JP7125702B2 - fullerene derivative - Google Patents

Description

The present invention relates to fullerene derivatives.

An organic thin-film solar cell uses an organic compound as a photoelectric conversion material and is formed by a coating method from a solution.
1) low cost in device fabrication;
2) it is easy to increase the area;
3) it is more flexible than inorganic materials such as silicon and can be used in a wider range of places;

Therefore, research and development of organic thin-film solar cells have been actively carried out until now.
However, even considering the above advantages, organic thin-film solar cells are inferior to inorganic thin-film solar cells currently in widespread use in terms of performance (e.g., photoelectric conversion efficiency) and manufacturing costs. There is still room for improvement, and therefore vigorous research and development of new organic thin-film solar cells continues through various approaches.
As a representative example of such an approach, Patent Document 1 proposes a solar cell using a C70 fullerene derivative that can absorb energy on the longer wavelength side of sunlight than C60 fullerene.

Japanese Patent Laid-Open No. 2009-076683

However, derivatives of C70 fullerene are expensive to produce, mainly due to the high price of C70 fullerene.
Therefore, it is desirable to provide a new C60 fullerene derivative that can be produced using the C60 derivative that is advantageous in terms of production cost of the present invention and that enables the production of an organic thin film solar cell with high photoelectric conversion efficiency. aim.

［式中、
Ｒ^１１は、１個以上の置換基を有していてもよいフェニル基であり、
Ｒ^１２は、各オルト位に、同一又は異なって、Ｃ３－Ｃ１２アルキル基、又はＣ３－１２アルコキシ基を有し、及び更に１～３個の置換基を有していてもよい、フェニル基であり、
Ｒ^１３は、
（１）水素、又は
（２）１個以上の置換基を有していてもよい直鎖状又は分岐状の脂肪族基であり、及び
環Ａは、Ｃ６０フラーレン環を表す。］
で表されるフラーレン誘導体を含有する、フラーレン誘導体
によって、前記課題が解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found formula (1):

[In the formula,
R ¹¹ is a phenyl group optionally having one or more substituents,
R ¹² is a phenyl group having the same or different C3-C12 alkyl group or C3-12 alkoxy group at each ortho position and optionally having 1 to 3 substituents; can be,
^R13 is
(1) hydrogen, or (2) a linear or branched aliphatic group optionally having one or more substituents, and ring A represents a C60 fullerene ring. ]
The present inventors have found that the above problems can be solved by a fullerene derivative containing a fullerene derivative represented by and have completed the present invention.

The present invention includes the following aspects.

［式中、
Ｒ^１１は、１個以上の置換基を有していてもよいフェニル基であり、
Ｒ^１２は、各オルト位に、同一又は異なって、Ｃ３－Ｃ１２アルキル基、又はＣ３－１２アルコキシ基を有し、及び更に１～３個の置換基を有していてもよい、フェニル基であり、
Ｒ^１３は、
（１）水素、又は
（２）１個以上の置換基を有していてもよい直鎖状又は分岐状の脂肪族基であり、及び
環Ａは、Ｃ６０フラーレン環を表す。］
で表されるフラーレン誘導体を含有する、フラーレン誘導体。
項２．
Ｒ^１１は、フェニル基である、項１に記載のフラーレン誘導体。
項３．
Ｒ^１２は、各オルト位に、Ｃ３－Ｃ１２アルキル基、又はＣ３－１２アルコキシ基を有し、及び更に１～３個の置換基を有していてもよいフェニル基である、項１又は２に記載のフラーレン誘導体。
項４．
Ｒ^１２は、各オルト位に、Ｃ３－Ｃ１２アルキル基、又はＣ３－１２アルコキシ基を有し、及び更に１～３個の置換基を有するフェニル基である、項１又は２に記載のフラーレン誘導体。
項５．
Ｒ^１２は、各オルト位に、互いに同一の置換基を有するフェニル基である、項１～４のいずれか一項に記載のフラーレン誘導体。
項６．
４５０～５５０ｎｍの全波長領域にわたって２０００以上の光吸収係数を有する、項１～４のいずれか一項に記載のフラーレン誘導体。
項７．
項１～６のいずれか一項に記載のフラーレン誘導体を含有するｎ型半導体材料。
項８．
光電変換用である、項７に記載のｎ型半導体材料。
項９．
項８に記載の型半導体材料を含有する光電変換層。
項１０．
項９に記載の光電変換層を含有する光電変換素子。
項１１．
項９に記載の光電変換層を含有する有機薄膜太陽電池。
項１２．
項９に記載の光電変換層を含有する光センサー。
項１３．
項１～６のいずれか一項に記載のフラーレン誘導体を含有するペロブスカイト太陽電池。
項１４．
項１～６のいずれか一項に記載のフラーレン誘導体を含有する組成物。 Section 1.
Formula (1):

