JP2011116963A - Compound and element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound in which the light absorption terminal wavelength is a long wavelength. <P>SOLUTION: The compound includes a structure unit represented by formula (1) wherein Ar<SP>1</SP>and Ar<SP>2</SP>represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, provided that, at least one of Ar<SP>1</SP>and Ar<SP>2</SP>is a trivalent heterocyclic group, Z<SP>1</SP>and Z<SP>2</SP>are the same or different and represent -O-, -S-, -C(R<SP>1</SP>)(R<SP>2</SP>)-, -Si(R<SP>3</SP>)(R<SP>4</SP>)-, -N(R<SP>5</SP>)-, -B(R<SP>6</SP>)-, -P(R<SP>7</SP>)-, -P(=O)(R<SP>8</SP>)-, -Se(R<SP>9</SP>)(R<SP>10</SP>)-, -CO-, -SO<SB>2</SB>- or -C(R<SP>11</SP>)=C(R<SP>12</SP>)-, n represents an integer of 1 or more, and m represents an integer of 0 or more. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a compound having a specific structure and a 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, it has been proposed to switch to a solar system using a pn-junction type silicon solar cell on the roof of a house. The single crystal, polycrystalline and amorphous silicon used in the silicon solar cell are manufactured in the process of However, there is a problem that high temperature and high vacuum conditions are required.

  On the other hand, organic thin-film solar cells have been attracting attention in recent years because they can omit the high-temperature and high-vacuum processes used in the manufacturing process of silicon-based electronic elements and can be manufactured at low cost by only the coating process. As a polymer compound used for an organic thin film solar cell, a polymer compound composed of a repeating unit (A) and a repeating unit (B) is described (Non-Patent Document 1).

繰り返し単位（Ａ） 繰り返し単位（Ｂ）

Repeating unit (A) Repeating unit (B)

Applied Physics Letters Vol. 84, No. 10 1653-1655 (2004).

  However, the polymer compound has a short light absorption terminal wavelength, and the wavelength range of sunlight that can be absorbed is not sufficient.

  An object of this invention is to provide the compound whose light absorption terminal wavelength is a long wavelength.

（１）
〔式中、Ａｒ^１及びＡｒ^２は、同一又は相異なり、３価の芳香族炭化水素基又は３価の複素環基を表す。ただし、Ａｒ^１、Ａｒ^２のうち少なくとも一方は３価の複素環基である。Ｚ^１及びＺ^２は、同一又は相異なり、−Ｏ−、−Ｓ−、−Ｃ（Ｒ^１）（Ｒ^２）−、−Ｓｉ（Ｒ^３）（Ｒ^４）−、−Ｎ（Ｒ^５）−、−Ｂ（Ｒ^６）−、−Ｐ（Ｒ^７）−、−Ｐ（＝Ｏ）（Ｒ^８）−、−Ｓe（Ｒ^９）（Ｒ^１０）−、−ＣＯ−、−ＳＯ_２−又は−Ｃ（Ｒ^１１）＝Ｃ（Ｒ^１２）−を表す。Ｒ^１〜Ｒ^１２、Ｘ^１及びＸ^２は、同一又は相異なり、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、複素環オキシ基、複素環チオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基又はシアノ基を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。Ｚ^１が複数個ある場合、それらは同一であっても相異なってもよい。Ｚ^２が複数個ある場合、それらは同一であっても相異なってもよい。〕 That is, the present invention first provides a compound containing the structural unit represented by the formula (1).

(1)
[Wherein, Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group. However, at least one of Ar ¹ and Ar ² is a trivalent heterocyclic group. Z ¹ and Z ² are the same or different and are —O—, —S—, —C (R ¹ ) (R ² ) —, —Si (R ³ ) (R ⁴ ) —, —N (R ⁵ ). ^{-, - B (R 6)} -, - P (R 7) -, - P (= O) (R 8) -, - Se (R 9) (R 10) -, - CO -, - SO 2 - Or -C (R < ¹¹ >) = C (R < ¹² >)-is represented. R ^{1 to} R ¹² , X ¹ and X ² are the same or different and are a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyl. Oxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, It represents a heterocyclic oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, or a cyano group. n represents an integer of 1 or more, and m represents an integer of 0 or more. When there are a plurality of Z ¹ , they may be the same or different. When there are a plurality of Z ² , they may be the same or different. ]

  Secondly, the present invention provides a thin film containing the compound.

