JP2013220994A - Compound and electronic element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which when used for an active layer of a photoelectric conversion element, can increases an open end voltage of the element.SOLUTION: A compound is represented by formula (wherein: each of Xand Xindependently represents a nitrogen atom or =CH-; each of Yand Yindependently represents a sulfur atom, an oxygen atom, a selenium atom, or -N(R)-; Yrepresents a sulfur atom, an oxygen atom, a selenium atom, -N(R)-, or -CR=CR-; Z represents an oxygen atom, a sulfur atom, a carbonyl group, a direct bond, -C(R)(R)-, or -N(R)-; each of Arand Arindependently represents an arylene group or a divalent heterocyclic group optionally having a substituent; each of Aand Aindependently represents an aryl group or a heterocyclic group optionally having a substituent; at least one of Aand Ais a group represented by predetermined formula).

Description

  The present invention relates to a compound having a specific structure and an electronic device using the same.

In recent years, in order to prevent global warming, reduction of CO ₂ released into the atmosphere has been demanded. For example, although the adoption of a solar system using a pn junction type silicon solar cell or the like on the roof of a house has been proposed, the single crystal, polycrystalline and amorphous silicon used in the silicon solar cell are in the manufacturing process. There is a problem that high temperature and high vacuum conditions are required.

  On the other hand, the organic thin film solar cell which is one aspect of the photoelectric conversion element can omit the high-temperature and high-vacuum process used in the manufacturing process of the silicon-based solar cell, and can be manufactured at low cost only by the coating process. Has been. As a compound used for an organic thin film solar cell, a polymer compound composed of a repeating unit (A) and a repeating unit (B) has been proposed (Patent Document 1).

Special table 2009-506519

  However, a photoelectric conversion element having an active layer containing the polymer compound does not necessarily have a sufficiently high open end voltage.

  An object of the present invention is to provide a compound that increases the open-circuit voltage when used in an active layer of a photoelectric conversion device, and an electronic device using the compound.

（１）
〔式（１）中、Ｘ^１及びＸ^２は、それぞれ独立に、窒素原子又は＝ＣＨ−を表す。Ｙ^１及びＹ^２は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、又は−Ｎ（Ｒ^５）−を表す。Ｙ^３は、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^５）−又は−ＣＲ^６＝ＣＲ^７−を表す。Ｚは、酸素原子、硫黄原子、カルボニル基、直接結合、−Ｃ（Ｒ^８）（Ｒ^９）−又は−Ｎ（Ｒ^１０）−を表す。Ｒ^１〜Ｒ^１０は、それぞれ独立に、水素原子又は置換基を表す。ｑは、１〜３の整数を表す。Ｙ^１が複数個ある場合は、それらは同一でも相異なってもよい。Ｙ^２が複数個ある場合は、それらは同一でも相異なってもよい。Ｙ^３が複数個ある場合は、それらは同一でも相異なってもよい。Ｚが複数個ある場合は、それらは同一でも相異なってもよい。Ｒ^１が複数個ある場合は、それらは同一でも相異なってもよい。Ｒ^２が複数個ある場合は、それらは同一でも相異なってもよい。Ｒ^３が複数個ある場合は、それらは同一でも相異なってもよい。Ｒ^４が複数個ある場合は、それらは同一でも相異なってもよい。Ｘ^１が複数個ある場合は、それらは同一でも相異なってもよい。Ｘ^２が複数個ある場合は、それらは同一でも相異なってもよい。Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換基を有していてもよいアリーレン基又は２価の複素環基を表す。ｐ及びｒは、それぞれ独立に、０〜２の整数を表す。ｐが２である場合、２個あるＡｒ^１は同一でも相異なってもよい。ｒが２である場合、２個あるＡｒ^２は同一でも相異なってもよい。Ａ^１及びＡ^２は、それぞれ独立に、置換基を有していてもよいアリール基又は複素環基を表す。ただし、Ａ^１とＡ^２の少なくとも一方は、式（Ａ−１）で表される基又は式（Ａ−２）で表される基である。

（Ａ−１） （Ａ−２）
（式（Ａ−１）及び式（Ａ−２）中、Ｗ^１〜Ｗ^８は、それぞれ独立に、水素原子、フッ素原子、又は置換基を有していてもよいアルキル基を表す。Ｙ^４は、硫黄原子、酸素原子、セレン原子、又は−Ｎ（Ｒ^１１）−を表す。Ｒ^１１は、水素原子又は置換基を表す。）〕 The present invention first provides a compound represented by the formula (1).

(1)
[In ^the formula (1), ^{X 1} and ^{X 2} each independently represent a nitrogen atom or = CH-. Y ¹ and Y ² each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R ⁵ ) —. Y ³ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 5)} - represents a - or ^-CR 6 = CR ^7. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a direct bond, —C (R ⁸ ) (R ⁹ ) — or —N (R ¹⁰ ) —. R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. q represents an integer of 1 to 3. When there are a plurality of Y ¹ , they may be the same or different. When there are a plurality of Y ² , they may be the same or different. When there are a plurality of Y ³ , they may be the same or different. When there are a plurality of Z, they may be the same or different. When there are a plurality of R ^{1 s} , they may be the same or different. When there are a plurality of R ^{2 s} , they may be the same or different. When there are a plurality of R ³ , they may be the same or different. When there are a plurality of R ⁴ , they may be the same or different. When there are a plurality of X ¹ , they may be the same or different. If X ² is in plurality, they may be the same or different. Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group which may have a substituent. p and r each independently represents an integer of 0 to 2. When p is 2, two Ar ¹ may be the same or different. When r is 2, two Ar ² may be the same or different. A ¹ and A ² each independently represents an aryl group or a heterocyclic group which may have a substituent. However, at least one of A ¹ and A ² is a group represented by the formula (A-1) or a group represented by the formula (A-2).

(A-1) (A-2)
(In Formula (A-1) and Formula (A-2), W ^{1 to} W ⁸ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group that may have a substituent. Y ⁴ Represents a sulfur atom, an oxygen atom, a selenium atom, or —N (R ¹¹ ) —, where R ¹¹ represents a hydrogen atom or a substituent.

  Secondly, the present invention provides the above compound, wherein the energy of the highest occupied orbit calculated using the density functional method is −4.55 eV or less.

  Thirdly, the present invention provides the above compound, wherein Z is an oxygen atom.

The present invention fourthly provides the compound, wherein both R ³ and R ⁴ are fluorine atoms.

Fifthly, the present invention provides the compound, wherein both A ¹ and A ² are a group represented by the formula (A-1) or a group represented by the formula (A-2).

  Sixthly, this invention provides the thin film containing the said compound.

  Seventhly, this invention provides the composition containing the said compound and an electron-accepting compound.

  Eighth, the present invention provides the composition, wherein the electron accepting compound is a fullerene derivative.

  Ninthly, this invention provides the thin film containing the said composition.

  Tenthly, the present invention provides a solution containing the compound or the composition and a solvent.

  Eleventhly, the present invention has a first electrode and a second electrode, and an active layer is provided between the first electrode and the second electrode, and the active layer includes the compound, or An electronic device containing the composition is provided.

  12thly this invention provides the said electronic element which is a photoelectric conversion element.

  13thly this invention provides a solar cell module provided with the said photoelectric conversion element.

  14thly this invention provides the image sensor provided with the said photoelectric conversion element.

  Fifteenth, the present invention provides an organic thin film transistor comprising a gate electrode, a source electrode, a drain electrode, and an active layer, wherein the active layer contains the compound or the composition.

（１−２）
〔式中、Ｘ^１及びＸ^２は、それぞれ独立に、窒素原子又は＝ＣＨ−を表す。Ｙ^１及びＹ^２は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、又は−Ｎ（Ｒ^５）−を表す。Ｙ^３は、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^５）−又は−ＣＲ^６＝ＣＲ^７−を表す。Ｚは、酸素原子、硫黄原子、カルボニル基、直接結合、−Ｃ（Ｒ^８）（Ｒ^９）−又は−Ｎ（Ｒ^１０）−を表す。Ｒ^１〜Ｒ^１０は、それぞれ独立に、水素原子又は置換基を表す。２個あるＲ^３は同一でも相異なってもよい。２個あるＲ^４は同一でも相異なってもよい。２個あるＸ^１は同一でも相異なってもよい。２個あるＸ^２は同一でも相異なってもよい。２個あるＹ^３は同一でも相異なってもよい。Ｑ^１及びＱ^２は、それぞれ独立に、ハロゲン原子を表す。〕 Sixteenth, the present invention provides a compound represented by formula (1-2).

