５７（ｓ） The analytical results of the obtained compound 2 are shown below.
H-NMR (600MHz, CDCl3 )
δ: 0.93 (3H, t, J = 7.1 Hz), 1.10-1.22 (2H, m), 1.22-1.45 (10H, m), 2.41-2.53 (2H, m), 6.65 (1H, d, J = 7.5Hz), 6.95 (1H, d, J = 7.5Hz), 6.95 (1H, s), 7.06 (1H , dd, J = 7.5, 7.5 Hz), 7.13 (1H, s), 7.19 (1H, s), 7.27 (1H, t, J = 7.6 Hz), 7 .34 (2H, dd, J = 7.6, 7.3 Hz), 7.64 (2H, d, J = 8.1 Hz), 7.83 (2H, d, J = 7.3 Hz), 7.98 (2H,d,J=8.1Hz).
F-NMR (500 MHz, CDCl 3 ) δ: -62.57 (s)
（化合物３の合成）
（３－オクチルベンツアルデヒドの合成）
窒素雰囲気下に容量２００ｍＬの２口フラスコ中の９－ＢＢＮ（９－ボラビシクロ［３．３．１］ノナン）のＴＨＦ溶液（０．５Ｍ，４０ｍＬ，２０ｍｍｏｌ）に、０℃で１－オクテン（３．２ｍＬ，２０ｍｍｏｌ）をシリンジを用いて滴下した。１５分間この温度で撹拌した後、室温に戻しジムロート冷却器を装着した。得られた溶液中に、炭酸カリウム（８．３ｇ，６０ｍｍｏｌ）、酢酸パラジム（２３４ｍｇ，１ｍｍｏｌ）、トリフェニルホスフィン（５３０ｍｇ、２ｍｍｏｌ）、３－ブロモベンツアルデヒド（２．５ｍＬ，２０ｍｍｏｌ）、ＴＨＦ（４０ｍＬ）、および水（１０ｍＬ）を入れた。この反応溶液をオイルバスに浸けて、２時間加熱還流した。冷後、反応液を飽和重曹水に注ぎ、酢酸エチルで抽出した。有機相を減圧濃縮した後、得られた反応物をシリカゲルカラムクロマトグラフィー（溶離液　ヘプタン：酢酸エチル＝６：１）により精製し、中間体３１（３－オクチルベンツアルデヒド）３．５ｇを得た（収率：８５％）。 (Synthesis of compound 3)
(Synthesis of 3-octylbenzaldehyde)
1-octene (3 .2 mL, 20 mmol) was added dropwise using a syringe. After stirring at this temperature for 15 minutes, it was returned to room temperature and equipped with a Dimroth condenser. Potassium carbonate (8.3 g, 60 mmol), palladium acetate (234 mg, 1 mmol), triphenylphosphine (530 mg, 2 mmol), 3-bromobenzaldehyde (2.5 mL, 20 mmol), THF (40 mL) were added to the resulting solution. ), and water (10 mL). This reaction solution was immersed in an oil bath and heated under reflux for 2 hours. After cooling, the reaction solution was poured into saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate. After the organic phase was concentrated under reduced pressure, the obtained reaction product was purified by silica gel column chromatography (eluent heptane:ethyl acetate=6:1) to obtain 3.5 g of intermediate 31 (3-octylbenzaldehyde). (Yield: 85%).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
得られた中間体３１の分析結果を以下に示す。
ＭＳ（ＥＩ）２１８（Ｍ＋）
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：０．８８（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．２０－１．４５（１０Ｈ，ｍ），１．５５－１．７５（２Ｈ，ｍ），２．６８（２Ｈ，ｔ，Ｊ＝７．６Ｈｚ），７．４１－７．４８（２Ｈ，ｄ，ｍ），７．６６－７．７３（２Ｈ，ｍ），１０．００（１Ｈ，ｓ）． The analytical results of the obtained intermediate 31 are shown below.
MS (EI) 218 (M+)
H-NMR (500MHz, CDCl3 )
δ: 0.88 (3H, t, J = 7.1Hz), 1.20-1.45 (10H, m), 1.55-1.75 (2H, m), 2.68 (2H, t , J=7.6 Hz), 7.41-7.48 (2H, d, m), 7.66-7.73 (2 H, m), 10.00 (1 H, s).
（フラーレン誘導体（ＰＰＯＮＰＯ）の合成）
側管にガス導入管を装着した容量５００ｍＬの２口フラスコ中に、２－［（３－オクチルフェニル）アミノ］－２－フェニル酢酸（１．０３ｇ，３．０ｍｍｏｌ）、３－オクチルベンツアルデヒド（１．３２ｇ，６．０ｍｍｏｌ）、フラーレン（Ｃ６０、１．１０ｇ、１．５ｍｍｏｌ）を入れ、溶媒（ｏ－キシレン）３００ｍＬを加える。上記溶液をガス導入管から窒素バブリング（１時間）を行い、系中から酸素を除去した。オイルバス中１５０℃（バス温）で１５時間加熱撹拌した。溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン＝５０：１）さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ２８ｍｍ×２５０ｍｍ、溶離液：トルエン、１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物３（フラーレン誘導体（ＰＰＯＮＰＯ））を６９０ｍｇ得た（収率：３８％）。 (Synthesis of fullerene derivative (PPONPO))
2-[(3-octylphenyl)amino]-2-phenylacetic acid (1.03 g, 3.0 mmol), 3-octylbenzaldehyde ( 1.32 g, 6.0 mmol), fullerene (C60, 1.10 g, 1.5 mmol), and 300 mL of solvent (o-xylene) are added. Nitrogen bubbling (1 hour) was performed on the above solution from the gas inlet tube to remove oxygen from the system. The mixture was heated and stirred in an oil bath at 150°C (bath temperature) for 15 hours. The solvent was concentrated by evaporation, and the resulting reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene = 50:1) and preparative HPLC (column: Buckyprep 28 mm × 250 mm, eluent: toluene, 10 mL /min, detector: RI) to obtain 690 mg of compound 3 (fullerene derivative (PPONPO)) (yield: 38%).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
得られた化合物３の分析結果を以下に示す。
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：０．８４（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），０．９０（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．０４－１．５２（２４Ｈ，ｍ），２．３３－２．６２（４Ｈ，ｍ），６．５７（１Ｈ，ｄ，Ｊ＝７．３Ｈｚ），６．９２－７．０５（４Ｈ，ｍ），７．０９（１Ｈ，ｓ），７．１３（１Ｈ，ｓ），７．１８－７．２６（２Ｈ，ｍ），７．３３（２Ｈ，ｔ，Ｊ＝７．６Ｈｚ），７．６０（１Ｈ，ｓ），７．６１（１Ｈ，ｄ，Ｊ＝７．３Ｈｚ），７．８１（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ）． The analysis results of the obtained compound 3 are shown below.