  Thirdly, the present invention provides a composition comprising the compound.

  Fourthly, the present invention provides a thin film containing the composition.

  Fifth, the present invention provides an ink containing the composition and a solvent.

  Sixth, the present invention includes a first electrode and a second electrode, an active layer between the first electrode and the second electrode, and the active layer containing the compound. An element is provided.

  Seventhly, this invention provides the said element which is a photoelectric conversion element.

  Eighth, the present invention provides an image sensor including the element.

  The compound of the present invention is extremely useful because the light absorption terminal wavelength is a long wavelength.

  Hereinafter, the present invention will be described in detail.

〔式中、Ａｒ^１及びＡｒ^２は、同一又は相異なり、３価の芳香族炭化水素基又は３価の複素環基を表す。ただし、Ａｒ^１、Ａｒ^２のうち少なくとも一方は３価の複素環基である。Ｚ^１及びＺ^２は、同一又は相異なり、−Ｏ−、−Ｓ−、−Ｃ（Ｒ^１）（Ｒ^２）−、−Ｓｉ（Ｒ^３）（Ｒ^４）−、−Ｎ（Ｒ^５）−、−Ｂ（Ｒ^６）−、−Ｐ（Ｒ^７）−、−Ｐ（＝Ｏ）（Ｒ^８）−、−Ｓe（Ｒ^９）（Ｒ^１０）−、−ＣＯ−、−ＳＯ_２−又は−Ｃ（Ｒ^１１）＝Ｃ（Ｒ^１２）−を表す。Ｒ^１〜Ｒ^１２、Ｘ^１及びＸ^２は、同一又は相異なり、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、複素環オキシ基、複素環チオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基又はシアノ基を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。Ｚ^１が複数個ある場合、それらは同一であっても相異なってもよい。Ｚ^２が複数個ある場合、それらは同一であっても相異なってもよい。〕 The compound of this invention has the structural unit represented by Formula (1), It is characterized by the above-mentioned.

[Wherein, Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group. However, at least one of Ar ¹ and Ar ² is a trivalent heterocyclic group. Z ¹ and Z ² are the same or different and are —O—, —S—, —C (R ¹ ) (R ² ) —, —Si (R ³ ) (R ⁴ ) —, —N (R ⁵ ). ^{-, - B (R 6)} -, - P (R 7) -, - P (= O) (R 8) -, - Se (R 9) (R 10) -, - CO -, - SO 2 - Or -C (R < ¹¹ >) = C (R < ¹² >)-is represented. R ^{1 to} R ¹² , X ¹ and X ² are the same or different and are a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyl. Oxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, It represents a heterocyclic oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, or a cyano group. n represents an integer of 1 or more, and m represents an integer of 0 or more. When there are a plurality of Z ¹ , they may be the same or different. When there are a plurality of Z ² , they may be the same or different. ]

  Here, the alkyl group may be linear or branched, and may be a cycloalkyl group. Carbon number of an alkyl group is 1-30 normally. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, n-pentyl group, isopentyl group, 2- Methylbutyl group, 1-methylbutyl group, n-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, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group and other chain alkyl groups, cyclopentyl group, cyclohexyl group, adamantyl group and other cycloalkyl groups Can be mentioned.

  The alkyloxy group may be linear or branched, and may be a cycloalkyloxy group. The alkyloxy group may have a substituent. The carbon number of the alkyloxy group is usually about 1 to 20, and specific examples of the alkyloxy group include methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, butoxy group, iso-butoxy group, tert -Butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, tri Examples include a fluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyl group, a perfluorooctyl group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

  The alkylthio group may be linear or branched, and may be a cycloalkylthio group. The alkylthio group may have a substituent. Carbon number of the alkylthio group is usually about 1 to 20, and specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, iso-propylthio group, butylthio group, iso-butylthio group, tert-butylthio group, Examples include pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, and trifluoromethylthio group.