(1-2)
[Wherein, X ¹ and X ² each independently represent a nitrogen atom or ═CH—. Y ¹ and Y ² each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R ⁵ ) —. Y ³ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 5)} - represents a - or ^-CR 6 = CR ^7. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a direct bond, —C (R ⁸ ) (R ⁹ ) — or —N (R ¹⁰ ) —. R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. Two R ³ may be the same or different. Two R ⁴ may be the same or different. Two X ¹ may be the same or different. Two X ² may be the same or different. Two Y ³ may be the same or different. Q ¹ and Q ² each independently represents a halogen atom. ]

  Since the photoelectric conversion element which has the active layer containing the compound of this invention has a high open end voltage, this invention is very useful.

  Hereinafter, embodiments of the present invention will be described in detail.

The compound of this invention is a compound represented by Formula (1).

In formula (1), X ¹ and X ² each independently represent a nitrogen atom or ═CH—. X ¹ and X ² are preferably nitrogen atoms from the viewpoint of improving the open-circuit voltage of the photoelectric conversion element containing the compound of the present invention.
In formula (1), Y ¹ and Y ² each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R ⁵ ) —. Y ¹ and Y ² are preferably a sulfur atom, an oxygen atom, and —N (R ⁵ ) —, more preferably a sulfur atom and an oxygen atom, and particularly preferably a sulfur atom, from the viewpoint of the stability of the compound.
Y ³ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 5)} - represents a - or ^-CR 6 = CR ^7. Y ³ is preferably a sulfur atom, an oxygen atom, and —CR ⁶ ═CR ⁷ —, more preferably a sulfur atom and an oxygen atom, and particularly preferably a sulfur atom, from the viewpoint of improving the stability of the compound.
Z represents an oxygen atom, a sulfur atom, a carbonyl group, a direct bond, —C (R ⁸ ) (R ⁹ ) — or —N (R ¹⁰ ) —. Z is preferably an oxygen atom, a sulfur atom, a carbonyl group or a direct bond, more preferably an oxygen atom, a carbonyl group or a direct bond, further preferably an oxygen atom or a direct bond, from the viewpoint of ease of synthesis of the compound, Atoms are particularly preferred.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. An aryl group that may have a substituent, an aryloxy group that may have a substituent, an arylthio group that may have a substituent, an arylalkyl group that may have a substituent, and a substituent. Arylalkoxy group which may be substituted, arylalkylthio group which may have substituent, acyl group, acyloxy group, amide group, imide group, imino group, amino group, substituted amino group, silyl group, substituted silyl group Substituted silyloxy group, substituted silylthio group, substituted silylamino group, arylalkenyl group optionally having substituent, arylalkynyl group optionally having substituent, substituted Rubokishi group, a carboxy group, a heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, a nitro group and a cyano group.

  Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

  The alkyl group may be linear, branched, or cyclic. The carbon number of an alkyl group is 1-30 normally, and 1-20 are preferable. The alkyl group may have a substituent, and examples of the substituent include a halogen atom. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl. Group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group And chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.

  The alkyl group portion of the alkoxy group may be linear, branched, or cyclic. The carbon atom number of an alkoxy group is 1-20 normally, and 1-15 are preferable. The alkoxy group may have a substituent, and examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyl group. Oxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group Perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group and 2-methoxyethyloxy group.

  The alkyl group portion of the alkylthio group may be linear, branched, or cyclic. The number of carbon atoms of the alkylthio group is usually 1-20, preferably 1-15. The alkylthio group may have a substituent, and examples of the substituent include a halogen atom. Specific examples of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, and a cyclohexylthio group. Group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and trifluoromethylthio group.

The aryl group means a group obtained by removing one hydrogen atom bonded to an aromatic ring from an aromatic hydrocarbon, and the aryl group usually has 6 to 60 carbon atoms. The aryl group may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group that may have a substituent, and an alkylthio group that may have a substituent. . The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the aryl group which may have a substituent include a phenyl group and a C1-C12 alkoxyphenyl group (where the number attached to “C” meaning a carbon atom means the number of carbon atoms). “C1-C12 alkoxy” means that the group contains an alkoxy group having 1 to 12 carbon atoms, and the alkoxy group in the alkoxyphenyl group is preferably C1-C8 alkoxy, more C1 to C6 alkoxy is preferable, C1 to C8 alkoxy represents alkoxy having 1 to 8 carbon atoms, and C1 to C6 alkoxy represents alkoxy having 1 to 6 carbon atoms. ~C12 alkoxy, specific examples of C1~C8 alkoxy and C1~C6 alkoxy, specific examples of the alkoxy group represented by ^R 1 ^{to R 10} described above The same applies to the following.), C1-C12 alkylphenyl group ("C1-C12 alkyl" means that an alkyl group having 1 to 12 carbon atoms is contained in the group. The alkyl group in the alkylphenyl group is preferably C1 to C8 alkyl, more preferably C1 to C6 alkyl, and C1 to C8 alkyl represents alkyl having 1 to 8 carbon atoms, C6 alkyl represents alkyl having 1 to 6 carbon atoms, and specific examples of C1 to C12 alkyl, C1 to C8 alkyl, and C1 to C6 alkyl include alkyl represented by the aforementioned R ^{1 to} R ^10. Specific examples of the group include the groups exemplified below, and the same applies to the following.), 1-naphthyl group, 2-naphthyl group, and pentafluorophenyl group.

The aryloxy group usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the aryloxy group which may have a substituent include phenoxy group, C1-C12 alkoxyphenoxy group, C1-C12 alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and pentafluorophenyl. An oxy group is mentioned.

The arylthio group usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the arylthio group which may have a substituent include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenylthio. Groups.

The arylalkyl group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the arylalkyl group which may have a substituent include a phenyl-C1-C12 alkyl group, a C1-C12 alkoxyphenyl-C1-C12 alkyl group, a C1-C12 alkylphenyl-C1-C12 alkyl group, Examples include 1-naphthyl-C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group.

The arylalkoxy group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the arylalkoxy group which may have a substituent include a phenyl-C1-C12 alkoxy group, a C1-C12 alkoxyphenyl-C1-C12 alkoxy group, a C1-C12 alkylphenyl-C1-C12 alkoxy group, Examples include 1-naphthyl-C1 to C12 alkoxy groups and 2-naphthyl-C1 to C12 alkoxy groups.

The arylalkylthio group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the arylalkylthio group which may have a substituent include a phenyl-C1-C12 alkylthio group, a C1-C12 alkoxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, Examples include 1-naphthyl-C1-C12 alkylthio group and 2-naphthyl-C1-C12 alkylthio group.

  An acyl group means the group except the hydroxyl group in carboxylic acid, and the carbon atom number is 2-20 normally. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, an alkylcarbonyl group which may be substituted with a halogen atom having 2 to 20 carbon atoms, a benzoyl group And a phenylcarbonyl group which may be substituted with a halogen atom such as a pentafluorobenzoyl group.

  An acyloxy group means the group remove | excluding the hydrogen atom in carboxylic acid, and the carbon atom number is 2-20 normally. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

  An amide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, and the carbon number is usually 1-20. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

  The imide group is a group obtained by removing one hydrogen atom bonded to a nitrogen atom in an imide (a compound containing a divalent group represented by —CO—NH—CO—). Specific examples of the imide group include a succinimide group and a phthalimide group.