H-NMR (500MHz, CDCl3 )
δ: 0.84 (3H, t, J = 7.0Hz), 0.90 (3H, t, J = 7.1Hz), 1.04-1.52 (24H, m), 2.33-2 .62 (4H, m), 6.57 (1H, d, J = 7.3 Hz), 6.92-7.05 (4H, m), 7.09 (1H, s), 7.13 (1H , s), 7.18-7.26 (2H, m), 7.33 (2H, t, J = 7.6 Hz), 7.60 (1H, s), 7.61 (1H, d, J = 7.3 Hz), 7.81 (2H, d, J = 7.3 Hz).
（化合物４の合成）
（フラーレン誘導体（ＨＰｄＦＮＰ）の合成）
側管にガス導入管を装着した容量５００ｍＬの２口フラスコ中に、２－（フェニルアミノ）－オクタン酸（７１０ｍｇ，３．０ｍｍｏｌ）、２，４－ジフルオロベンツアルデヒド（２ｍＬ）、フラーレン（Ｃ６０、７２０ｍｇ、１．０ｍｍｏｌ）を入れ、溶媒（ｏ－キシレン）３００ｍＬを加えた。上記溶液をガス導入管から窒素バブリング（１時間）を行い、系中から酸素を除去した。オイルバス中１５０℃（バス温）で１５時間加熱撹拌した。
溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン　１００：１～５０：１）さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ２８ｍｍｘ２５０ｍｍ、溶離液：トルエン、１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物４（フラーレン誘導体（ＨＰｄＦＮＰ））を得た（収率３２％）。 (Synthesis of compound 4)
(Synthesis of fullerene derivative (HPdFNP))
2-(phenylamino)-octanoic acid (710 mg, 3.0 mmol), 2,4-difluorobenzaldehyde (2 mL), fullerene (C60, 720 mg, 1.0 mmol) was added, and 300 mL of solvent (o-xylene) was added. Nitrogen bubbling (1 hour) was performed on the above solution from the gas inlet tube to remove oxygen from the system. The mixture was heated and stirred in an oil bath at 150°C (bath temperature) for 15 hours.
The solvent was concentrated by evaporation, and the obtained reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene 100:1 to 50:1) and preparative HPLC (column: Buckyprep 28 mm x 250 mm, eluent: toluene, 10 mL/min, detector: RI) to obtain compound 4 (fullerene derivative (HPdFNP)) (32% yield).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
得られた化合物４の分析結果を以下に示す。
Ｈ－ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ３）
δ：０．８１（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），１．１０－１．４０（６Ｈ，ｍ），１．４３－１．７５（２Ｈ，ｍ），２．２０－２．３０（１Ｈ，ｍ），２．７８－２．８８（１Ｈ，ｍ），５．６０－５．６６（１Ｈ，ｍ），６．６９－６．７５（１Ｈ，ｍ），６．８２－６．９０（１Ｈ，ｍ），７．０７（１Ｈ，ｔ，７．３Ｈｚ），７．１０－７．３２（２Ｈ，ｍ），７．２４（１Ｈ，ｓ），７．３５（２Ｈ，ｄ－ｄ，Ｊ＝７．３，７．３Ｈｚ），７．６２－７．７２（１Ｈ，ｍ）．
Ｆ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：－１０９．５－－１０９．８（１Ｆ，ｍ），－１１２．４－－１１２．６（１Ｆ，ｍ）， The analysis results of the obtained compound 4 are shown below.
H-NMR (600MHz, CDCl3 )
δ: 0.81 (3H, t, J = 7.0 Hz), 1.10-1.40 (6H, m), 1.43-1.75 (2H, m), 2.20-2.30 (1H, m), 2.78-2.88 (1H, m), 5.60-5.66 (1H, m), 6.69-6.75 (1H, m), 6.82-6 .90 (1H, m), 7.07 (1H, t, 7.3 Hz), 7.10-7.32 (2H, m), 7.24 (1H, s), 7.35 (2H, d -d, J=7.3, 7.3 Hz), 7.62-7.72 (1 H, m).
F-NMR (500 MHz, CDCl 3 ) δ: -109.5--109.8 (1 F, m), -112.4--112.6 (1 F, m),
（化合物５の合成）
２－（フェニルアミノ）－２－［４－（トリフルオロメチル）フェニル］酢酸（１．１８ｇ，４ｍｍｏｌ）、フラーレン（Ｃ６０，１．４４ｇ，２．０ｍｍｏｌ）、ヘプタナール（２ｍＬ）のｏ－キシレン（４００ｍＬ）溶液を１５０℃で２４時間加熱撹拌した。
溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン＝１００：１）により、さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ２８ｍｍ×２５０ｍｍ、溶離液：トルエン　１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物５を７０４ｍｇ得た（収率：３３％）。 (Synthesis of compound 5)
2-(Phenylamino)-2-[4-(trifluoromethyl)phenyl]acetic acid (1.18 g, 4 mmol), fullerene (C60, 1.44 g, 2.0 mmol), heptanal (2 mL) of o-xylene ( 400 mL) solution was heated and stirred at 150° C. for 24 hours.