[In the formula,
R ¹¹ is a phenyl group optionally having one or more substituents,
R ¹² is a phenyl group having the same or different C3-C12 alkyl group or C3-12 alkoxy group at each ortho position and optionally having 1 to 3 substituents; can be,
^R13 is
(1) hydrogen, or (2) a linear or branched aliphatic group optionally having one or more substituents, and ring A represents a C60 fullerene ring. ]
A fullerene derivative containing a fullerene derivative represented by
Section 2.
Item 2. The fullerene derivative according to Item 1, wherein R ¹¹ is a phenyl group.
Item 3.
Item 1 or 2, wherein R ¹² is a phenyl group having a C3-C12 alkyl group or a C3-12 alkoxy group at each ortho position and optionally having 1 to 3 substituents. The fullerene derivative described in .
Section 4.
Item 3. The fullerene derivative according to Item 1 or 2, wherein R ¹² is a phenyl group having a C3-C12 alkyl group or a C3-12 alkoxy group at each ortho position and further having 1 to 3 substituents. .
Item 5.
Item 5. The fullerene derivative according to any one of items 1 to 4, wherein R ¹² is a phenyl group having the same substituent at each ortho position.
Item 6.
Item 5. The fullerene derivative according to any one of Items 1 to 4, which has a light absorption coefficient of 2000 or more over the entire wavelength range of 450 to 550 nm.
Item 7.
An n-type semiconductor material containing the fullerene derivative according to any one of Items 1 to 6.
Item 8.
Item 8. The n-type semiconductor material according to item 7, which is for photoelectric conversion.
Item 9.
Item 9. A photoelectric conversion layer containing the type semiconductor material according to item 8.
Item 10.
Item 10. A photoelectric conversion device comprising the photoelectric conversion layer according to Item 9.
Item 11.
Item 9. An organic thin-film solar cell comprising the photoelectric conversion layer according to item 9.
Item 12.
Item 10. An optical sensor comprising the photoelectric conversion layer according to item 9.
Item 13.
A perovskite solar cell containing the fullerene derivative according to any one of Items 1 to 6.
Item 14.
A composition containing the fullerene derivative according to any one of Items 1 to 6.

It is an object of the present invention to provide a new C60 fullerene derivative that can be manufactured using a C60 derivative that is advantageous in terms of manufacturing cost and that enables the manufacture of an organic thin film solar cell with high photoelectric conversion efficiency. do.

1 is an ultraviolet-visible absorption spectrum chart of a fullerene derivative (Synthesis Example 1). 1 is an ultraviolet-visible absorption spectrum chart of a fullerene derivative (Synthesis Example 2). 4 is an ultraviolet-visible absorption spectrum chart of a fullerene derivative (Synthesis Example 3) (Comparative Example). 4 is an ultraviolet-visible absorption spectrum chart of a fullerene derivative (Synthesis Example 4) (Comparative Example).

Terms Symbols and abbreviations used in the present specification can be understood as meanings commonly used in the technical field to which the present invention belongs, in accordance with the context of the present specification, unless otherwise specified.
As used herein, the phrase "comprising" is intended to encompass the phrase "consisting essentially of" and the phrase "consisting of".
Unless otherwise limited, any step, treatment, or operation described herein may be performed at room temperature.
Herein room temperature can mean a temperature within the range of 10-40°C.
In the present specification, the notation "Cn-Cm" (where n and m are numbers, respectively) means that the number of carbon atoms is n or more and m or less, as is commonly understood by those skilled in the art. represents

In this specification, unless otherwise specified,
Examples of "halo" are
fluoro (group), chloro (group), bromo (group), and iodo (group)
can include
In this specification, unless otherwise specified,
Examples of "halogen (atom)" include fluorine (atom), chlorine (atom), bromine (atom), and iodine (atom)
can include

In this specification, unless otherwise specified,
"Organic group" means
Groups containing one or more carbon atoms (or groups formed by removing one hydrogen atom from an organic compound)
can mean

In this specification, unless otherwise specified,
A "heteroatom" is
Atoms other than hydrogen and carbon can be meant.

In this specification, unless otherwise specified,
Examples of "heteroatoms" are
nitrogen (atomic), oxygen (atomic), and sulfur (atomic)
can include

In this specification, unless otherwise specified,
"Organic group" means
It may refer to a group containing one or more carbon atoms as its constituent atoms.

In this specification, unless otherwise specified,
Examples of "organic groups" are
(1) a hydrocarbon group (which may have one or more substituents),
(2) a hydrocarbon group into which one or more heteroatoms are inserted (which may have one or more substituents);
can include

In this specification, unless otherwise specified,
Examples of such substituents are
Halo, nitro, cyano, oxo, thioxo, sulfo, sulfamoyl, sulfinamoyl, sulfenamoyl, and amino optionally having one or two substituents may be included.

In this specification, unless otherwise specified,
A "hydrocarbon group" (or hydrocarbyl group) is
It may refer to a group containing one or more carbon atoms and one or more hydrogen atoms as its constituent atoms.

In this specification, unless otherwise specified,
"Insertion" of a heteroatom or the like into a hydrocarbon group can mean insertion within it or at its cohesive end to the mother nucleus.

In this specification, unless otherwise specified,
Examples of the above "(1) hydrocarbon group" are
Aliphatic hydrocarbon groups optionally substituted with one or more aromatic hydrocarbon groups (e.g., benzyl group), and aromatic hydrocarbon groups optionally substituted with one or more aliphatic hydrocarbon groups (aryl group).

In this specification, unless otherwise specified,
Examples of the above "(2) a hydrocarbon group into which one or more heteroatoms are inserted" are
Alkoxy groups, ether groups, and heterocyclic groups may be included.

In this specification, unless otherwise specified,
The structure of the "aliphatic hydrocarbon group" is
It may include linear, branched, cyclic, or combinations thereof.

In this specification, unless otherwise specified,
"Aliphatic hydrocarbon group"
It can be saturated or unsaturated.