  The aryl group usually has about 6 to 60 carbon atoms and may have a substituent. Specific examples of the aryl group include a phenyl group and a C1 to C12 alkyloxyphenyl group (C1 to C12 alkyl is an alkyl having 1 to 12 carbon atoms. The C1 to C12 alkyl is preferably a C1 to C8 alkyl. More preferably C1-C6 alkyl, C1-C8 alkyl indicates alkyl having 1 to 8 carbon atoms, and C1-C6 alkyl indicates alkyl having 1 to 6 carbon atoms. Specific examples of C1 to C12 alkyl, C1 to C8 alkyl, and C1 to C6 alkyl include those described and exemplified for the above alkyl group, and the same applies to the following.), C1 to C12 alkylphenyl group, 1 -A naphthyl group, 2-naphthyl group, a pentafluorophenyl group is mentioned.

  The aryloxy group usually has about 6 to 60 carbon atoms and may have a substituent on the aromatic ring. Specific examples of the aryloxy group include a phenoxy group, a C1-C12 alkyloxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.

  The arylthio group usually has about 6 to 60 carbon atoms and may have a substituent on the aromatic ring. Specific examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

  The arylalkyl group usually has about 7 to 60 carbon atoms and may have a substituent. Specific examples of the arylalkyl group include a phenyl-C1-C12 alkyl group, a C1-C12 alkyloxyphenyl-C1-C12 alkyl group, a C1-C12 alkylphenyl-C1-C12 alkyl group, and a 1-naphthyl-C1-C12 alkyl group. Group, 2-naphthyl-C1-C12 alkyl group.

  The arylalkyloxy group usually has about 7 to 60 carbon atoms and may have a substituent. Specific examples of the arylalkyloxy group include phenyl-C1-C12 alkyloxy group, C1-C12 alkyloxyphenyl-C1-C12 alkyloxy group, C1-C12 alkylphenyl-C1-C12 alkyloxy group, 1-naphthyl- A C1-C12 alkyloxy group and a 2-naphthyl-C1-C12 alkyloxy group are mentioned.

  The arylalkylthio group usually has about 7 to 60 carbon atoms and may have a substituent. Specific examples of the arylalkylthio group include a phenyl-C1-C12 alkylthio group, a C1-C12 alkyloxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, and a 1-naphthyl-C1-C12 alkylthio group. Group, 2-naphthyl-C1-C12 alkylthio group.

  The acyl group usually has about 2 to 20 carbon atoms. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 20 carbon atoms. 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.

  The amide group usually has about 2 to 20 carbon atoms. An amide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an amide. Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

  An acid imide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide. Specific examples of the acid imide group include a succinimide group and a phthalimide group.

  The substituted amino group usually has about 1 to 40 carbon atoms. Specific examples of the substituent 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 al Ruoxyphenylamino group, di (C1-C12 alkyloxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkyloxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 Alkylamino group, di (C1-C12 alkyloxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group, 2- Naphthyl-C1-C 2 alkylamino group.

  Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, and tribenzyl. Examples thereof include a silyl group, a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

  Examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri-iso-propylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p -Xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, tert-butyldiphenylsilyloxy group, dimethylphenylsilyloxy group and the like.

  Examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri-iso-propylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, tri-p -Xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, tert-butyldiphenylsilylthio group, dimethylphenylsilylthio group and the like.

  Examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-iso-propylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p -Xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di ( Tri-n-propylsilyl) amino group, di (tri-iso-propylsilyl) amino group, di (tert-butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-xylylsilyl) Amino group, di (tribe Jirushiriru) amino group, di (diphenylmethyl silyl) amino, di (tert- butyldiphenylsilyl) amino group, di (dimethylphenylsilyl) and amino group.

  Examples of the monovalent heterocyclic group include 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, naphthyl Quinoxaline, quinazoline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine, etc. A group obtained by removing one hydrogen atom from a compound can be mentioned. As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable.

Examples of the heterocyclic oxy group and the heterocyclic thio group include a group in which an oxygen atom or a sulfur atom is bonded to the monovalent heterocyclic group.
The heterocyclic oxy group usually has about 4 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 about 4 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.