The solvent was concentrated by evaporation, and the obtained reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene = 100:1), followed by preparative HPLC (column: Buckyprep 28 mm × 250 mm, eluent: toluene 10 mL/min, detector: RI) to obtain 704 mg of compound 5 (yield: 33%).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
得られた化合物５の分析結果を以下に示す。
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：０．８１（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），１．１２－１．４２（４Ｈ，ｍ），１．４５－１．７０（２Ｈ，ｍ），２．２０－２．３２（１Ｈ，ｍ），２．７７－２．８６（１Ｈ，ｍ），５．６３－５．７３（１Ｈ，ｍ），６．３５（１Ｈ，ｓ），７．０５（１Ｈ，ｔ，Ｊ＝７．３Ｈｚ），７．１３－７．３３（２Ｈ，ｍ），７．３４（２Ｈ，ｔ，Ｊ＝７．９Ｈｚ），７．５３（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ），７．８３（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ）．
Ｆ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：－６２．３６（ｓ） The analysis results of the obtained compound 5 are shown below.
H-NMR (500 MHz, CDCl 3 ) δ: 0.81 (3H, t, J = 7.0 Hz), 1.12-1.42 (4H, m), 1.45-1.70 (2H, m ), 2.20-2.32 (1H, m), 2.77-2.86 (1H, m), 5.63-5.73 (1H, m), 6.35 (1H, s), 7.05 (1H, t, J = 7.3Hz), 7.13-7.33 (2H, m), 7.34 (2H, t, J = 7.9Hz), 7.53 (2H, d , J=8.0 Hz), 7.83 (2H, d, J=8.0 Hz).
F-NMR (500 MHz, CDCl 3 ) δ: -62.36 (s)
（化合物６の合成）
４－（トリフルオロメチル）フェニル酢酸（２．０ｇ，１０．０ｍｍｏｌ）のエタノール溶液中に濃硫酸０．５ｍＬを加え、室温で１５時間撹拌した。ＴＬＣで反応を追跡し、原料消失後、反応液を水で薄めて酢酸エチルで抽出した。有機相を重曹、水洗後、エバポレーションにより濃縮した（２．３ｇ，１００％）。
ここで得られた反応物を１，３－ビス（トリフルオロメチル）ベンゼン３０ｍＬに溶解し、ここにＮＢＳ（Ｎ－ブロモスクシンイミド）（１．７８ｇ，１０．０ｍｍｏｌ），ＡＩＢＮ（アゾビスイソブチロニトリル）（２００ｍｇ）を加えて、９０℃で１５時間加熱撹拌した。反応液をヘプタンで希釈し、水洗後エバポレーションにより濃縮した。得られた反応物にアニリン（１ｍＬ），トリエチルアミン４ｍＬ、メタノール２ｍＬを加えて、室温で１８時間撹拌した。反応液を酢酸エチルで希釈し、水洗後、エバポレーションにより濃縮した。ここで得られた反応物をシリカゲルカラムクロマトグラフィー（ＳｉＯ２（２００ｇ），溶離液　ヘプタン：酢酸エチル＝２０：１）で精製し、２－（フェニルアミノ）－２－［４－（トリフルオロメチル）フェニル］酢酸エチルエステル２．４ｇを得た（収率：８３％（３工程））。上記エステル体に水酸化ナトリウム（１．８ｇ）、メタノール４０ｍＬ、水２０ｍＬを加えて、室温下に２４時間撹拌した。反応液を希塩酸でｐＨ３まで酸性にし、酢酸エチルで抽出した。エバポレーションにより濃縮し、２－（フェニルアミノ）－２－［４－（トリフルオロメチル）フェニル］酢酸２．１ｇを得た（９３％）。 (Synthesis of compound 6)
0.5 mL of concentrated sulfuric acid was added to an ethanol solution of 4-(trifluoromethyl)phenylacetic acid (2.0 g, 10.0 mmol), and the mixture was stirred at room temperature for 15 hours. The reaction was followed by TLC, and after the raw material disappeared, the reaction solution was diluted with water and extracted with ethyl acetate. The organic phase was washed with sodium bicarbonate and water, and concentrated by evaporation (2.3 g, 100%).
The reactant obtained here was dissolved in 30 mL of 1,3-bis(trifluoromethyl)benzene, and NBS (N-bromosuccinimide) (1.78 g, 10.0 mmol), AIBN (azobisisobutyro nitrile) (200 mg) was added, and the mixture was heated and stirred at 90°C for 15 hours. The reaction solution was diluted with heptane, washed with water and concentrated by evaporation. Aniline (1 mL), triethylamine (4 mL), and methanol (2 mL) were added to the obtained reaction product, and the mixture was stirred at room temperature for 18 hours. The reaction solution was diluted with ethyl acetate, washed with water, and concentrated by evaporation. The reaction product obtained here was purified by silica gel column chromatography (SiO 2 (200 g), eluent heptane:ethyl acetate=20:1), 2-(phenylamino)-2-[4-(trifluoromethyl ) 2.4 g of phenyl]acetic acid ethyl ester were obtained (yield: 83% (3 steps)). Sodium hydroxide (1.8 g), 40 mL of methanol and 20 mL of water were added to the above ester, and the mixture was stirred at room temperature for 24 hours. The reaction solution was acidified to pH 3 with dilute hydrochloric acid and extracted with ethyl acetate. Concentration by evaporation gave 2.1 g of 2-(phenylamino)-2-[4-(trifluoromethyl)phenyl]acetic acid (93%).
（フラーレン誘導体（ＥＨＰＴＦＮＰ）の合成）
２－（フェニルアミノ）－２－［４－（トリフルオロメチル）フェニル］酢酸（３４０ｍｇ，１．４ｍｍｏｌ）、フラーレン（Ｃ６０，７２０ｍｇ，１．０ｍｍｏｌ）、３－エチルヘプタナール（１ｍＬ）のｏ－キシレン（２００ｍＬ）溶液を１５０℃で２４時間加熱撹拌した。溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン＝５０：１）さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ２８ｍｍ×２５０ｍｍ、溶離液：トルエン、１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物６（フラーレン誘導体（ＥＨＰＴＦＮＰ））５３６ｍｇを得た（収率：４９％）。 (Synthesis of fullerene derivative (EHPTFNP))
o- of 2-(phenylamino)-2-[4-(trifluoromethyl)phenyl]acetic acid (340 mg, 1.4 mmol), fullerene (C60, 720 mg, 1.0 mmol), 3-ethylheptanal (1 mL) A xylene (200 mL) solution was heated and stirred at 150° C. for 24 hours. The solvent was concentrated by evaporation, and the resulting reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene = 50:1) and preparative HPLC (column: Buckyprep 28 mm × 250 mm, eluent: toluene, 10 mL /min, detector: RI) to obtain 536 mg of compound 6 (fullerene derivative (EHPTFNP)) (yield: 49%).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
得られた化合物６の分析結果を以下に示す。
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：０．６２（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），０．７５－０．９５（４Ｈ，ｍ），０．９５－１．７０（９Ｈ，ｍ），２．００－２．１０（１Ｈ，ｍ），２．８０－２．９２（１Ｈ，ｍ），５．６５－５．７２（１Ｈ，ｍ），６．３５（１Ｈ，ｓ），７．０３－７．３０（１Ｈ，ｍ），７．２０－７．３０（２Ｈ，ｍ），７．３４（２Ｈ，ｔ，Ｊ＝７．８Ｈｚ），７．５３（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ），７．８３（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ）．
Ｆ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：－６２．３８（ｓ） The analysis results of the obtained compound 6 are shown below.