The substituted amino group is a group in which one or two of the hydrogen atoms of the amino group are substituted with a substituent. Examples of the substituent include an alkyl group which may have a substituent, and The aryl group which may have a substituent is mentioned. The definition and specific examples of the alkyl group which may have the substituent and the aryl group which may have the substituent may have the substituent represented by R ^{1 to} R ¹⁰ described above. The definition and specific examples of a good alkyl group and an aryl group which may have a substituent are the same. The number of carbon atoms of the substituted amino group is usually 1-40. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alcohol Ruoxyphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkoxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 alkylamino group Groups, di (C1-C12 alkoxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group and 2-naphthyl-C1 ~ C12 Archi And amino group.

Substituted silyl group means a group in which one, two or three of the hydrogen atoms of the silyl group are substituted with substituents. In general, all three hydrogen atoms of a silyl group are substituted with substituents. Group. As this substituent, the alkyl group which may have a substituent, and the aryl group which may have a substituent are mentioned, for example. The definition and specific examples of the alkyl group which may have the substituent and the aryl group which may have the substituent may have the substituent represented by R ^{1 to} R ¹⁰ described above. The definition and specific examples of a good alkyl group and an aryl group which may have a substituent are the same. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

  The substituted silyloxy group is a group in which an oxygen atom is bonded to the above substituted silyl group. Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group. Examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

  The substituted silylthio group is a group in which a sulfur atom is bonded to the above substituted silyl group. Specific examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, and tri-p-xylyl. Examples thereof include a silylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

  The substituted silylamino group is a group in which one or two of the hydrogen atoms of the amino group are substituted with a substituted silyl group, and the substituted silyl group is as described above. Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl. Silylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (tripropylsilyl) ) Amino group, di (triisopropylsilyl) amino group, di (tert-butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-xylylsilyl) amino group, di (tribenzylsilyl) A Amino group, di (diphenylmethyl silyl) amino, di (tert- butyldiphenylsilyl) amino group and di (dimethylphenylsilyl) and amino group.

The arylalkenyl group usually has 8 to 20 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the arylalkenyl group which may have a substituent include a styryl group.

The arylalkynyl group usually has 8 to 20 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent. Specific examples of the arylalkynyl group which may have a substituent include a phenylacetylenyl group.

  The substituted carboxy group means a group in which a hydrogen atom in the carboxy group is substituted with an alkyl group or an aryl group, and the number of carbon atoms is usually 2-20. Examples of the substituted carboxy group include a methoxycarbonyl group, an ethoxycarbonyl group, and a phenoxycarbonyl group.

Heterocyclic groups are furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, oxadiazole, tetrazole, Pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chroman, isochroman, benzopyran, quinoline , Isoquinoline, quinolidine, benzimidazole, benzothiazole, indazole, naphthyridine, quinoki Has substituents such as phosphorus, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine Means a group obtained by removing one hydrogen atom from an optionally substituted heterocyclic compound. Examples of the substituent include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. An aryl group that may have, an aryloxy group that may have a substituent, an arylthio group that may have a substituent, an arylalkyl group that may have a substituent, and a substituent; An arylalkoxy group which may have a substituent, an arylalkylthio group which may have a substituent, an acyl group, an acyloxy group, an amide group, an amino group, a substituted amino group, a silyl group, a substituted silyl group and a substituent. An arylalkenyl group which may be substituted, an arylalkynyl group which may have a substituent, a substituted carboxy group, a carboxy group, a nitro group and a cyano group. The halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryl which may have a substituent Group, aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, aryl which may have a substituent Alkoxy group, arylalkylthio group optionally having substituent, acyl group, acyloxy group, amide group, substituted amino group, substituted silyl group, arylalkenyl group optionally having substituent, having substituent definitions and examples of good arylalkynyl group and substituted carboxyl group which may include a halogen atom represented by R ¹ to R ¹⁰ described above, which may have a substituent alkyl group, a substituted group An optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, and a substituent. An arylthio group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, an arylalkylthio group which may have a substituent, an acyl group, Definitions and specific examples of acyloxy group, amide group, substituted amino group, substituted silyl group, arylalkenyl group which may have a substituent, arylalkynyl group which may have a substituent and substituted carboxy group It is. As the heterocyclic group, an aromatic heterocyclic group is preferable.

〔式（１１）及び式（１２）中、Ａｒ^７は、複素環基を表す。〕 Examples of the heterocyclic oxy group include a group represented by the formula (11) in which an oxygen atom is bonded to the above heterocyclic group.
Examples of the heterocyclic thio group include a group represented by the formula (12) in which a sulfur atom is bonded to the above heterocyclic group.

[In Formula (11) and Formula (12), Ar ⁷ represents a heterocyclic group. ]

  The heterocyclic oxy group usually has 2 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.

  The heterocyclic thio group usually has 2 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have a hydrogen atom, a halogen atom or a substituent from the viewpoint of improving the solubility of the compound in an organic solvent. An alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and an aryloxy group which may have a substituent are preferable. An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable, and an alkyl group which may have a substituent is particularly preferable.
R ³ and R ⁴ have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or a substituent from the viewpoint of improving the open-circuit voltage of the photoelectric conversion element containing the compound of the present invention. An alkoxy group which may have a substituent, an aryl group which may have a substituent, and an aryloxy group which may have a substituent are preferable, and may have a hydrogen atom, a halogen atom and a substituent. An alkoxy group is more preferable, and a hydrogen atom and a halogen atom are particularly preferable. The halogen atom represented by R ³ and R ⁴ is preferably a fluorine atom, a chlorine atom and a bromine atom, more preferably a fluorine atom and a chlorine atom, and particularly preferably a fluorine atom.

  In formula (1), q represents an integer of 1 to 3. q is preferably 1 or 2 and particularly preferably 1 from the viewpoint of improving the open-circuit voltage of the photoelectric conversion element containing the compound of the present invention.

Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group which may have a substituent.

An arylene group means a group excluding two of the hydrogen atoms bonded to an aromatic ring contained in an aromatic hydrocarbon. The arylene group includes a group containing a benzene ring, a group containing a condensed ring, a group in which two or more independent benzene rings or condensed rings are directly bonded, and a group in which two or more independent benzene rings or condensed rings are vinylene. Also included are groups bonded through each other.
The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 20. The arylene group may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. . The definition and specific examples of the halogen atom, the optionally substituted alkoxy group and the optionally substituted alkylthio group are the halogen atoms and substituents represented by the aforementioned R ^{1 to} R ^10. The same as the definition and specific examples of the alkoxy group which may have a substituent and the alkylthio group which may have a substituent.

The divalent heterocyclic group includes furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, oxadi Azole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chroman, isochroman , Benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole, indazole, naphthyridine Has substituents such as quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine Means a group obtained by removing two hydrogen atoms from an optionally substituted heterocyclic compound. Examples of the substituent include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. An aryl group that may have, an aryloxy group that may have a substituent, an arylthio group that may have a substituent, an arylalkyl group that may have a substituent, and a substituent; An arylalkoxy group which may have a substituent, an arylalkylthio group which may have a substituent, an acyl group, an acyloxy group, an amide group, an amino group, a substituted amino group, a silyl group, a substituted silyl group and a substituent. An arylalkenyl group which may be substituted, an arylalkynyl group which may have a substituent, a substituted carboxy group, a carboxy group, a nitro group and a cyano group. The halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryl which may have a substituent Group, aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, aryl which may have a substituent Alkoxy group, arylalkylthio group optionally having substituent, acyl group, acyloxy group, amide group, substituted amino group, substituted silyl group, arylalkenyl group optionally having substituent, having substituent definitions and examples of good arylalkynyl group and substituted carboxyl group which may include a halogen atom represented by R ¹ to R ¹⁰ described above, which may have a substituent alkyl group, a substituted group An optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, and a substituent. An arylthio group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, an arylalkylthio group which may have a substituent, an acyl group, Definitions and specific examples of acyloxy group, amide group, substituted amino group, substituted silyl group, arylalkenyl group which may have a substituent, arylalkynyl group which may have a substituent and substituted carboxy group It is. The number of carbon atoms in the divalent heterocyclic group is usually 2 to 60, preferably 6 to 20. The number of carbon atoms here is a carbon atom constituting a heterocyclic ring, and does not include the number of carbon atoms contained in the substituent when it has a substituent. The divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.