In this specification, unless otherwise specified,
Examples of "aliphatic hydrocarbon groups" are
Alkyl groups, alkenyl groups, alkynyl groups, and cycloalkyl groups can be included.

In this specification, unless otherwise specified,
Examples of "alkyl groups" are
Linear or branched C 1-10 alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl)
can include

In this specification, unless otherwise specified,
Examples of "alkenyl groups" are
Linear or branched alkenyl groups having 1 to 10 carbon atoms (e.g. vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl -1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl, etc. )
can include

In this specification, unless otherwise specified,
Examples of "alkynyl groups" are
A linear or branched alkynyl group having 2 to 6 carbon atoms (e.g., ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3- pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl)
can include

In this specification, unless otherwise specified,
Examples of "cycloalkyl groups" are
cycloalkyl groups having 3 to 8 carbon atoms (eg, cyclopentyl, cyclohexyl, and cycloheptyl)
can include

In this specification, unless otherwise specified,
Examples of "aromatic hydrocarbon group (aryl group)" are
Phenyl, naphthyl, phenanthryl, anthryl, and pyrenyl groups can be included.

In this specification, unless otherwise specified,
Examples of "alkoxy group" are
A group represented by RO-- (wherein R is an alkyl group) may be included.

In this specification, unless otherwise specified,
An "ester group" is
It can refer to an organic group having an ester bond (ie, -C(=O)-O-, or -O-C(=O)-).

In this specification, unless otherwise specified,
Examples of "ester groups" are
(1) Formula: a group represented by RCO ₂ — (wherein R is an alkyl group), and (2) Formula: R ^a —CO ₂ —R ^b — (wherein R ^a is is an alkyl group, and R ^b is an alkylene group.).

In this specification, unless otherwise specified,
An "ether group" is
A group (preferably an organic group) having one or more ether bonds (--O--)
can mean

That is, unless otherwise specified in this specification,
Examples of "ether groups" are
Hydrocarbyl-O-hydrocarbyl groups, and polyether groups may be included.

In this specification, unless otherwise specified,
Polyether group means a group (preferably an organic group) having two or more ether bonds (-O-),
and examples of which are
(1) monovalent, of the formula: R ^a —(O—R ^b ) _n — (wherein R ^a is an alkyl group, R ^b is the same or different at each occurrence and is an alkylene group, and n is an integer of 2 or more.), and (2) a divalent group represented by the formula: —R ^b —(OR ^b ) _n — (wherein R ^b is each occurrence are the same or different, are alkylene groups, and n is an integer of 2 or more.).

In this specification, unless otherwise specified,
Alkylene groups are
It may be a divalent group formed by removing one hydrogen atom from the alkyl group.

In this specification, unless otherwise specified,
Examples of "ether groups" are
It also includes hydrocarbyl ether groups.

In this specification, unless otherwise specified,
A "hydrocarbyl ether group" is
It can refer to a hydrocarbon radical having one or more ether linkages.

In this specification, unless otherwise specified,
"Hydrocarbyl group having one or more ether bonds"
It can be a hydrocarbyl group into which one or more ether linkages are inserted.

In this specification, unless otherwise specified,
Examples may include benzyloxy groups.

In this specification, unless otherwise specified,
Examples of "a hydrocarbon group having one or more ether bonds" are
Alkyl groups having one or more ether linkages may be included.

In this specification, unless otherwise specified,
"Alkyl group having one or more ether bonds"
It can be an alkyl group into which one or more ether linkages are inserted.
In this specification, such groups may be referred to as alkyl ether groups.

In this specification, unless otherwise specified,
Examples of "acyl groups" are
Alkanoyl groups may be included.

In this specification, unless otherwise specified,
Examples of "alkanoyl group" are
A group represented by RCO- (wherein R is an alkyl group) may be included.

In this specification, unless otherwise specified,
Examples of the "5-membered heteroaryl group" are
A 5-membered heteroaryl group having one or more (eg, 1, 2, or 3) heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen as ring-constituting atoms [eg,
pyrrolyl (e.g. 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl),
Furyl (e.g. 2-furyl, 3-furyl),
thienyl (e.g. 2-thienyl, 3-thienyl),
pyrazolyl (e.g. 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl),
imidazolyl (e.g. 1-imidazolyl, 2-imidazolyl, 4-imidazolyl),
isoxazolyl (e.g. 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl),
oxazolyl (e.g. 2-oxazolyl, 4-oxazolyl, 5-oxazolyl),
isothiazolyl (e.g. 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl),
thiazolyl (e.g. 2-thiazolyl, 4-thiazolyl, 5-thiazolyl),
triazolyl (e.g. 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl),
oxadiazolyl (e.g. 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl),
Thiadiazolyl (e.g. 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl)]
can include

Examples of aliphatic groups herein are:
(1) aliphatic hydrocarbon groups; and (2) aliphatic hydrocarbon groups with one or more heteroatoms inserted therein.