H-NMR (500MHz, CDCl3 )
δ: 0.62 (2H, t, J = 7.3Hz), 0.75-0.95 (4H, m), 0.95-1.70 (9H, m), 2.00-2.10 (1H, m), 2.80-2.92 (1H, m), 5.65-5.72 (1H, m), 6.35 (1H, s), 7.03-7.30 (1H , m), 7.20-7.30 (2H, m), 7.34 (2H, t, J = 7.8 Hz), 7.53 (2H, d, J = 8.0 Hz), 7.83 (2H, d, J=8.0 Hz).
F-NMR (500 MHz, CDCl 3 ) δ: -62.38 (s)
（化合物７の合成）
２－ブロモフェニル酢酸（２．１５ｇ，１０．０ｍｍｏｌ），アニリン（４．０９ｇ，４４．０ｍｍｏｌ）を、無溶媒で１００℃、７２時間加熱した。冷却後、反応液を酢酸エチルで希釈し、５％水酸化ナトリウムで抽出した。ここで得られた水相を１Ｎ塩酸でｐＨ４とし、酢酸エチルで抽出した。有機相を硫酸マグネシウムで乾燥後、減圧下に濃縮した。得られた粗生成物を水－エタノールで再結晶し、中間体７１を５６０ｍｇ（２４．０％）得た。得られた中間体７１（Ｎ－フェニル－２－フェニルグリシン）（１１２ｍｇ，０．５ｍｍｏｌ），４－エチルヘプタナール（１４２ｍｇ，１ｍｍｏｌ），Ｃ６０フラーレン（３６０ｍｇ，０．５ｍｍｏｌ）のクロロベンゼン溶液（２００ｍＬ）を４８時間加熱還流した。反応生成液を減圧下に濃縮し、反応物をカラムクロマトグラフィー（ＳｉＯ２，ヘキサン－トルエン＝１００：１～２０：１）で精製し、目的とする化合物７を１５４．５ｍｇ（３０．０％）（純度：９９％以上）得た。 (Synthesis of compound 7)
2-Bromophenylacetic acid (2.15 g, 10.0 mmol) and aniline (4.09 g, 44.0 mmol) were heated at 100° C. for 72 hours without solvent. After cooling, the reaction was diluted with ethyl acetate and extracted with 5% sodium hydroxide. The aqueous phase obtained here was adjusted to pH 4 with 1N hydrochloric acid and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and then concentrated under reduced pressure. The resulting crude product was recrystallized with water-ethanol to obtain 560 mg (24.0%) of Intermediate 71. Obtained intermediate 71 (N-phenyl-2-phenylglycine) (112 mg, 0.5 mmol), 4-ethylheptanal (142 mg, 1 mmol), C60 fullerene (360 mg, 0.5 mmol) in chlorobenzene solution (200 mL) was heated to reflux for 48 hours. The reaction product solution was concentrated under reduced pressure, and the reaction product was purified by column chromatography (SiO 2 , hexane-toluene = 100:1 to 20:1) to obtain 154.5 mg (30.0% ) (purity: 99% or more).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
（化合物８の合成）
２－ブロモオクタン酸（１．２８ｇ，５．７４ｍｍｏｌ），アニリン（５３４ｍｇ，５．７４ｍｍｏｌ），炭酸カリウム（８００ｍｇ，５．７４ｍｍｏｌ）のエタノール溶液（３ｍＬ）を４８時間加熱還流した。冷却後、反応生成液を水で薄めて、エーテルで抽出した。さらに、ここで有られた水相を１Ｎ塩酸でｐＨ３に調性し、酢酸エチルで抽出した。有機相を硫酸マグネシウムで乾燥後、減圧下に濃縮し、中間体８１を９８２ｍｇ（７２．８％）得た。中間体８１（２－（フェニルアミノ）－オクタン酸）（１１８ｍｇ，０．５ｍｍｏｌ），ヘプタナール（２ｍＬ），フラーレン（３６０ｍｇ，０．５ｍｍｏｌ）のクロロベンゼン溶液（１５０ｍＬ）を４８時間加熱還流した。反応生成液を減圧下に濃縮し、反応物をカラムクロマトグラフィー（ＳｉＯ２，ヘキサン－トルエン＝１００：１～２０：１）、およびさらにＨＰＬＣ（Ｂｕｃｋｙｐｒｅｐ：トルエン）で精製し、目的とする化合物８を１１３ｍｇ（２２．４％）得た。（純度：９９％以上） (Synthesis of Compound 8)
An ethanol solution (3 mL) of 2-bromooctanoic acid (1.28 g, 5.74 mmol), aniline (534 mg, 5.74 mmol) and potassium carbonate (800 mg, 5.74 mmol) was heated under reflux for 48 hours. After cooling, the reaction product was diluted with water and extracted with ether. Further, the aqueous phase obtained here was adjusted to pH 3 with 1N hydrochloric acid and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and then concentrated under reduced pressure to obtain 982 mg (72.8%) of intermediate 81. A chlorobenzene solution (150 mL) of intermediate 81 (2-(phenylamino)-octanoic acid) (118 mg, 0.5 mmol), heptanal (2 mL), and fullerene (360 mg, 0.5 mmol) was heated under reflux for 48 hours. The reaction product was concentrated under reduced pressure, and the reaction product was purified by column chromatography (SiO 2 , hexane-toluene = 100:1 to 20:1) and further by HPLC (Buckyprep: toluene) to give the target compound 8. 113 mg (22.4%) of (Purity: 99% or more)