  The divalent heterocyclic group includes a group obtained by removing two hydrogen atoms from a monocyclic heterocyclic compound, a group obtained by removing two hydrogen atoms from a heterocyclic compound containing a condensed ring, and two or more A group obtained by removing two hydrogen atoms from a bridged polycyclic heterocyclic compound having a structure in which the above heterocyclic compounds are directly bonded or bridged by a divalent group such as a methylene group, an ethylene group or a carbonyl group. Is included.

Examples of the arylene group which may have a substituent include groups represented by Formulas 1 to 44.

In formulas 1 to 44, R represents a hydrogen atom or a substituent. When there are a plurality of Rs, the plurality of Rs may be the same or different. The definition and specific examples of the substituent represented by R are the same as the definition and specific examples of the substituent represented by R ^{1 to} R ¹⁰ described above. R has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aryloxy group, a nitro group and a cyano group which may be optionally substituted are preferable, a hydrogen atom, an alkyl group which may have a substituent and an alkoxy group which may have a substituent are more preferable, and a hydrogen atom And an alkyl group which may have a substituent is particularly preferable.

  Of the groups represented by Formula 1 to Formula 44, the group represented by Formula 1, the group represented by Formula 20, and the group represented by Formula 36 are preferred, and the group represented by Formula 1 and Formula 36 are preferred. Is more preferable, and the group represented by Formula 1 is particularly preferable.

  Examples of the divalent heterocyclic group include groups represented by Formula 101 to Formula 244.

  In formula 101 to formula 244, R represents the same meaning as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different.

Ar ¹ and Ar ² are preferably a divalent heterocyclic group from the viewpoint of improving the photoelectric conversion efficiency of the photoelectric conversion element having an active layer containing the compound of the present invention.
Examples of the divalent heterocyclic group include Formula 153, Formula 154, Formula 155, Formula 156, Formula 157, Formula 165, Formula 166, Formula 167, Formula 168, Formula 169, Formula 170, Formula 171, Formula 172, Formula 173. , Formula 175, Formula 175, Formula 176, Formula 177, Formula 178, Formula 184, Formula 190, Formula 191, Formula 192, Formula 193, Formula 194, Formula 195, Formula 196, Formula 197, Formula 198, Formula 203, Formula 208, Formula 213, Formula 218, Formula 223, Formula 228, Formula 233, and Formula 234 are preferred, and Formula 156, Formula 165, Formula 169, Formula 170, Formula 171, Formula 172, Formula 173, Formula 173 174, Formula 175, Formula 176, Formula 178, Formula 184, Formula 198, Formula 208, Formula 218, and the group represented by Formula 223 are more preferable, Formula 156, Formula 171, Formula 172, Formula 178, Formula 184, Equation 19 Formula 208, group is more preferably represented by the formula 218, and Formula 223, the group represented by the formula 156, a group represented by the formula 171, and a group represented by the formula 218 particularly preferred.

  In formula (1), p and r each independently represent an integer of 0 to 2. p is preferably 0 or 2. r is preferably 1.

（Ａ−１） （Ａ−２） A ¹ and A ² each independently represents an aryl group or a heterocyclic group which may have a substituent. However, at least one of A ¹ and A ² is a group represented by the formula (A-1) or a group represented by the formula (A-2).

(A-1) (A-2)

The definition and specific examples of the aryl group and the heterocyclic group which may have a substituent represented by A ¹ and A ² may have the substituent represented by the aforementioned R ^{1 to} R ^10. The definitions and specific examples of good aryl groups and heterocyclic groups are the same.
As the aryl group, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a fluorenyl group which may have a substituent are preferable, and the aryl group has a substituent. The phenyl group which may be substituted and the fluorenyl group which may have a substituent are more preferable, and the phenyl group which may have a substituent is particularly preferable.
The heterocyclic group is preferably an aromatic heterocyclic group, selected from the group consisting of optionally substituted furan, thiophene, pyrrole, thiazole, benzothiadiazole, quinoxaline, thienothiophene, thiazolothiazole, and thienopyrazine. A group obtained by removing one hydrogen atom bonded to the heterocyclic ring of the compound is more preferable, and bonded to the heterocyclic ring of the compound selected from the group consisting of optionally substituted thiophene, benzothiadiazole, and quinoxaline. More preferably a group in which one hydrogen atom is removed, and one hydrogen atom bonded to the heterocyclic ring of a compound selected from the group consisting of optionally substituted thiophene and benzothiadiazole is removed. And more preferably a thienyl group which may have a substituent.

In formula (A-1) and formula (A-2), W ¹ , W ² , W ³ , W ⁴ , W ⁵ , W ⁶ , W ⁷ , and W ⁸ are each independently a hydrogen atom or a fluorine atom Or an alkyl group which may have a substituent. From the viewpoint of improving the stability of the compound, both A ¹ and A ² are preferably a group represented by the formula (A-1) or a group represented by the formula (A-2).

The definition and specific examples of the alkyl group which may have a substituent represented by W ^{1 to} W ⁸ are the same as those of the alkyl group which may have a substituent represented by the aforementioned R ^{1 to} R ¹⁰ . Definitions and specific examples are the same.

In formula (A-2), Y ⁴ represents a sulfur atom, an oxygen atom, a selenium atom, or —N (R ¹¹ ) —. R ¹¹ represents a hydrogen atom or a substituent. The definition and specific examples of the substituent represented by R ¹¹ are the same as the definition and specific examples of the substituent represented by R ^{1 to} R ¹⁰ described above. Y ⁴ is preferably a sulfur atom from the viewpoint of improving the stability of the compound.

The compound of the present invention preferably has a maximum occupied orbital (HOMO) energy of −4.55 eV or less calculated using a density functional method.
Methods for calculating HOMO include quantum chemical methods such as semi-empirical molecular orbital method, density functional theory method, and ab initio molecular orbital method. From the viewpoint of calculation accuracy of energy of molecular structure and occupied orbital. The density functional method and the ab initio molecular orbital method are preferred, the density functional method is more preferred, the hybrid density functional method is more preferred, and the B3LYP method is particularly preferred. In the case of using the density functional method or the ab initio molecular orbital method, 3-21G * and 6-31G (d) are preferably used as basis functions from the viewpoint of shortening the calculation time and calculation accuracy. (D) is more preferable. As for the molecular structure, it is more preferable to obtain a stable structure by optimizing the structure. In order to perform the above calculation, a quantum chemistry calculation program package such as Gaussian 09 or GAMESS can be used. The larger the difference between the energy of the highest occupied orbit of the compound represented by the formula (1) and the energy of the lowest unoccupied orbit of the electron-accepting compound such as a fullerene derivative, the higher the open end voltage is expected. That is, as the energy of the highest occupied orbit of the compound represented by the formula (1) is smaller, it is expected that the above-described energy difference becomes larger and the open-circuit voltage becomes larger. The energy of the highest occupied trajectory is preferably −4.60 eV or less, more preferably −4.65 eV or less.

  The method for producing the compound of the present invention is not particularly limited, and a Stille coupling reaction, a Suzuki coupling reaction, a Kumada coupling reaction, a Yamamoto coupling reaction, an oxidative coupling reaction, and the like can be used. From the viewpoint of ease of synthesis of the compound, a method using a Stille coupling reaction and a method using a Suzuki coupling reaction are preferable.

（１−１）
〔式中、Ｘ^１、Ｘ^２、Ｙ^１、Ｙ^２、Ｙ^３、Ｙ^４、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｗ^６、Ｗ^７、Ｗ^８、Ａｒ^１、及びＡｒ^２は、前述と同じ意味を表す。〕 A method for producing the compound represented by formula (1-1), which is one embodiment of the compound of the present invention, will be described.