［式中、
Ｒ^１１は、１個以上の置換基を有していてもよいフェニル基であり、
Ｒ^１２は、各オルト位に、同一又は異なって、Ｃ３－Ｃ１２アルキル基、又はＣ３－１２アルコキシ基を有し、及び更に１～３個の置換基を有していてもよい、フェニル基であり、
Ｒ^１３は、
（１）水素、又は
（２）１個以上の置換基を有していてもよい直鎖状又は分岐状の脂肪族基
であり、及び
環Ａは、Ｃ６０フラーレン環を表す。］
で表されるフラーレン誘導体
である。 Fullerene Derivative The fullerene derivative of the present invention is
Formula (1):

[In the formula,
R ¹¹ is a phenyl group optionally having one or more substituents,
R ¹² is a phenyl group having the same or different C3-C12 alkyl group or C3-12 alkoxy group at each ortho position and optionally having 1 to 3 substituents; can be,
^R13 is
(1) hydrogen, or (2) a linear or branched aliphatic group optionally having one or more substituents, and ring A represents a C60 fullerene ring. ]
is a fullerene derivative represented by

で表す場合がある。 In this specification, the C60 fullerene ring is represented by the following structural formula, as is often done in the technical field:

may be represented by

R ¹¹ is preferably halo;
nitro;
Cyano;
Oxo;
Thioxo;
Sulfo;
sulfamoyl;
sulfinamoyl;
sulfenamoyl; and phenyl optionally having one or more substituents selected from the group consisting of organic groups.
The number of such substituents can be 1, 2, 3, 4, or 5.
The position of the one or more substituents can independently be ortho, meta, or para.

R ¹¹ is more preferably a phenyl group.

R ¹² is preferably a phenyl group having a C3-C12 alkyl group or a C3-12 alkoxy group at each ortho position and optionally having 1 to 3 substituents.

R ¹² is more preferably a phenyl group having a C6-C12 alkyl group or a C8-C12 alkoxy group at each ortho position and further optionally having 1 to 3 substituents.

R ¹² preferably has no unsubstitutions other than at the ortho position.
That is, R ¹² is preferably a phenyl group having a C3-C12 alkyl group or a C3-12 alkoxy group at each ortho position and further having 1 to 3 substituents.

R ¹² is preferably a phenyl group having mutually identical substituents at each ortho position

The fullerene derivative of the present invention preferably has a light absorption coefficient of 2000 or more over the entire wavelength range of 450-550 nm.
The fullerene derivative of the present invention more preferably has a light absorption coefficient of 2200 or more over the entire wavelength range of 450-550 nm.

^R13 is
(1) hydrogen or (2) a linear or branched aliphatic group optionally having one or more substituents.
Preferred examples of such substituents include halogen atoms, hydroxy groups and ether groups.
A suitable number and type of the substituents are
for example,
1 to 8 (preferably 2 to 4) halogen atoms,
There can be 1-4 (preferably 0-1) hydroxy groups, or 1-4 (preferably 1-2) ether groups, or combinations thereof.
Method for producing fullerene derivative
The fullerene derivative of the present invention can be produced by a known fullerene derivative production method or a method based thereon.
Specifically, the fullerene derivative of the present invention can be synthesized, for example, according to the scheme shown below.
Symbols in the schemes have the same meanings as above, and as is obvious to those skilled in the art, each symbol in formulas (a) and (b) corresponds to each symbol in formula (1).

<Process A>
In step A, a glycine derivative [compound (b)] is reacted with an aldehyde compound [compound (a)] and C60 fullerene [compound (c)] to obtain a fullerene derivative represented by formula (1) (compound (1) ).

The amount ratio of the aldehyde compound [compound (a)], glycine derivative [compound (b)] and fullerene [compound (c)] is arbitrary, but from the viewpoint of increasing the yield, usually fullerene [compound (c)] 1 The aldehyde compound [compound (a)] and the glycine derivative [compound (b)] are each used in an amount of 0.1 to 10 mol, preferably 0.5 to 2 mol, per mol.

The reaction is carried out without solvent or in a solvent.
Examples of the solvent include carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like. Among them, chloroform, toluene, xylene, chlorobenzene and the like are preferable. These solvents may be mixed in an appropriate ratio and used.

The reaction temperature is usually in the range of room temperature to about 150°C, preferably in the range of about 80 to about 120°C. The room temperature here can preferably be in the range from 15 to 30.degree.

The reaction time is generally within the range of about 1 hour to about 4 days, preferably within the range of about 10 to about 48 hours.

The obtained compound (1) can be purified by a conventional purification method, if necessary.
For example, the obtained compound (1) is purified by silica gel column chromatography (preferable developing solvent is, for example, hexane-chloroform, hexane-toluene, or hexane-carbon disulfide), and then further purified by HPLC ( Preparative GPC) (preferable developing solvent is, for example, chloroform or toluene).

The aldehyde compound [compound (a)], glycine derivative [compound (b)] and fullerene [compound (c)] used in the step A are each known compounds, and are prepared by known methods or according to the same. method or commercially available.

<Method for Synthesizing Raw Aldehyde Compound [Compound (a)]>
Specifically, the aldehyde compound [compound (a)] can be synthesized, for example, by methods (a1), (a2), or (a3) described below.
In the reaction formulas showing these methods, R ¹² has the same definition as R ¹² in the above formula (1) and corresponds to R ¹² of the target fullerene derivative.

Method (a1): Oxidation of Alcohol Represented by R ¹² —CH ₂ OH Oxidation in this method includes known methods such as (i) a method using chromic acid, manganese oxide, etc. as an oxidizing agent, and (ii) Swern oxidation using dimethylsulfoxide as an oxidizing agent, or (iii) a method of oxidation using hydrogen peroxide, oxygen, air, etc. in the presence of a catalyst, or the like can be applied.