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
（化合物９の合成）
側管にガス導入管を装着した容量５０ｍＬの２口フラスコ中に、２－［（３－オクチルフェニル）アミノ］－２－フェニル酢酸（５４ｍｇ，０．２ｍｍｏｌ）、ベンツアルデヒド（２ｍＬ）、フラーレン（Ｃ６０、１４０ｍｇ、０．２ｍｍｏｌ）を入れ、溶媒（ｏ－キシレン）３０ｍＬを加えた。上記溶液をガス導入管から窒素バブリング（１時間）を行い、系中から酸素を除去した。オイルバス中１５０℃（浴温）で１５時間加熱撹拌した。溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン＝５０：１）により、さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ２８ｍｍ×２５０ｍｍ、溶離液：トルエン　１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物９（フラーレン誘導体（ＰＰＮＰＯ））９３ｍｇを得た（収率：４２％）。 (Synthesis of compound 9)
2-[(3-octylphenyl)amino]-2-phenylacetic acid (54 mg, 0.2 mmol), benzaldehyde (2 mL), fullerene ( C60, 140 mg, 0.2 mmol) was added, and 30 mL of solvent (o-xylene) was added. Nitrogen bubbling (1 hour) was performed on the above solution from the gas inlet tube to remove oxygen from the system. The mixture was heated and stirred in an oil bath at 150°C (bath temperature) for 15 hours. The solvent was concentrated by evaporation, and the obtained reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene = 50:1), and further to preparative HPLC (column: Buckyprep 28 mm × 250 mm, eluent: toluene 10 mL/min, detector: RI) to obtain 93 mg of compound 9 (fullerene derivative (PPNPO)) (yield: 42%).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
得られた化合物９の分析結果を以下に示す。
Ｈ－ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ３）
δ：０．９３（３Ｈ，ｔ，Ｊ＝７．３Ｈｚ），１．０６－１．５４（１２Ｈ，ｍ），１．２２－１．４５（１０Ｈ，ｍ），２．４０－２．５６（２Ｈ，ｍ），６．６１（１Ｈ，ｄ，Ｊ＝７．３Ｈｚ），６．９４－７．００（１Ｈ，ｍ），６．９９（１Ｈ，ｓ），７．０４（１Ｈ，ｔ，Ｊ＝７．５Ｈｚ），７．１４（２Ｈ，Ｓ），７．２５（２Ｈ，ｔ，Ｊ＝７．５Ｈｚ），７．３７（４Ｈ，ｔ，Ｊ＝７．６Ｈｚ），７．８４（１Ｈ，ｄ，Ｊ＝７．４Ｈｚ）． The analysis results of the obtained compound 9 are shown below.
H-NMR (600MHz, CDCl3 )
δ: 0.93 (3H, t, J = 7.3Hz), 1.06-1.54 (12H, m), 1.22-1.45 (10H, m), 2.40-2.56 (2H, m), 6.61 (1H, d, J = 7.3 Hz), 6.94-7.00 (1H, m), 6.99 (1H, s), 7.04 (1H, t , J = 7.5 Hz), 7.14 (2H, S), 7.25 (2H, t, J = 7.5 Hz), 7.37 (4H, t, J = 7.6 Hz), 7.84 (1H,d,J=7.4Hz).
（化合物１０の合成）
２－（フェニルアミノ）－２－フェニル］酢酸（３３０ｍｇ，１．５ｍｍｏｌ）、フラーレン（Ｃ６０，７２０ｍｇ，１．０ｍｍｏｌ）、４－トリフルオロメチルベンズアルデヒド（１ｍＬ）のｏ－キシレン（２００ｍＬ）溶液を１５０℃で４８時間加熱撹拌した。溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン＝５０：１）により、さらに分取ＨＰＬＣ（カラム　Ｂｕｃｋｙｐｒｅｐ　２８ｍｍ×２５０ｍｍ、溶離液：トルエン、１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物１０（フラーレン誘導体（ＰＰＴＦＮＰ））３４０ｍｇを得た（収率：３２％）。 (Synthesis of Compound 10)
A solution of 2-(phenylamino)-2-phenyl]acetic acid (330 mg, 1.5 mmol), fullerene (C60, 720 mg, 1.0 mmol), and 4-trifluoromethylbenzaldehyde (1 mL) in o-xylene (200 mL) was added to 150 The mixture was heated and stirred at °C for 48 hours. The solvent was concentrated by evaporation, and the obtained reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene = 50:1), followed by preparative HPLC (column Buckyprep 28mm x 250mm, eluent: toluene , 10 mL/min, detector: RI) to obtain 340 mg of compound 10 (fullerene derivative (PPTFNP)) (yield: 32%).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
得られた化合物１０の分析結果を以下に示す。
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：７．１０（１Ｈ，ｓ），７．１０－７．２０（４Ｈ，ｍ），７．２０（１Ｈ，ｓ），７．２０－７．４０（４Ｈ，ｍ），７．６５（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ），７．８２（２Ｈ，ｄ，７．５Ｈｚ），７．９５（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ）．Ｆ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：－６２．４２（ｓ） The analysis results of the obtained compound 10 are shown below.