(1-1)
[Wherein X ¹ , X ² , Y ¹ , Y ² , Y ³ , Y ⁴ , R ¹ , R ² , R ³ , R ⁴ , W ⁶ , W ⁷ , W ⁸ , Ar ¹ , and Ar ² are Represents the same meaning as described above. ]

（１−２）
〔式中、Ｘ^１、Ｘ^２、Ｙ^１、Ｙ^２、Ｙ^３、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、前述と同じ意味を表す。Ｑ^１及びＱ^２は、それぞれ独立に、ハロゲン原子を表す。〕

（Ａ−３） （Ａ−４）
〔式（Ａ−３）及び（Ａ−４）中、Ｙ^４、Ｗ^６、Ｗ^７、Ｗ^８、Ａｒ^１、及びＡｒ^２は、前述と同じ意味を表し、Ｕ^１及びＵ^２は、それぞれ独立に、ホウ酸エステル残基又はジヒドロキシボリル基を表す。〕 Examples of the method for producing the compound represented by the formula (1-1) include a compound represented by the formula (1-2), a compound represented by the formula (A-3), and a formula (A-4). And a method of reacting at least one compound selected from the group consisting of compounds represented by (2) using a Suzuki coupling reaction.

(1-2)
[Wherein, X ¹ , X ² , Y ¹ , Y ² , Y ³ , R ¹ , R ² , R ³ , and R ⁴ represent the same meaning as described above. Q ¹ and Q ² each independently represents a halogen atom. ]

(A-3) (A-4)
[In formulas (A-3) and (A-4), Y ⁴ , W ⁶ , W ⁷ , W ⁸ , Ar ¹ , and Ar ² represent the same meaning as described above, and U ¹ and U ² are respectively Independently, it represents a boric acid ester residue or a dihydroxyboryl group. ]

  A compound in which the sum of the number of moles of the compound represented by formula (A-3) and the number of moles of the compound represented by formula (A-4) used in the Suzuki coupling reaction is represented by formula (1-2) It is preferable that the amount is excessive with respect to the number of moles. When the number of moles of the compound represented by formula (1-2) used in the reaction is 1 mole, the number of moles of the compound represented by formula (A-3) and the mole of the compound represented by formula (A-4) The total number is preferably 1.05 mol to 10 mol, and more preferably 1.1 mol to 5 mol.

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。）
で表される基が例示される。 The boric acid ester residue means a group obtained by removing a hydroxyl group from a boric acid diester, and examples thereof include a dialkyl ester residue, a diaryl ester residue, and a di (arylalkyl) ester residue. Specific examples of the boric acid ester residue include the following formula:

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
The group represented by these is illustrated.

Examples of the halogen atom represented by Q ¹ and Q ² in Formula (1-2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of the ease of synthesis of the compound, a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.

  Specific examples of the method for carrying out the Suzuki coupling reaction include a method in which a palladium catalyst is used as a catalyst in an arbitrary solvent and the reaction is carried out in the presence of a base.

Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetate, dichlorobis ( Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium, and dichlorobis (triphenylphosphine) palladium from the viewpoint of ease of reaction operation and reaction rate. , Palladium acetate, and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol, preferably 1 mol with respect to 1 mol of the compound represented by the formula (1-2). 0.0003 mol to 0.1 mol.

  When palladium acetate is used as the palladium catalyst used in the Suzuki coupling reaction, for example, a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine is added as a ligand. be able to. In this case, the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the palladium catalyst.

Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, and inorganic salts. Examples of the inorganic base include potassium carbonate, sodium carbonate, and barium hydroxide. Examples of the organic base include triethylamine and tributylamine. An example of the inorganic salt is cesium fluoride.
The addition amount of the base is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the compound represented by the formula (1-2).

The Suzuki coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. From the viewpoint of the solubility of the compound used in the present invention, toluene and tetrahydrofuran are preferred. Further, the base may be added as an aqueous solution and reacted in a two-phase system. When an inorganic salt is used as the base, it is usually added as an aqueous solution and reacted from the viewpoint of solubility of the inorganic salt.
In addition, when adding a base as aqueous solution and making it react with a two-phase system, you may add phase transfer catalysts, such as a quaternary ammonium salt, as needed.

  Although the temperature at which the Suzuki coupling reaction is performed depends on the solvent, it is usually 50 to 160 ° C., and 60 to 120 ° C. is preferable from the viewpoint of improving the conversion rate of the raw material compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the conversion rate of the desired product is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

  The Suzuki coupling reaction is performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the reaction system is sufficiently substituted with nitrogen gas and degassed, the compound represented by the formula (1-2), the compound represented by the formula (A-3) and / or Alternatively, the compound represented by (A-4), dichlorobis (triphenylphosphine) palladium (II) is charged, and the air in the container is sufficiently substituted with nitrogen gas, deaerated, and then bubbled with nitrogen gas in advance. After adding a degassed solvent, for example, toluene, to this solution, a base degassed by bubbling with nitrogen gas in advance, for example, an aqueous sodium carbonate solution was dropped, and then heated, heated, for example, The reaction is carried out at the reflux temperature for 8 hours while maintaining an inert atmosphere.

  The reaction product obtained by the above reaction is subjected to usual post-treatment such as, for example, extraction with an organic solvent after dilution by adding water, and distillation of the solvent in the organic layer, and the formula (1-1) ) Can be obtained. Isolation and purification of the reaction product can be performed by a method such as fractionation by chromatography or recrystallization.

（１−３）
〔式中、Ｙ^１、Ｙ^２、Ｚ、Ｒ^１、及びＲ^２は、前述と同じ意味を表す。Ｔ¹及びＴ²は、それぞれ独立に、置換スタンニル基を表す。〕

（１−４）
〔式中、Ｘ^１、Ｘ^２、Ｙ^３、Ｒ^３、Ｒ^４、Ｑ^１及びＱ^２は、前述と同じ意味を表す。〕 As a method for producing the compound represented by the formula (1-2), for example, a compound represented by the formula (1-3) and a compound represented by the formula (1-4) The method of making it react using Stille coupling reaction in presence is mentioned.

(1-3)
[Wherein Y ¹ , Y ² , Z, R ¹ , and R ² represent the same meaning as described above. T ¹ and T ² each independently represents a substituted stannyl group. ]

(1-4)
[Wherein, X ¹ , X ² , Y ³ , R ³ , R ⁴ , Q ¹ and Q ² represent the same meaning as described above. ]

Examples of the substituted stannyl group include a group represented by —SnR ¹⁰⁰ ₃ . Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group and an aryl group.
The number of carbon atoms of the alkyl group is usually 1-30. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl. Group, hexyl group, isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl And chain alkyl groups such as a group, tetradecyl group, hexadecyl grave, octadecyl group, and eicosyl group, and cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Specific examples of the aryl group include a phenyl group and a naphthyl group. Preferably -SnMe ₃ as a substituent stannyl group, -SnEt _3, a -SnBu _3, and -SnPh _3, more preferably -SnMe _3, -SnEt _3, and is -SnBu _3. In the above preferred examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Specifically, examples of the catalyst include a method of reacting in an arbitrary solvent under a palladium catalyst.
Examples of the palladium catalyst used in the Stille coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specific examples include palladium [tetrakis (triphenylphosphine)], palladium acetate, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium. From the viewpoint of ease of reaction operation and reaction rate, palladium [tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferable.
The addition amount of the palladium catalyst used in the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (1-4). Mol to 0.5 mol, preferably 0.0003 to 0.2 mol.

Moreover, in a Stille coupling reaction, a ligand and a co-catalyst can also be used as needed. Examples of the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, triphenylarsine, and triphenoxyarsine. Examples include arsenic compounds. Cocatalysts include copper iodide, copper bromide, copper chloride, and copper (I) 2-thenoylate.
When using a ligand or a cocatalyst, the amount of the ligand or cocatalyst added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably, relative to 1 mol of the palladium catalyst. 1 mol to 10 mol.

  The Stille coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, and tetrahydrofuran. From the viewpoint of the solubility of the compound used in the present invention, toluene and tetrahydrofuran are preferred.

The temperature at which the Stille coupling reaction is performed depends on the solvent, but is usually 50 to 160 ° C, preferably 60 to 120 ° C. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for performing the reaction (reaction time) may be the end point when the target conversion rate is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

  The Stille coupling reaction is performed in a reaction system in which the Pd catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the reaction system is sufficiently substituted with nitrogen gas and deaerated, the compound represented by the formula (1-3), the compound represented by the formula (1-4), palladium, The catalyst is charged, and the container is sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent, for example, toluene. A co-catalyst is added, and then heated and heated, for example, at a reflux temperature for 8 hours while maintaining an inert atmosphere.