  The arylalkenyl group usually has 7 to 20 carbon atoms, and specific examples of the arylalkenyl group include a styryl group.

  The arylalkynyl group usually has 7 to 20 carbon atoms, and specific examples of the arylalkynyl group include a phenylacetylenyl group.

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

From the viewpoint of ease of production of the monomer, X ¹ and X ² are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group or a cyano group, more preferably a hydrogen atom, an alkyl group or an aryl group. And particularly preferably a hydrogen atom or an alkyl group.

Z ¹ and Z ² are —O—, —S—, —C (R ¹ ) (R ² ) —, —Si (R ³ ) (R ⁴ ) —, —N (R ⁵ ) —, —B ( ^{R 6) -, - P (} R 7) -, - P (= O) (R 8) -, - Se (R 9) (R 10) -, - CO -, - SO 2 - or -C (R ^{11) = C (R 12)} - represents a. R ¹ to R ¹² are as defined above ^X 1, ^{X 2.} Z ¹ and Z ² are preferably —O—, —CO—, —C (R ¹ ) (R ² ) —, —C (R ¹¹ ) ═C (R ¹² ) —, more preferably —C (R ¹ ) (R ² )-, -C (R ¹¹ ) = C (R ¹² )-.
n represents an integer of 1 or more, and m represents an integer of 0 or more. n is preferably 1 to 10, more preferably 1 to 5. m is preferably 0 to 10, more preferably 0 to 5. When there are a plurality of Z ¹ , they may be the same or different. When there are a plurality of Z ² , they may be the same or different. The sum of m and n is preferably 2 or more.

Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group.
Here, the trivalent aromatic hydrocarbon group means a remaining atomic group obtained by removing 3 hydrogen atoms from a benzene ring or condensed ring, and usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. The group of is illustrated.

  The aromatic hydrocarbon group may have a substituent, and as the substituent, as described above, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, Arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, 1 Examples thereof include a valent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, arylethynyl group, carboxyl group, and cyano group. The carbon number of the trivalent aromatic hydrocarbon group does not include the carbon number of the substituent.

  A trivalent heterocyclic group means the remaining atomic group which remove | excluded three hydrogen atoms from the heterocyclic compound, and carbon number is 4-60 normally, Preferably it is 4-20. In addition, you may have a substituent on a heterocyclic group, and the same thing as what was illustrated by description about a trivalent aromatic hydrocarbon group is mentioned as a substituent. The carbon number of the trivalent heterocyclic group does not include the carbon number of the substituent.

  Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Say.

  Examples of the trivalent heterocyclic group include the following groups.

In formulas (201) to (284), R ′ is the same or different and is a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, An arylalkyloxy group, an arylalkylthio group, a substituted amino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group is represented.
R ″ is the same or different and represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.

R ′ halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide Group, arylalkenyl group, arylalkynyl group, definition of monovalent heterocyclic group, specific examples are the halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group represented by the aforementioned X ¹ , Arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide group, arylalkenyl group, arylalkynyl group, definition of monovalent heterocyclic group, the same as specific examples .
Definition of alkyl group, aryl group, arylalkyl group, substituted silyl group, acyl group, monovalent heterocyclic group represented by R ″, specific examples are the alkyl group represented by X ¹ above, aryl Group, arylalkyl group, substituted silyl group, acyl group, definition of monovalent heterocyclic group, and specific examples are the same.

At least one of Ar ¹ and Ar ² is a trivalent heterocyclic group, and preferably both are trivalent heterocyclic groups.

The compounds of the present invention, ^{Z 1} and Ar ² are bonded to the adjacent position Ar ^1, it is preferable ^{that Z 2} and Ar ¹ are joined to the adjacent position Ar ^2.

  The structural unit represented by the formula (1) is preferably further substituted on the structural unit represented by the formula (301) to the formula (540) and the aromatic hydrocarbon ring or heterocyclic ring contained in these structural units. A structural unit having a group. Examples of the substituent include the same substituents as exemplified for R described later.