Method (a2): Reduction of a carboxylic acid represented by R ¹² —COOH, its acid halide, its ester, or its acid amide. A method using a hydride, (ii) a method of hydrogen reduction in the presence of a catalyst, or (iii) a method using hydrazine as a reducing agent can be applied.

Method (a3): Carbonylation of a halide represented by R ¹² -X (X represents a halogen). A method of introducing a carbonyl group into this can be applied. As the carbonyl group-introducing reagent here, N,N-dimethylformamide (DMF); or an amide compound such as an N-formyl derivative of piperidine, morpholine, piperazine or pyrrolidine is used.

In particular, a benzaldehyde derivative having an ortho-positioned alkoxy group can be easily synthesized according to a known method (F. Diederich et al., Chem. Eur. J., 2009, vol. 15, p. 125).

<Method for Synthesizing Raw Glycine Derivative [Compound (b)]>
Specifically, the glycine derivative [compound (b)] can be synthesized, for example, by method (b1), method (b2), or method (b3) described below.
In the reaction formulas showing these methods, R ¹¹ and R ¹³ have the same meanings as R ¹¹ and R ¹³ in formula (1) above, and R ¹¹ and R ¹³ of the desired fullerene derivative correspond to .

当該反応は、水、メタノール、エタノール、又はそれらの混合物などを溶媒として用い、及び必要に応じて塩基の存在下で実施できる。 Method (b1): Reaction of Aniline Derivative with Halogenated Acetic Acid

The reaction can be carried out using solvents such as water, methanol, ethanol, or mixtures thereof, and optionally in the presence of a base.

この方法において、アニリン誘導体とハロゲン化酢酸エステルの反応は、例えば、メタノール、エタノールなどを溶媒として用い、酢酸塩、炭酸塩、リン酸塩、３級アミンなどの塩基の存在下に行うことができる。
グリシン誘導体エステルの加水分解は、通常、水溶性アルカリの存在下に、室温で行うことができる。 Method (b2): Reaction of an aniline derivative with a halogenated acetic ester, and hydrolysis of the glycine derivative ester obtained by the reaction

In this method, the reaction between the aniline derivative and the halogenated acetic ester can be carried out in the presence of a base such as acetate, carbonate, phosphate, tertiary amine, or the like, using methanol, ethanol, or the like as a solvent. .
Hydrolysis of the glycine derivative ester can usually be carried out at room temperature in the presence of a water-soluble alkali.

この反応は、例えば、触媒として一価銅を用い、及びバルキーなアミン、アミノ酸、又はアミノアルコールなどの存在下で行うことができる。反応溶媒としては、水、メタノール、エタノール、又はこれらの混合物が好ましく用いられる。
反応温度は、室温～１００℃程度である。 Method (b3): Reaction of Aromatic Halide with Glycine

This reaction can be carried out, for example, using monovalent copper as a catalyst and in the presence of bulky amines, amino acids, aminoalcohols, and the like. Water, methanol, ethanol, or a mixture thereof is preferably used as the reaction solvent.
The reaction temperature is room temperature to about 100°C.

Since the fullerene derivative of the present invention can be synthesized by a simple method using C60 fullerene, a glycine derivative, and an aldehyde compound as raw materials, it can be produced at low cost.

Uses of the Fullerene Derivative of the Present Invention The fullerene derivative of the present invention can be suitably used as an n-type semiconductor material, particularly as an n-type semiconductor material for photoelectric conversion elements such as organic thin-film solar cells.
The fullerene derivative of the present invention can also be used as an electron transport material in transistors, perovskite solar cells, and the like.
These uses can be implemented based on common technical knowledge.

When using the fullerene derivative of the present invention as an n-type semiconductor material, it is usually used in combination with an organic p-type semiconductor material (organic p-type semiconductor compound).

Examples of the organic p-type semiconductor material include poly-3-hexylthiophene (P3HT), poly-p-phenylenevinylene, poly-alkoxy-p-phenylenevinylene, poly-9,9-dialkylfluorene, poly-p- Examples include phenylene vinylene.

Since these solar cells have been studied in many cases and are readily available, devices with stable performance can be easily obtained.

In order to obtain a higher conversion efficiency, a donor-acceptor type π-conjugated polymer, which enables absorption of long-wavelength light by narrowing the bandgap (low bandgap), is effective.

These donor-acceptor type π-conjugated polymers have a structure in which donor units and acceptor units are alternately arranged.

Examples of donor units used here include benzodithiophene, dithienosilol, and N-alkylcarbazole, and examples of acceptor units include benzothiadiazole, thienothiophene, thiophenepyrroledione, and the like.
Specifically, poly(thieno[3,4-b]thiophene-co-benzo[1,2-b:4,5-b′]thiophene) (PTBx series), poly( Polymer compounds such as dithieno[1,2-b:4,5-b′][3,2-b:2′,3′-d]silole-alt-(2,1,3-benzothiadiazole) are exemplified.

Among these, the preferred ones are
(1) Poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[ (2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7, structural formula shown below),
(2) poly[(4,8-di(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene)-2,6-diyl-alt-((5-octylthieno[3 ,4-c]pyrrole-4,6-dione)-1,3-diyl) (PBDTTPD, structural formula shown below),
(3) poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3 -benzothiadiazole)-4,7-diyl] (PSBTBT, structural formula shown below),
(4) Poly[N-9″-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) ] (PCDTBT, structural formula shown below), and (5) poly[1-(6-{4,8-bis[(2-ethylhexyl)oxy]-6-methylbenzo[1,2-b:4, 5-b′]dithiophen-2-yl}{3-fluoro-4-methylthieno[3,4-b]thiophen-2-yl}-1-octanone) (PBDTTT-CF, structural formula shown below)
etc. are exemplified.