  The reaction product obtained by the above reaction is subjected to normal post-treatment such as, for example, extraction with an organic solvent after dilution by adding water, and evaporation of the solvent in the organic layer. ) Can be obtained. Isolation and purification of the reaction product can be performed by a method such as fractionation by chromatography or recrystallization.

  Since the compound of the present invention can exhibit high electron and / or hole transport properties, when a thin film containing the compound is used in an element, electrons or holes injected from an electrode, or charges generated by light absorption. Can be transported. Taking advantage of these characteristics, it can be suitably used for various electronic devices such as a photoelectric conversion device, an organic thin film transistor, and an organic electroluminescence device. Hereinafter, these elements will be described individually.

<Photoelectric conversion element>
The photoelectric conversion element of the present invention has one or more active layers containing the compound of the present invention between the first electrode and the second electrode.
The photoelectric conversion element of the present invention is a photoelectric conversion element having a pair of electrodes, at least one of which is transparent or translucent, and an active layer formed from an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. preferable. The compound of the present invention is preferably used as a p-type organic semiconductor.

  In another aspect of the photoelectric conversion element of the present invention, a first active layer containing the compound of the present invention is interposed between a pair of electrodes, at least one of which is transparent or translucent, and adjacent to the first active layer. And a photoelectric conversion element including a second active layer containing an electron-accepting compound such as a fullerene derivative.

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

Examples of the material for the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA , Gold, platinum, silver, and copper, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
As the electrode, a transparent conductive film formed from an organic compound such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used.

  One electrode may not be transparent, and examples of the material of the electrode include metals and conductive polymers. Specific examples of electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. Selected from the group consisting of metals, alloys of two or more of those metals, one or more of those metals, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin And alloys with one or more metals, graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  As a means for improving the photoelectric conversion efficiency, an additional intermediate layer other than the active layer may be used. Materials used for the intermediate layer include alkali metal or alkaline earth metal halides such as lithium fluoride, oxides such as titanium oxide, PEDOT (poly- (3,4-ethylenedioxythiophene-2,5- Diyl)) and the like.

<Active layer>
The active layer may contain the compound of the present invention alone or in combination of two or more. Moreover, in order to improve the hole transport property of the said active layer, compounds other than the compound of this invention can also be mixed and used as an electron-donating compound and / or an electron-accepting compound in the said active layer. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

  Examples of the electron donating compound include, in addition to the compound of the present invention, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, side Examples thereof include polysiloxane derivatives having an aromatic amine residue in the chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof.

Examples of the electron-accepting compound include, in addition to the compound of the present invention, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof. , Anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof , Polyfluorenes and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocuproin), fullerenes and fullerene derivatives. Ku is titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. The fullerene derivative represents a compound in which at least a part of fullerene is modified.

（Ｉ） （ＩＩ） （ＩＩＩ） （ＩＶ）

（式（Ｉ）〜（ＩＶ）中、Ｒ^ａは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基又はエステル構造を有する基を表す。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂは置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by formula (I), a compound represented by formula (II), a compound represented by formula (III), and a compound represented by formula (IV). .

(I) (II) (III) (IV)

(In the formulas (I) to (IV), R ^a is an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl which may have a substituent. A group having a group or an ester structure, a plurality of R ^a may be the same or different, and R ^b has an alkyl group which may have a substituent or a substituent; (A plurality of R ^b may be the same or different.)

The definition and specific examples of the aryl group, which may have an alkyl group which may have a substituent represented by R ^a and R ^b and a substituent, are represented by the aforementioned R ^{1 to} R ^10. The definition and specific examples of the alkyl group which may have a substituent and the aryl group which may have a substituent are the same.

Examples of the heteroaryl group represented by ^Ra include a thiophenediyl group, a pyridinediyl group, a furandiyl group, and a pyrrolediyl group.

（Ｖ）
（式中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基又は置換基を有していてもよいヘテロアリール基を表す。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (V).

(V)
(In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c may have an alkyl group which may have a substituent, or a substituent. It represents a heteroaryl group which may have a good aryl group or substituent.)

Definitions and specific examples of the alkyl group that may have a substituent represented by R ^c , the aryl group that may have a substituent, and the heteroaryl group that may have a substituent include R The definition and specific examples of the alkyl group that may have a substituent represented by ^a , the aryl group that may have a substituent, and the heteroaryl group that may have a substituent are the same. .

Specific examples of the C ₆₀ derivative include the following compounds.

Specific examples of the C ₇₀ derivative include the following compounds.

  Examples of fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] phenyl-C71 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), [6,6] thienyl- Examples thereof include C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).

When using the compound of this invention for a photoelectric conversion element, it is preferable to use the composition containing the compound of this invention and an electron-accepting compound for the active layer of a photoelectric conversion element. When the active layer contains the compound of the present invention and the electron-accepting compound, the amount of the electron-accepting compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the compound of the present invention, and 20 to 500 parts by weight. Is more preferable.
As an electron-accepting compound, a fullerene derivative is preferable. When the compound of the present invention and the fullerene derivative are included in the active layer, the amount of the fullerene derivative is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, with respect to 100 parts by weight of the compound of the present invention.

  The thickness of the active layer is preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, further preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

  The method for producing the active layer may be produced by any method, and examples thereof include a film formation from a solution containing a compound and a solvent, and a film formation method by a vacuum deposition method.

<Method for producing photoelectric conversion element>
A preferred method for producing a photoelectric conversion element is a method for producing an element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode, An element having a step of forming an active layer by applying a solution (ink) containing the compound of the present invention and a solvent on the first electrode by a coating method, and a step of forming a second electrode on the active layer It is a manufacturing method.

  The solvent used for film formation from a solution may be any that dissolves the compound of the present invention. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Examples thereof include halogenated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. The compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Application methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, capillary coating, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an inkjet coating method and a spin coating method are preferred.
From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

<Application of photoelectric conversion element>
The photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by irradiating light such as sunlight to generate a photovoltaic force between the electrodes. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  Further, by irradiating light with a voltage applied between the electrodes or without applying a voltage, a photocurrent flows, and the organic light sensor can be operated. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

<Solar cell module>
The organic thin film solar cell can basically have the same module structure as a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. The organic thin-film solar cell produced using the compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, the place of use and the environment.

In a typical super straight type or substrate type module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. The current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside. Depending on the purpose, various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or filled resin in order to protect the cell and improve the current collection efficiency. In addition, when used in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side.
The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. A module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 can also be used. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

<Organic thin film transistor>
The compound of the present invention can also be used for organic thin film transistors. The organic thin film transistor has a configuration including a source electrode and a drain electrode, an active layer (organic semiconductor layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path And the compound of the present invention is contained in the active layer. Examples of the organic thin film transistor include a field effect organic thin film transistor and an electrostatic induction organic thin film transistor.

A field effect organic thin film transistor includes a source electrode and a drain electrode, an active layer (organic semiconductor layer) serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode. It is preferable to provide an insulating layer disposed between the two.
In particular, the source electrode and the drain electrode are preferably provided in contact with the active layer, and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween. In the field effect organic thin film transistor, the active layer is composed of an organic thin film containing the compound of the present invention.

  The electrostatic induction organic thin film transistor has a source electrode and a drain electrode, an active layer (organic semiconductor layer) serving as a current path between them, and a gate electrode for controlling the amount of current passing through the current path. It is preferable to be provided in the active layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the active layer are preferably provided in contact with the active layer. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned. Also in the static induction organic thin film transistor, the active layer is constituted by an organic thin film containing the compound of the present invention.

  The organic thin film transistor can be used, for example, as a pixel driving element used for controlling a pixel of an electrophoretic display, a liquid crystal display, an organic electroluminescence display or the like, and controlling the uniformity of screen luminance and the screen rewriting speed.