〔式中、Ｘ^１及びＸ^２は前述と同じ意味を表す。〕

[Wherein, X ¹ and X ² represent the same meaning as described above. ]

  In the formula, R represents a hydrogen atom or a substituent. A plurality of R may be the same or different, and may be bonded to each other to form a ring. When R is a substituent, examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an aryl Alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, nitro group, And a group selected from a cyano group. The hydrogen atom contained in these substituents may be substituted with a fluorine atom.

An alkyl group represented by R, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a substituted amino group, Definition of substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent heterocyclic group, specific examples are the alkyl group, alkyloxy group, alkylthio group, aryl group represented by the aforementioned X ¹ , Aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent Definition of the heterocyclic group of, the same as the specific example It is.

  As the substituted carboxyl group, those having 2 to 20 carbon atoms are usually used, and examples thereof include a group having a methyl ester structure, a group having an ethyl ester structure, and a group having a butyl ester structure.

  Among the structural units represented by Formula (301) to Formula (540), Formula (301) to Formula (340), Formula (351) to Formula (360), Formula (401) to Formula (410), Formula (431) ) To formula (450) and structural units represented by formula (481) to formula (510) are preferred, structural units represented by formula (301) to formula (310) are more preferred, and formula (301) to formula (305). ), Structural units represented by formula (309) and formula (310) are particularly preferred.

In a preferred embodiment of the structural unit represented by the formula (1), at least one of Ar ¹ and Ar ² is a group in which three hydrogen atoms are removed from a thiophene ring.

The compound of the present invention preferably has a structural unit different from the structural unit represented by the formula (1) in addition to the structural unit represented by the formula (1). In this case, it is preferable that the structural unit represented by the formula (1) and the structural unit different from the structural unit represented by the formula (1) form a conjugate. Conjugation in the present invention is chained in the order of unsaturated bond-single bond-unsaturated bond, two π bonds of π orbitals are adjacent, and each π electron is arranged in parallel to form a double bond or It refers to a state in which π electrons are not localized on a triple bond but spread on an adjacent single bond and the π electrons are delocalized. Here, the unsaturated bond refers to a double bond or a triple bond.
Examples of the structural unit different from the structural unit represented by the formula (1) include an arylene group and a divalent heterocyclic group. Preferably, the structural unit different from the structural unit represented by the formula (1) is an arylene group or a divalent aromatic heterocyclic group.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and the number of carbon atoms constituting the ring is usually about 6 to 60, preferably 6 to 20. Here, aromatic hydrocarbons include those having a benzene ring, those having a condensed ring, those having two or more independent benzene rings or condensed rings directly bonded, or bonded via a group such as vinylene. It is.
Examples of the arylene group include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalenediyl group (formulas 4 to 13 in the following figure), an anthracenediyl group (formulas 14 to 19 in the following figure), and a biphenyl-diyl group (the formula in the following figure). 20-25), a terphenyl-diyl group (formulas 26 to 28 in the lower figure), a condensed ring compound group (formulas 29 to 38 in the lower figure), and the like. The condensed ring compound group includes a fluorene-diyl group (formulas 36 to 38 in the following figure).

The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and the number of carbon atoms constituting the ring is usually about 3 to 60.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom: pyridine-diyl group (formulas 39 to 44 in the following figure), diazaphenylene group (formulas 45 to 48 in the following figure), quinoline diyl group (formulas 49 to 63 in the following figure) A quinoxaline diyl group (formulas 64-68 in the figure below), an acridine diyl group (formulas 69-72 in the figure below), a bipyridyldiyl group (formulas 73-75 in the figure below), a phenanthroline diyl group (formulas 76-78 in the figure below);
Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure);
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulae 94 to 98 in the following figure);
5-membered ring condensed hetero groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 99 to 110 in the following figure);
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, bonded at the α-position of the heteroatom to form a dimer or oligomer (formulas 111 to 112 in the following figure);
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom, which is bonded to the phenyl group at the α-position of the heteroatom (formulas 113 to 119 in the figure below);
Groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom (formulas 120 to 127 in the following figure);
Examples include groups in which a 5-membered heterocyclic ring containing nitrogen, sulfur, selenium, etc. as a hetero atom is condensed (see FIGS. 128 to 139 below); groups in which a benzene ring and a thiophene ring are condensed (see FIGS. 140 to 143 below). I can do it.