H-NMR (500MHz, CDCl3 )
δ: 7.10 (1H, s), 7.10-7.20 (4H, m), 7.20 (1H, s), 7.20-7.40 (4H, m), 7.65 ( 2H, d, J = 8.0 Hz), 7.82 (2H, d, 7.5 Hz), 7.95 (2H, d, J = 8.0 Hz). F-NMR (500 MHz, CDCl 3 ) δ: -62.42 (s)
（化合物１１の合成）
２－（フェニルアミノ）－２－（フェニル）酢酸（１．１８ｇ，４ｍｍｏｌ）、フラーレン（Ｃ６０，１．４４ｇ，２．０ｍｍｏｌ）、ベンズアルデヒド（２ｍＬ）のｏ－キシレン（４００ｍＬ）溶液を１５０℃で２４時間加熱撹拌した。
溶媒をエバポレーションして濃縮し、得られた反応生成物をシリカゲルカラムクロマトグラフィー（溶離液　ｎ－ヘプタン：トルエン＝１００：１）により、さらに分取ＨＰＬＣ（カラム：Ｂｕｃｋｙｐｒｅｐ　２８ｍｍ×２５０ｍｍ、溶離液：トルエン　１０ｍＬ／ｍｉｎ、検出器：ＲＩ）により精製し、化合物１１（１，２，５－トリフェニルピロリジン誘導体（トリフェニルフラーロピロリジン））７０４ｍｇを得た（収率：３３％）。 (Synthesis of Compound 11)
A solution of 2-(phenylamino)-2-(phenyl)acetic acid (1.18 g, 4 mmol), fullerene (C60, 1.44 g, 2.0 mmol) and benzaldehyde (2 mL) in o-xylene (400 mL) at 150°C. The mixture was heated and stirred for 24 hours.
The solvent was concentrated by evaporation, and the obtained reaction product was subjected to silica gel column chromatography (eluent n-heptane: toluene = 100: 1), followed by preparative HPLC (column: Buckyprep 28mm x 250mm, eluent: Toluene 10 mL/min, detector: RI) to obtain 704 mg of compound 11 (1,2,5-triphenylpyrrolidine derivative (triphenylfuraropyrrolidine)) (yield: 33%).
得られた化合物１１の分析結果を以下に示す。
Ｈ－ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）
δ：７．１２－７．２０（３Ｈ，ｍ），７．１４（１Ｈ，ｓ），７．１５（１Ｈ，ｔ，Ｊ＝７．３Ｈｚ），７．２０－７．３０（４Ｈ，ｍ），７．３６（４Ｈ，ｄ－ｄ，Ｊ＝８．１，７．５Ｈｚ），７．８２（４Ｈ，ｄ，Ｊ＝７．５Ｈｚ）． The analytical results of the obtained compound 11 are shown below.
H-NMR (500MHz, CDCl3 )
δ: 7.12-7.20 (3H, m), 7.14 (1H, s), 7.15 (1H, t, J = 7.3 Hz), 7.20-7.30 (4H, m ), 7.36 (4H, dd, J=8.1, 7.5 Hz), 7.82 (4H, d, J=7.5 Hz).
得られた化合物について、以下の試験を行った。 The compounds obtained were subjected to the following tests.
（１）試験用太陽電池の作製
化合物１～１０をｎ型半導体材料として用いて、試験用太陽電池を作製し、変換効率を評価した。ｐ型半導体材料としては、ＰＤＴＰ－ＤＦＢＴ（下記化学式参照）を、電荷輸送層材料としてはＰＦＮ（ポリ［９，９－ビス（３'－（Ｎ，Ｎ－ジメチルアミノ）プロピル－２，７－フルオレン）－ａｌｔ－２，７－（９，９－ジオクチルフルオレン）］）及びＭｏＯ３（酸化モリブデン）を、電極としてはＩＴＯ（酸化インジウムスズ）（陰極）及びアルミニウム（陽極）をそれぞれ用いた。 (1) Preparation of test solar cells Using Compounds 1 to 10 as n-type semiconductor materials, test solar cells were prepared and their conversion efficiencies were evaluated. As the p-type semiconductor material, PDTP-DFBT (see the chemical formula below) is used, and as the charge transport layer material, PFN (poly[9,9-bis(3′-(N,N-dimethylamino)propyl-2,7- fluorene)-alt-2,7-(9,9-dioctylfluorene)]) and MoO3 (molybdenum oxide), and ITO (indium tin oxide) (cathode) and aluminum (anode) as electrodes, respectively.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
（１－１）基板の前処理
プラズマ洗浄機で、酸素ガスを流入しながら、発生したプラズマにより、ＩＴＯパターニングガラス板の基板表面を、１０分間洗浄処理した。 (1-1) Pretreatment of Substrate The substrate surface of the ITO patterned glass plate was cleaned for 10 minutes with generated plasma while oxygen gas was introduced in a plasma cleaner.
（１－２）陰極側電荷輸送層の作製
スピンコート法製膜装置を用い、ＰＦＮメタノール溶液（２％w／v）を用いて、前処理を施したＩＴＯガラス板上に、ＰＦＮ薄膜を形成した。形成されたＰＦＮ薄膜の膜厚は約１０ｎｍであった。 (1-2) Preparation of Cathode Side Charge Transport Layer A PFN thin film was formed on an ITO glass plate pretreated with a PFN methanol solution (2% w/v) using a spin coating film forming apparatus. . The film thickness of the formed PFN thin film was about 10 nm.
（１－３）有機半導体膜（有機発電層）の作製
得られた化合物１～１０、ＰＤＴＰ－ＤＦＢＴをオルトキシレンに溶かし、有機半導体膜形成用オルトキシレン溶液１～１０を得た。
グローブボックス中で、スピンコート法製膜装置を用い、得られた陰極側電荷輸送層を有する基板に、有機半導体膜形成用オルトキシレン溶液１～１０をスピンコート（１０００ｒｐｍ、２分間）し、厚さ約９０～１１０ｎｍの有機半導体薄膜（有機発電層）を形成し、積層体を得た。 (1-3) Preparation of organic semiconductor film (organic power generation layer) Compounds 1 to 10 and PDTP-DFBT thus obtained were dissolved in ortho-xylene to obtain ortho-xylene solutions 1 to 10 for forming organic semiconductor films.
In a glove box, using a spin-coating film forming apparatus, the substrate having the cathode-side charge transport layer obtained was spin-coated with ortho-xylene solutions 1 to 10 for forming an organic semiconductor film (1000 rpm, 2 minutes), and the thickness was An organic semiconductor thin film (organic power generation layer) having a thickness of about 90 to 110 nm was formed to obtain a laminate.
（１－４）陽極側電荷輸送層及び金属電極の真空蒸着
得られた積層体に、小型高真空蒸着装置を用い、陽極側電荷輸送層としてのＭｏＯ３層（１０ｎｍ）、及び金属電極としてのアルミニウム層（８０ｎｍ）を順次蒸着し、試験用太陽電池１～１０を得た。 (1-4) Vacuum deposition of anode-side charge-transporting layer and metal electrode The resulting laminate was coated with a small high-vacuum deposition apparatus to form MoO 3 layers (10 nm) as the anode-side charge-transporting layer and a metal electrode as a metal electrode. Aluminum layers (80 nm) were sequentially deposited to obtain test solar cells 1-10.