<Organic electroluminescence device>
The compound of this invention can also be used for an organic electroluminescent element (organic EL element). The organic EL element has a light emitting layer between the first electrode and the second electrode. The organic EL element may include a hole transport layer and an electron transport layer in addition to the light emitting layer. The compound of the present invention is contained in any one of the light emitting layer, the hole transport layer, and the electron transport layer. In addition to the compound of the present invention, the light emitting layer may contain a charge transport material (which means a generic term for an electron transport material and a hole transport material). As an organic EL element, an element having an anode, a light emitting layer, and a cathode, and an anode, a light emitting layer, and an electron having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer. An element having a transport layer and a cathode, and an anode, a hole transport layer, a light emitting layer, and a cathode having a hole transport layer containing a hole transport material adjacent to the light emitting layer between the anode and the light emitting layer. And an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. At least one of the first electrode and the second electrode is preferably transparent or translucent.

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

化合物１ 化合物２ 化合物３

内部の空気をアルゴンで置換した１００ｍＬフラスコに、特開２０１２−３６３５７号公報の実施例５３に記載された方法により合成した化合物１を５００ｍｇ（０．４７５ｍｍｏｌ）、特開２０１２−３６３５７号公報の参考例１４に記載された方法により合成した化合物２を３９３ｍｇ（１．１９ｍｍｏｌ）、トリス(２−トリル)ホスフィンを１３．０ｍｇ（０．０４２６ｍｍｏｌ）、脱水トルエンを１０ｍｌ入れた。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを６．５ｍｇ（０．００７１ｍｍｏｌ）加え、１０５℃で６時間攪拌した。その後、フラスコを室温までに冷却し、有機層を水５０ｍＬで２回洗浄した。有機層を硫酸ナトリウムで乾燥させ、濾過した後、エバポレーターで溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィで精製して化合物３を２０９ｍｇ得た。 Example 1
(Synthesis of Compound 3)

Compound 1 Compound 2 Compound 3

500 mg (0.475 mmol) of Compound 1 synthesized by the method described in Example 53 of JP2012-36357A, a reference of JP2012-36357A, to a 100 mL flask in which the internal air was replaced with argon. 393 mg (1.19 mmol) of Compound 2 synthesized by the method described in Example 14, 13.0 mg (0.0426 mmol) of tris (2-tolyl) phosphine, and 10 ml of dehydrated toluene were added. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 6.5 mg (0.0071 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, and the mixture was stirred at 105 ° C. for 6 hours. Thereafter, the flask was cooled to room temperature, and the organic layer was washed twice with 50 mL of water. The organic layer was dried over sodium sulfate and filtered, and then the solvent was distilled off with an evaporator. The obtained residue was purified by silica gel column chromatography to obtain 209 mg of Compound 3.

内部の空気をアルゴンで置換した１００ｍＬフラスコに、化合物３を２００ｍｇ（０．２０６ｍｍｏｌ）、化合物４（シグマアルドリッチ社製）を５７１ｍｇ（１．５２ｍｍｏｌ）、メチルトリアルキルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、シグマアルドリッチ社製）を５０ｍｇ加え、トルエン２０ｍＬに溶解させ、得られたトルエン溶液をアルゴンで３０分バブリングした。その後、酢酸パラジウムを０．６７ｍｇ、トリス(２−メトキシフェニル)ホスフィンを３．７ｍｇ、１６．７重量％の炭酸ナトリウム水溶液を２ｍＬ加え、１００℃で６時間攪拌を行った。分液ロートを用いて水層を除去した後、有機層を水で２回洗浄した。有機層を硫酸ナトリウムで乾燥させ、濾過した後、エバポレーターで溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィで精製して化合物５を２２０ｍｇ得た。 Example 2
(Synthesis of Compound 5)

In a 100 mL flask in which the air inside was replaced with argon, 200 mg (0.206 mmol) of compound 3, 571 mg (1.52 mmol) of compound 4 (manufactured by Sigma-Aldrich), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark)) ), 50 mg of Sigma-Aldrich) was added and dissolved in 20 mL of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 0.67 mg of palladium acetate, 3.7 mg of tris (2-methoxyphenyl) phosphine, and 2 mL of 16.7 wt% sodium carbonate aqueous solution were added, and the mixture was stirred at 100 ° C. for 6 hours. After removing the aqueous layer using a separatory funnel, the organic layer was washed twice with water. The organic layer was dried over sodium sulfate and filtered, and then the solvent was distilled off with an evaporator. The obtained residue was purified by silica gel column chromatography to obtain 220 mg of compound 5.

Example 3
(Production and evaluation of organic thin-film solar cells)
[6,6] phenyl-C71 butyric acid methyl ester (C70PCBM) (trade name: ADS71BFA, lot number: 10E39E), which is an electron-accepting compound, and compound 5, which is an electron-donating compound, The mixture was mixed so that the weight ratio of C70PCBM to the weight of Compound 5 was 2, and dissolved in o-dichlorobenzene so that the concentration of the mixture was 1.5% by weight. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.5 μm to prepare a coating solution 1.

A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering was washed with an ultraviolet ozone battlefield apparatus and subjected to surface treatment. Next, a liquid (PEDOT: PSS liquid) containing poly (3,4-ethylenedioxythiophene-2,5-diyl) and polystyrene sulfonic acid (manufactured by Heraeus, CleviosP VP AI4083) is spin coated on the ITO film. And heated at 120 ° C. for 10 minutes in the atmosphere to form a hole injection layer having a thickness of 50 nm. Next, the coating solution 1 was applied onto the hole injection layer by spin coating to obtain an active layer. The thickness of the active layer was 100 nm. Then, the organic thin film solar cell was produced by vapor-depositing calcium with a film thickness of 4 nm on an active layer with a vacuum evaporation machine, and vapor-depositing aluminum with a film thickness of 100 nm then. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa. The shape of the obtained organic thin film solar cell was a square of 2 mm × 2 mm. The obtained organic thin film solar cell was irradiated with constant light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.), and the generated voltage was measured. The open circuit voltage was 0.79V.

Example 4
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was prepared in the same manner as in Example 3 except that the weight ratio of C70PCBM to the weight of compound 5 was 3/7, and the concentration of the mixture in the solution was 2.14% by weight. The end voltage was measured. The open circuit voltage was 0.84V.

内部の空気をアルゴンで置換した四つ口フラスコに、化合物６を４６６．８ｍｇ（０．３００ｍｍｏｌ）、テトラヒドロフランを２０ｍＬ加え、均一な溶液とし、室温（２５℃）で、３０分間アルゴンでバブリングを行った。その後、トリス（ジベンジリデンアセトン）パラジウムを１３．７４ｍｇ（０．０１５ｍｍｏｌ）、［トリ（ターシャリーブチル）ホスホニウム］テトラフルオロボレートを１７．４１ｍｇ（０．０６０ｍｍｏｌ）、３ｍｏｌ／Ｌのリン酸カリウム水溶液を１．０ｍＬ（３．０ｍｍｏｌ）加えた。６０℃に加熱したオイルバスにフラスコを浸し、攪拌しながら、フェニルボロン酸７３．２ｍｇ（０．６００ｍｍｏｌ）をテトラヒドロフラン（１０ｍＬ）に溶かした溶液を５分かけて滴下した。１時間後、液体クロマトグラフィーにより原料の消失を確認した。反応液に水を加え、有機層をヘキサンで抽出し、展開溶媒にヘキサンを用いたカラムで精製を行い、その後、乾燥させて化合物７を３９０ｍｇ得た。 Example 5
(Synthesis of Compound 7)

466.8 mg (0.300 mmol) of compound 6 and 20 mL of tetrahydrofuran were added to a four-necked flask whose internal air was replaced with argon, to obtain a homogeneous solution, and bubbled with argon at room temperature (25 ° C.) for 30 minutes. It was. Thereafter, 13.74 mg (0.015 mmol) of tris (dibenzylideneacetone) palladium, 17.41 mg (0.060 mmol) of [tri (tertiary butyl) phosphonium] tetrafluoroborate, 3 mol / L potassium phosphate aqueous solution were added. 1.0 mL (3.0 mmol) was added. The flask was immersed in an oil bath heated to 60 ° C., and a solution obtained by dissolving 73.2 mg (0.600 mmol) of phenylboronic acid in tetrahydrofuran (10 mL) was added dropwise over 5 minutes while stirring. After 1 hour, disappearance of the raw material was confirmed by liquid chromatography. Water was added to the reaction solution, the organic layer was extracted with hexane, purified with a column using hexane as a developing solvent, and then dried to obtain 390 mg of Compound 7.