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（式中、ｎは繰り返し数を表す。）

(In the formula, n represents the number of repetitions.)

(In the formula, n represents the number of repetitions.)

(In the formula, n represents the number of repetitions.)

(In the formula, n represents the number of repetitions.)

(In the formula, n represents the number of repetitions.)

Among them, more preferred examples include PTB compounds having a fluorine atom at the 3-position of thieno[3,4-b]thiophene as the acceptor unit, and particularly preferred examples include PBDTTT-CF and PTB7. be done.

An organic power generation layer prepared by using the fullerene derivative of the present invention in combination with an organic p-type semiconductor material as an n-type semiconductor material can exhibit high conversion efficiency.
Since the fullerene derivative of the present invention exhibits good solubility in various organic solvents, when it is used as an n-type semiconductor material, it is possible to prepare an organic power generation layer by a coating method. Preparation of the power generation layer is also easy.

In addition, the fullerene derivative of the present invention is a compound having good compatibility with organic p-type semiconductor materials and moderate self-aggregating properties. Therefore, an organic power generation layer having a bulk junction structure is easily formed using the fullerene derivative as an n-type semiconductor material (organic n-type semiconductor material). By using this organic power generation layer, an organic thin-film solar cell or a photosensor with high conversion efficiency can be obtained.

Therefore, by using the fullerene derivative of the present invention as an n-type semiconductor material, it becomes possible to produce an organic thin-film solar cell having excellent performance at low cost.

Another application of the organic power-generating layer containing (or consisting of) the n-type semiconductor material of the present invention is an image sensor for a digital camera.

In response to the demand for higher functionality (higher definition) of digital cameras, it has been pointed out that existing image sensors made of silicon semiconductors have a problem of reduced sensitivity. In contrast, image sensors made of organic materials with high photosensitivity are expected to enable high sensitivity and high definition.

The materials that make up the light-receiving part of such sensors are required to absorb light with high sensitivity and generate electrical signals from it with high efficiency.

In response to such demands, the organic power generation layer containing (or consisting of) the n-type semiconductor material of the present invention can efficiently convert visible light into electrical energy. High function can be expressed.

N-Type Semiconductor Material The n-type semiconductor material of the present invention contains the fullerene derivative of the present invention.
The n-type semiconductor material of the present invention can preferably consist of the fullerene derivative of the present invention.

The n-type semiconductor material of the present invention and its use can be understood from the description of this specification and common general technical knowledge.
The n-type semiconductor material of the present invention can be suitably used for photoelectric conversion.

Photovoltaic Conversion Layer The present invention also provides a photovoltaic conversion layer.
The photoelectric conversion layer of the present invention contains the fullerene derivative of the present invention as an n-type semiconductor material (n-type semiconductor compound).
The photoelectric conversion layer of the present invention can preferably be an organic power generation layer.

Moreover, the photoelectric conversion layer of the present invention usually contains the organic p-type semiconductor material (organic p-type semiconductor compound) in combination with the fullerene derivative of the present invention, that is, the n-type semiconductor material of the present invention.

Moreover, the photoelectric conversion layer of the present invention usually comprises the n-type semiconductor material of the present invention and the organic p-type semiconductor.

Preferably, in the photoelectric conversion layer of the present invention, the n-type semiconductor material of the present invention and the organic p-type semiconductor material form a bulk heterojunction structure.

The photoelectric conversion layer of the present invention can be produced, for example, by dissolving the n-type semiconductor material and the organic p-type semiconductor material of the present invention in an organic solvent, and applying the resulting solution by spin coating, casting, dipping, ink jet, It can be prepared by forming a thin film on a substrate using a known thin film forming method such as a doctor blade method and a screen printing method.

In the thin film formation of the photoelectric conversion layer, the fullerene derivative of the present invention has good compatibility with an organic p-type semiconductor material (preferably P3HT or PTB7) and has an appropriate self-aggregating property. A photoelectric conversion layer containing the fullerene derivative of the present invention as an n-type semiconductor material and an organic p-type semiconductor material and having a bulk heterojunction structure can be easily obtained.

Photoelectric Conversion Device The present invention also provides a photoelectric conversion device.
The photoelectric conversion element of the invention contains the photoelectric conversion layer of the invention.

The photoelectric conversion device can be understood from the description of the present specification including the description of the fullerene derivative and common general technical knowledge.

Organic Thin Film Solar Cell The organic thin film solar cell of the present invention contains the photoelectric conversion layer (or organic power generation layer) of the present invention described above.
As understood from this, the organic thin film solar cell of the present invention may contain the photoelectric conversion element of the present invention.
Based on this, the organic thin film solar cell of the present invention can have high conversion efficiency.

The structure of the organic thin-film solar cell is not particularly limited, and may have the same structure as a known organic thin-film solar cell. can be manufactured.