（２）疑似太陽光照射を用いた、試験用太陽電池の変換効率の評価
得られた試験用太陽電池に、擬似太陽光を照射し変換効率を求めた。電流測定には、ソースメーター、電流電圧計測ソフト及び疑似太陽光照射装置を用いた。得られた各試験用太陽電池１～１０に対して、１００ｍＷの疑似太陽光を照射して、発生した電流と電圧を測定して、以下の式によりエネルギー変換効率を算出した。結果を表に示す。
変換効率η（％）＝ＦＦ（Ｖｏｃ×Ｊｓｃ／Ｐｉｎ）×１００
ＦＦ：曲線因子、Ｖｏｃ：開放電圧、Ｊｓｃ：短絡電流、Ｐｉｎ：入射光強度（密度） (2) Evaluation of Conversion Efficiency of Test Solar Cell Using Pseudo-Sunlight Irradiation The obtained test solar cell was irradiated with pseudo-sunlight to determine the conversion efficiency. A source meter, current/voltage measurement software, and a simulated sunlight irradiation device were used for current measurement. Each of the obtained test solar cells 1 to 10 was irradiated with 100 mW of simulated sunlight, the generated current and voltage were measured, and the energy conversion efficiency was calculated by the following equation. The results are shown in the table.
Conversion efficiency η (%) = FF (Voc x Jsc/Pin) x 100
FF: fill factor, Voc: open circuit voltage, Jsc: short circuit current, Pin: incident light intensity (density)
（３）試験用太陽電池の加熱試験
得られた各試験用太陽電池１～１０を、窒素雰囲気中、８５℃で２時間加熱した。 (3) Heating test of test solar cells Each of the obtained test solar cells 1 to 10 was heated at 85°C for 2 hours in a nitrogen atmosphere.
（４）加熱後の試験用太陽電池の変換効率の評価
加熱試験後の試験用太陽電池１～１０について、（２）と同様の方法で、変換効率の評価を行った。結果を表に示す。 (4) Evaluation of Conversion Efficiency of Test Solar Cells After Heating The conversion efficiencies of the test solar cells 1 to 10 after the heating test were evaluated in the same manner as in (2). The results are shown in the table.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
（５）トルエン溶解度
紫外可視吸光光度計を用いて吸光度を測定することにより、トルエン溶解度を算出した。吸光度測定できる吸光度により算出した。まず、濃度既知のフラーレン誘導体のトルエン溶液を用いてモル吸光係数を求めた。次に、フラーレン誘導体の過飽和トルエン溶液の上澄み溶液を一定量秤量し、これの吸光度を測定した。以下の式に従い、濃度を算出した。
　　Ｃ＝Ａ／εｄ
［式中、Ｃ：濃度、Ａ：吸光度、ε：モル吸光係数、ｄ：吸光度測定用セル長（１ｃｍ）］ (5) Toluene solubility Toluene solubility was calculated by measuring the absorbance using a UV-visible spectrophotometer. It was calculated from the absorbance that can be measured. First, the molar extinction coefficient was obtained using a toluene solution of a fullerene derivative with a known concentration. Next, a certain amount of the supernatant solution of the supersaturated toluene solution of the fullerene derivative was weighed and the absorbance thereof was measured. Concentration was calculated according to the following formula.
C=A/εd
[In the formula, C: concentration, A: absorbance, ε: molar extinction coefficient, d: cell length for absorbance measurement (1 cm)]
結果を以下に示す。
・化合物２（ＰＰＴＦＮＰＯ）：２．５質量％
・化合物３（ＰＰＮＰＯ）：１．２質量％
・化合物１０（ＰＰＴＦＮＰ）：１．５質量％
一方、Ｒ１、Ｒ２、及びＲ３がすべてフェニル基であるフラーレン誘導体である、化合物１１（１，２，５－トリフェニルピロリジン誘導体（トリフェニルフラーロピロリジン））のトルエン溶解度は、０．４質量％であった。
１，２，５－トリフェニルピロリジン誘導体の溶解度は不十分で、塗布型光電変換素子を作製するには課題を有するが、ここのフェニル基に長鎖アルキル基の導入、或いは炭素１個では有るがフッ素を有するＣＦ３基の導入により溶解度が向上している。 The results are shown below.
・Compound 2 (PPTFNPO): 2.5% by mass
- Compound 3 (PPNPO): 1.2% by mass
・Compound 10 (PPTFNP): 1.5% by mass
On the other hand, the toluene solubility of Compound 11 (1,2,5-triphenylpyrrolidine derivative (triphenylfulleropyrrolidine)), which is a fullerene derivative in which R 1 , R 2 and R 3 are all phenyl groups, is 0.5. It was 4% by mass.
The solubility of the 1,2,5-triphenylpyrrolidine derivative is insufficient, and there is a problem in producing a coating-type photoelectric conversion element, but introduction of a long-chain alkyl group to the phenyl group here, or one carbon is sufficient. has improved solubility due to the introduction of CF3 groups with fluorine.
また、式（１）において、Ｒ１、Ｒ２、及びＲ３がすべてフェニル基であるフラーレン誘導体のＬＵＭＯ準位が、－３．６７ｅＶである。さらにはメタ位に電子供与基、又は、オルト位及び／又はパラ位に電子求引基を有する化合物２～６のフラーレン誘導体は、ＬＵＭＯ準位が、－３．６７ｅＶ未満である。 Also, in formula (1), the LUMO level of a fullerene derivative in which R 1 , R 2 and R 3 are all phenyl groups is −3.67 eV. Furthermore, fullerene derivatives of compounds 2 to 6 having an electron donating group at the meta position or an electron withdrawing group at the ortho and/or para positions have a LUMO level of less than -3.67 eV.