Example 6
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 3 except that Compound 7 was used instead of Compound 5, and the open-circuit voltage was measured. The open circuit voltage was 0.80V.

化合物８ 化合物９
フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、化合物８を５６１ｍｇ（１．００ｍｍｏｌ）、化合物９（シグマアルドリッチ社製）を３８８．１ｍｇ（１．００ｍｍｏｌ）、メチルトリアルキルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、シグマアルドリッチ社製）を２０２ｍｇ加え、トルエン２０ｍｌに溶解させ、得られたトルエン溶液をアルゴンで３０分バブリングした。その後、反応液に酢酸パラジウムを２．２５ｍｇ、トリス(２−メトキシフェニル)ホスフィンを１２．３ｍｇ、１６．７重量％の炭酸ナトリウム水溶液を６．５ｍＬ加え、１００℃で５時間攪拌を行った。その後、反応液にフェニルホウ酸５０ｍｇを加え、さらに７０℃で２時間反応させた。その後、反応液にジエチルジチオカルバミン酸ナトリウム２ｇと水２０ｍＬを加え、２時間還流下で攪拌を行った。水層を除去後、有機層を水２０ｍｌで２回洗浄し、次いで、３重量%の酢酸水溶液２０ｍＬで２回洗浄し、さらに水２０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、得られたポリマーをｏ−ジクロロベンゼン３０ｍＬに溶解させ、アルミナ／シリカゲルカラムに通し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、精製された重合体を２８０ｍｇ得た。以下、この重合体を高分子化合物Ａと呼称する。ＧＰＣで測定した高分子化合物Ａのポリスチレン換算の分子量は、重量平均分子量が３００００であり、数平均分子量が１４０００であった。 Reference example 1
(Synthesis of polymer compound A)

Compound 8 Compound 9
In a 200 mL flask in which the gas in the flask was replaced with argon, 561 mg (1.00 mmol) of Compound 8, 388.1 mg (1.00 mmol) of Compound 9 (manufactured by Sigma-Aldrich), methyltrialkylammonium chloride (trade name Aliquat 336) (Registered Trademark, manufactured by Sigma-Aldrich) (202 mg) was added and dissolved in 20 ml of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine, and 6.5 mL of a 16.7 wt% aqueous sodium carbonate solution were added to the reaction solution, followed by stirring at 100 ° C. for 5 hours. Thereafter, 50 mg of phenylboric acid was added to the reaction solution, and the mixture was further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added to the reaction solution, followed by stirring under reflux for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 20 ml of water, then twice with 20 mL of a 3% by weight acetic acid aqueous solution and further twice with 20 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved in 30 mL of o-dichlorobenzene, passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate the polymer. The polymer was filtered and dried to obtain 280 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A. The molecular weight in terms of polystyrene of the polymer compound A measured by GPC was a weight average molecular weight of 30,000 and a number average molecular weight of 14,000.

Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 3 except that the polymer compound A was used instead of the compound 5, and the open-circuit voltage was measured. The open circuit voltage was 0.60V.

Calculation example 1
A structure optimization calculation was performed on compound 5, a stable structure was obtained, and the energy of the highest occupied orbit of compound 5 was calculated. As a method for obtaining the energy of the highest occupied orbit, the B3LYP method, which is a hybrid density functional method, was used, and 6-31G (d) was used as the basis function. As the calculation software, Gaussian09 (manufactured by Gaussian Inc.) was used. The energy of the highest occupied orbit of Compound 5 was −4.59 eV.

Calculation example 2
Similar to compound 5, structure optimization calculation was performed on compound 7, a stable structure was obtained, and the energy of the highest occupied orbit of compound 7 was calculated. As a method for obtaining the energy of the highest occupied orbit, the B3LYP method, which is a hybrid density functional method, was used, and 6-31G (d) was used as the basis function. As the calculation software, Gaussian09 (manufactured by Gaussian Inc.) was used. The energy of the highest occupied orbit of Compound 7 was −4.71 eV.

Claims (16)

The compound represented by Formula (1).

(1)
[In ^the formula (1), ^{X 1} and ^{X 2} each independently represent a nitrogen atom or = CH-. Y ¹ and Y ² each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R ⁵ ) —. Y ³ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 5)} - represents a - or ^-CR 6 = CR ^7. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a direct bond, —C (R ⁸ ) (R ⁹ ) — or —N (R ¹⁰ ) —. R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. q represents an integer of 1 to 3. When there are a plurality of Y ¹ , they may be the same or different. When there are a plurality of Y ² , they may be the same or different. When there are a plurality of Y ³ , they may be the same or different. When there are a plurality of Z, they may be the same or different. When there are a plurality of R ^{1 s} , they may be the same or different. When there are a plurality of R ^{2 s} , they may be the same or different. When there are a plurality of R ³ , they may be the same or different. When there are a plurality of R ⁴ , they may be the same or different. When there are a plurality of X ¹ , they may be the same or different. If X ² is in plurality, they may be the same or different. Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group which may have a substituent. p and r each independently represents an integer of 0 to 2. When p is 2, two Ar ¹ may be the same or different. When r is 2, two Ar ² may be the same or different. A ¹ and A ² each independently represents an aryl group or a heterocyclic group which may have a substituent. However, at least one of A ¹ and A ² is a group represented by the formula (A-1) or a group represented by the formula (A-2).

(A-1) (A-2)
(In Formula (A-1) and Formula (A-2), W ^{1 to} W ⁸ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group that may have a substituent. Y ⁴ Represents a sulfur atom, an oxygen atom, a selenium atom, or —N (R ¹¹ ) —, where R ¹¹ represents a hydrogen atom or a substituent.   The compound according to claim 1, wherein the energy of the highest occupied orbit calculated using a density functional method is −4.55 eV or less.   The compound according to claim 1 or 2, wherein Z is an oxygen atom. The compound according to any one of claims 1 to 3, wherein both R ³ and R ⁴ are fluorine atoms. Both A < ¹ > and A < ² > are group represented by the group represented by Formula (A-1), or Formula (A-2), The compound as described in any one of Claims 1-4.   The thin film containing the compound as described in any one of Claims 1-5.   A composition comprising the compound according to any one of claims 1 to 5 and an electron-accepting compound.   The composition according to claim 7, wherein the electron-accepting compound is a fullerene derivative.   A thin film comprising the composition according to claim 7 or 8.   The solution containing the compound as described in any one of Claims 1-5, or the composition of Claim 7 or 8, and a solvent.   It has a 1st electrode and a 2nd electrode, An active layer is provided between this 1st electrode and this 2nd electrode, This active layer is as described in any one of Claims 1-5. An electronic device comprising the compound according to claim 7 or the composition according to claim 7 or 8.   The electronic device according to claim 11, which is a photoelectric conversion device.   A solar cell module provided with the photoelectric conversion element of Claim 12.   An image sensor comprising the photoelectric conversion element according to claim 12.   A gate electrode, a source electrode, a drain electrode, and an active layer are provided, and the compound according to any one of claims 1 to 5 or the composition according to claim 7 or 8 is provided in the active layer. Contains organic thin film transistor. A compound represented by formula (1-2).

(1-2)
[Wherein, X ¹ and X ² each independently represent a nitrogen atom or ═CH—. Y ¹ and Y ² each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R ⁵ ) —. Y ³ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 5)} - represents a - or ^-CR 6 = CR ^7. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a direct bond, —C (R ⁸ ) (R ⁹ ) — or —N (R ¹⁰ ) —. R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. Two R ³ may be the same or different. Two R ⁴ may be the same or different. Two X ¹ may be the same or different. Two X ² may be the same or different. Two Y ³ may be the same or different. Q ¹ and Q ² each independently represents a halogen atom. ]