As an example of the organic thin-film solar cell, for example, a solar cell having a structure in which a transparent electrode (cathode), a cathode-side charge transport layer, an organic power generation layer, an anode-side charge transport layer and a counter electrode (anode) are sequentially laminated on a substrate. A battery can be exemplified. The organic power generation layer preferably contains the fullerene derivative of the present invention as an organic p-type semiconductor material and an n-type semiconductor material, and is a semiconductor thin film layer having a bulk heterojunction structure [that is, a photoelectric conversion layer (organic power generation layer) ].

In the solar cell having such a structure, 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).

Photosensor The photosensor of the present invention contains the photoelectric conversion layer (or organic power generation layer) of the present invention described above.
As understood from this, the optical sensor of the present invention may contain the photoelectric conversion element of the present invention.
The photosensor of the present invention can have an electrode electrically connected to the photoelectric conversion layer.

As described above, the photoelectric conversion layer obtained by the present invention effectively functions as a light-receiving part for image sensors in high-performance products of digital cameras. Compared to photosensors using conventional silicon photodiodes, overexposure does not occur in bright areas, and clear images can be obtained even in dark areas. Therefore, it is possible to obtain a higher quality image than the conventional camera.

The optical sensor of the present invention can be constructed from a silicon substrate, an electrode, a light-receiving section composed of a photoelectric conversion layer, a color filter, and a microlens.
The thickness of the light-receiving part can be about several hundred nm, which is a fraction of the thickness of a conventional silicon photodiode.

Perovskite Solar Cells The present invention also provides perovskite solar cells.
The perovskite solar cell of the invention contains the fullerene derivative of the invention.
The perovskite solar cell of the invention can contain a perovskite layer, in combination with which the fullerene derivative of the invention can be used for the electron transport layer.

Composition The composition of the present invention contains the fullerene derivative of the present invention.
The composition of the present invention can contain other components (eg, solvents, additives) depending on its use as long as the object of the present invention is not significantly impaired.
The composition can be understood with reference to the description herein, including the description of the fullerene derivative.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
The meanings of the symbols and abbreviations in the examples are shown below.
EH: 2-ethylhexyl
Me: methyl
n-Bu: n-Butyl
n-Pr: n-Propyl

In the examples, the absorbance was measured using the following equipment and conditions.
Equipment: Shimadzu UV-3600 UV-visible spectrophotometer (Shimadzu Corporation)
Measuring cell: cell length atom (quartz);
Measurement solvent: Toluene

A 1.1 wt % toluene solution was prepared, and the absorbance was measured using the UV-visible spectrophotometer.
The measured absorption coefficients at absorption wavelengths of 500 nm and 550 nm are shown for each synthesis example.

Synthesis example 1

N-phenylglycine (151 mg, 1.0 mmol), 2,6-di(n-propoxy)benzaldehyde (447 mg, 1.9 mmol), fullerene (720 mg, 1.0 mmol) in chlorobenzene (200 mL) at 120°C for 48 hours. It was heated and stirred.
The reaction product solution was concentrated under reduced pressure, and the reactant was subjected to column chromatography (SiO2, hexane-toluene = 10:1 to 4:1).
Further purification by HPLC (Buckyprep: toluene) gave 220 mg (21%) of the desired product.

¹ H-NMR (CDCl ₃ )δ: 0.89 (6H, t, J=7.2 Hz), 1.70 - 1.90 (4H, m), 3.85 - 3.95 (2H, m), 4.05 - 4.15 (2H, m), 5.40 (1H, d, J=9.6 Hz), 5.77 (1H, d, J=9.6 Hz), 6.48 (1H, d, J=8.7 Hz), 6.57 (1H, d, J=8.7 Hz), 6.81 (1H , t, J=8.7 Hz), 7.00 (2H, d, J=8.2 Hz), 7.14 (1H, t, J=8.2 Hz), 7.30 (2H, t, J=8.2 Hz), 7.63 (1H, s ).
MS (FAB) m/z 1031 (M-1). HRMS calcd for _{C80H25NO2 1031.1885} ; found _1031.1858 .

Synthesis example 2

A solution of N-phenylglycine (76 mg, 0.5 mmol), 2,6-bis(2-ethylhexyloxy)benzaldehyde (427 mg, 1.0 mmol), and fullerene (360 mg, 0.5 mmol) in chlorobenzene (200 mL) was heated at 120°C to 48°C. Heated and stirred for hours.
The reaction product solution was concentrated under reduced pressure, and the reactant was subjected to column chromatography (SiO2, hexane-toluene = 50:1 to 10:1).
Further purification by HPLC (Buckyprep: toluene) gave 266 mg (45%) of the desired product.

¹ H-NMR (CDCl ₃ )δ: 0.78 - 1.01 (12H, m), 1.16 - 1.73 (17H, m), 2.00 - 2.12 (1H, m), 3.85 - 4.07 (4H, m), 5.37 (1H, d, J=9.6 Hz), 5.76 (1H, d, J=9.6 Hz), 6.52 (1H, d, J=8.7 Hz), 6.59 (1H, d, J=8.7 Hz), 6.81 (1H, t, J=8.7 Hz), 7.02 (2H, d, J=7.8 Hz), 7.16 (1H, t, J=7.8 Hz), 7.29 (2H, t, J=7.8 Hz), 7.54 (1H, s).
MS (FAB) m/z 1172 (M+). HRMS calcd for _{C90H45NO2 1171.3450} ; found _1171.3426 .