Claims (12)

  1. 下記式（１）で表されるフラーレン誘導体。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、
    　Ｒ１は、１個以上の置換基を有していてもよいアリール基を表し、
    　Ｒ２は、有機基を表し、
    　Ｒ３は、有機基を表し、
    　Ｒ２及びＲ３のうち少なくとも一方が、１個以上の置換基を有していてもよいアリール基を表し、
    　環Ａは、フラーレン環を表し、
    　式（１）は、下記の２つの条件のうち、少なくともいずれか１つを満たす。
    　ｉ）Ｒ１、Ｒ２、及び、Ｒ３が１個以上の置換基を有していてもよいアリール基であり、かつ、Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、置換基を有するアリール基である。
    　ｉｉ）Ｒ２及び／又はＲ３がフッ素含有置換基を有するアリール基である。）     A fullerene derivative represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (In formula (1),
    R 1 represents an aryl group optionally having one or more substituents,
    R 2 represents an organic group,
    R 3 represents an organic group,
    at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents;
    Ring A represents a fullerene ring,
    Formula (1) satisfies at least one of the following two conditions.
    i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group.
    ii) R2 and/or R3 are aryl groups with fluorine-containing substituents; )
  2. 式（１）において、
    Ｒ１が置換基を有しないアリール基、又は、１個以上の置換基を有するアリール基であって、
    Ｒ１が１個以上の置換基を有するアリール基である場合に、Ｒ１に含まれるアリール基が有する置換基を第１の置換基とすると、
    前記第１の置換基が、１個以上の置換基を有していてもよいアルキル基、及び、１個以上の置換基を有していてもよいアラルキル基からなる群から選択される少なくとも１つを含む、請求項１に記載のフラーレン誘導体。     In formula (1),
    R 1 is an unsubstituted aryl group or an aryl group with one or more substituents,
    When R 1 is an aryl group having one or more substituents, and the substituent of the aryl group contained in R 1 is the first substituent,
    The first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents The fullerene derivative of claim 1, comprising
  3. 式（１）において、
    Ｒ１、Ｒ２、及び、Ｒ３のうち少なくともいずれ一つが、メタ位に電子供与基を有するアリール基であり、及び／又は、
    Ｒ２、及び、Ｒ３のうち少なくともいずれ一つが、オルト位及び／又はパラ位に電子求引基を有するアリール基
    である、請求項１又は請求項２に記載のフラーレン誘導体。     In formula (1),
    at least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position; and/or
    3. The fullerene derivative according to claim 1, wherein at least one of R2 and R3 is an aryl group having an electron-withdrawing group at the ortho-position and/or para-position.
  4. 式（１）において、
    Ｒ１、Ｒ２、及び、Ｒ３のうち少なくとも１つが、１個以上の置換基を有していてもよいアルキル基を含み、前記アルキル基が、炭素数４以上１２以下の、直鎖又は分岐アルキル基である、請求項１又は請求項２に記載のフラーレン誘導体。     In formula (1),
    At least one of R 1 , R 2 , and R 3 contains an alkyl group optionally having one or more substituents, and the alkyl group has 4 to 12 carbon atoms, linear or 3. The fullerene derivative according to claim 1, which is a branched alkyl group.
  5. 式（１）において、
    Ｒ２、及び、Ｒ３のうち少なくとも１つが、フッ素原子及び炭素数が２以下のフッ化アルキル基のうちいずれか１つを含む、請求項１又は請求項２に記載のフラーレン誘導体。     In formula (1),
    3. The fullerene derivative according to claim 1, wherein at least one of R2 and R3 contains any one of a fluorine atom and a fluorinated alkyl group having 2 or less carbon atoms.
  6. ＬＵＭＯ準位の値が－３．６７ｅＶ未満であり、トルエン溶解度が０．５％以上である、請求項１又は請求項２に記載のフラーレン誘導体。 3. The fullerene derivative according to claim 1, which has a LUMO level value of less than −3.67 eV and a toluene solubility of 0.5% or more.
  7. 請求項１又は請求項２に記載のフラーレン誘導体を含む、ｎ型半導体材料。 An n-type semiconductor material comprising the fullerene derivative according to claim 1 or 2.
  8. 請求項７に記載のｎ型半導体材料、及び、ｐ型半導体材料を含有する有機発電層。 An organic power generating layer containing the n-type semiconductor material according to claim 7 and a p-type semiconductor material.
  9. 請求項８に記載の有機発電層を備える光電変換素子。 A photoelectric conversion device comprising the organic power generation layer according to claim 8 .
  10. 有機薄膜太陽電池である、請求項９に記載の光電変換素子。 The photoelectric conversion device according to claim 9, which is an organic thin film solar cell.
  11. 光センサーである、請求項９に記載の光電変換素子。 10. The photoelectric conversion device according to claim 9, which is an optical sensor.
  12. 初期エネルギー変換効率に対する８５℃で２時間加熱後のエネルギー変換効率の低下が５％以内である、請求項９に記載の光電変換素子。 10. The photoelectric conversion device according to claim 9, wherein the decrease in energy conversion efficiency after heating at 85[deg.] C. for 2 hours with respect to the initial energy conversion efficiency is within 5%.
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Publication number Priority date Publication date Assignee Title
JP2014218492A (en) * 2012-07-17 2014-11-20 株式会社リコー Fullerene derivative and method for producing the same
WO2014185536A1 (en) * 2013-05-16 2014-11-20 ダイキン工業株式会社 Fullerene derivative and n-type semiconductor material
JP2015113301A (en) * 2013-12-11 2015-06-22 株式会社リコー Fullerene derivative and method of producing the same
WO2017061543A1 (en) * 2015-10-06 2017-04-13 ダイキン工業株式会社 FULLERENE DERIVATIVE AND n-TYPE SEMICONDUCTOR MATERIAL

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014218492A (en) * 2012-07-17 2014-11-20 株式会社リコー Fullerene derivative and method for producing the same
WO2014185536A1 (en) * 2013-05-16 2014-11-20 ダイキン工業株式会社 Fullerene derivative and n-type semiconductor material
JP2015113301A (en) * 2013-12-11 2015-06-22 株式会社リコー Fullerene derivative and method of producing the same
WO2017061543A1 (en) * 2015-10-06 2017-04-13 ダイキン工業株式会社 FULLERENE DERIVATIVE AND n-TYPE SEMICONDUCTOR MATERIAL

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