Synthesis Example 3 (Comparative Example)

A chlorobenzene solution (300 mL) of N-phenylglycine (151 mg, 1.0 mmol), 2-butoxybenzaldehyde (2 mL, excess), and fullerene (720 mg, 1.0 mmol) was heated and stirred at 120° C. for 48 hours.
The reaction product was concentrated under reduced pressure, and the reaction product was purified by column chromatography (SiO2, hexane-toluene = 20:1 to 5:1), and further purified by HPLC (Buckyprep: toluene) to obtain 407 mg of the desired product. (41%) obtained.

¹ H-NMR (CDCl ₃ )δ: 0.93 (3H, t, J=7.3 Hz), 1.40 - 1.53 (2H, m), 1.55 - 1.80 (2H, m), 3.74 - 3.85 (1H, m), 4.05 - 4.14 (1H, m), 5.07 (1H, d, J=10.1Hz), 5.67 (1H, d, J=10.1Hz), 6.73 (1H, s), 6.89 (2H, d, J=7.8Hz) , 7.15 - 7.40 (6H, m), 7.77 (1H, d, J=7.8 Hz).
MS (FAB) m/z 988 (M+). HRMS calcd for _{C78H21NO 987.1623} ; found 987.1611.

Synthesis Example 4 (Comparative Example)

A chlorobenzene solution (200 mL) of N-phenylglycine (151 mg, 1.0 mmol), 2-ethoxybenzaldehyde (1 mL, excess), and fullerene (720 mg, 1.0 mmol) was heated and stirred at 120° C. for 48 hours.
The reaction product was concentrated under reduced pressure, and the reaction product was purified by column chromatography (SiO2, hexane-toluene = 10:1 to 3:1), and further purified by HPLC (Buckyprep: toluene) to obtain 326 mg of the desired product. (34%) obtained.

¹ H-NMR (CDCl ₃ ) δ: 1.29 (3H, t, J=6.9 Hz), 3.70 - 3.89 (1H, m), 4.12 - 4.24 (1H, m), 5.09 (1H, d, J=10.1 Hz ), 5.66 (1H, d, J=10.1 Hz), 6.76 (1H, s), 6.80 - 6.95 (2H, m), 7.10 - 7.40 (6H, m), 7.74 (1H, d, J=7.3 Hz) .
MS (FAB) m/z 959 (M-1). HRMS calcd for _{C76H17NO 959.1310} ; found 987.1311.

Example 1
An ultraviolet-visible absorption spectrum chart of the fullerene derivative of each synthesis example was obtained by the following method. A chart is shown in the figure. Furthermore, the molar absorption coefficients (500 nm and 550 nm, toluene solution) of the fullerene derivative of each synthesis example were obtained. This is shown below.
<Method>
A certain amount of the compound was weighed into a volumetric flask, and a homogeneous solution was prepared using toluene as a solvent. The absorbance of the toluene solution was measured using a quartz cell (cell length: 10 mm).
The molar extinction coefficient was calculated from the concentration and the absorbance by the following formula.
Molar extinction coefficient (ε) = absorbance (abs)/molar concentration × cell length (mm)
The chart is shown in each figure. The numbers on the vertical axis are absorbance values.

A comparison with the absorption spectrum data of the compound of the comparative example shows that the fullerene derivative having two substituents at the ortho-position to the phenyl group at the 2-position has significantly increased absorption in the region of 450 nm to 550 nm.

<Molar extinction coefficient>
Fullerene derivative of Synthesis Example 1
500 nm: 2430
550 nm: 2260
Fullerene derivative of Synthesis Example 2
500 nm: 2400
550 nm: 2200
Fullerene derivative of Synthesis Example 3 (Comparative Example)
500 nm: 1650
550 nm: 1120
Fullerene derivative of Synthesis Example 4 (Comparative Example)
500 nm: 1650
550 nm: 1110

Claims (13)

Formula (1):

[In the formula,
R ¹¹ is a phenyl group,
R ¹² is a phenyl group having the same or different C 3-12 alkoxy groups at each ortho position and optionally having 1 to 3 substituents;
^R13 is
(1) hydrogen, or (2) a linear or branched aliphatic group optionally having one or more substituents, and ring A represents a C60 fullerene ring. ]
A fullerene derivative containing a fullerene derivative represented by The fullerene derivative according to claim 1, wherein R ¹² is a phenyl group having a C 3-12 alkoxy group at each ortho position and further optionally having 1 to 3 substituents. A fullerene derivative according to claim 1 or 2, wherein R ¹² is a phenyl group having a C 3-12 alkoxy group at each ortho position and further having 1 to 3 substituents. The fullerene derivative according to any one of claims 1 to 3, wherein R ¹² is a phenyl group having mutually identical substituents at each ortho position. 5. The fullerene derivative according to any one of claims 1 to 4, which has a light absorption coefficient of 2000 or more over the entire wavelength range of 450 to 550 nm. An n-type semiconductor material containing the fullerene derivative according to any one of claims 1 to 5. The n-type semiconductor material according to claim 6, which is for photoelectric conversion. A photoelectric conversion layer containing the type semiconductor material according to claim 6 or 7. A photoelectric conversion device comprising the photoelectric conversion layer according to claim 8 . An organic thin-film solar cell comprising the photoelectric conversion layer according to claim 8 . An optical sensor comprising the photoelectric conversion layer according to claim 8 . A perovskite solar cell containing the fullerene derivative according to any one of claims 1 to 5. A composition containing the fullerene derivative according to any one of claims 1 to 5.

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