  In Formula 1 to Formula 143, R represents the same meaning as described above. a and b are the same or different and represent the number of repetitions, and are usually 1 to 5, preferably 1 to 3, and particularly preferably 1.

Although the compound of this invention should just have the structural unit represented by Formula (1), Preferably it is a high molecular compound. The polymer compound in the present invention refers to a compound having a weight average molecular weight of 1000 or more, and a polymer compound having a weight average molecular weight of 3000 to 10,000,000 is preferably used. If the weight average molecular weight is lower than 3000, defects may occur in film formation during device fabrication, and if it exceeds 10000000, solubility in a solvent and applicability during device fabrication may be degraded. More preferably, it is 8000-5 million as a weight average molecular weight, Most preferably, it is 10,000-1 million.
In addition, the weight average molecular weight in this invention refers to the weight average molecular weight of polystyrene conversion computed using the standard sample of polystyrene using gel permeation chromatography (GPC).

  When the compound of the present invention is a polymer compound, the content of the structural unit represented by the formula (1) in the polymer compound may be at least one in the average. Preferably, the polymer compound contains an average of 2 or more per polymer chain, and more preferably an average of 3 or more per polymer chain.

  Moreover, when the compound of this invention is used for an element, it is desirable that the solubility to a solvent is high from the ease of device preparation. Specifically, the compound of the present invention preferably has a solubility capable of producing a solution containing 0.01 wt% or more of the compound, and preferably has a solubility capable of producing a solution containing 0.1 wt% or more. More preferably, it has a solubility capable of producing a solution containing 0.4 wt% or more.

〔式中、Ａｒ^１、Ａｒ^２、Ｚ^１、Ｚ^２、Ｘ^１、Ｘ^２、ｎ、ｍは、前述と同じ意味を表す。Ｗ^１、Ｗ^２は、同一又は相異なり、水素原子、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル残基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、モノハロゲン化メチル基、ボロン酸残基、ホルミル基、ビニル基又は有機スズ残基を表す。Ｚ^１とＡｒ^２がＡｒ^１の隣接位に接合し、Ｚ^２とＡｒ^１がＡｒ^２の隣接位に接合しており、ｍ＋ｎ＝２である。〕 Hereafter, the manufacturing method of the compound of this invention is described.
Among the compounds of the present invention, the compound represented by the formula (1-2) is described in Journal of Organic Chemistry (J. Org. Chem.) 1998, 63, p. 6132-6136, a method of introducing an alkyl group or an aryl group into a compound having carbonyl obtained by reacting symmetric biaryl or asymmetric biaryl with acrylamide in the presence of a strong acid by a known Wittig reaction, etc. Is mentioned.

[Wherein, Ar ¹ , Ar ² , Z ¹ , Z ² , X ¹ , X ² , n, m represent the same meaning as described above. W ¹ and W ² are the same or different and are a hydrogen atom, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid ester residue, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a mono Represents a halogenated methyl group, boronic acid residue, formyl group, vinyl group or organotin residue. Z ¹ and Ar ² are bonded to the adjacent position of Ar ¹ , Z ² and Ar ¹ are bonded to the adjacent position of Ar ² , and m + n = 2. ]

Examples of the biaryl used for producing the compound represented by the formula (1-2) include bithiophene, biphenyl, bipyrrole, bifuran, furanothiophene, phenylthiophene, pyrrolothiophene, pyrrolophenyl, and phenylfuran. Bithiophene. Virial used for the reaction may have a group represented by W ¹ or W ² .

  As the strong acid, trifluorosulfonic anhydride, trifluoroacetic anhydride and the like are used, and trifluorosulfonic anhydride is preferable. As the acrylamides, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide and the like are used, and N, N-dimethylacrylamide is preferable.

  Examples of the reaction method include reacting strong acid with acrylamide and then reacting biaryl, reacting strong acid with acrylamide and biaryl at the same time, reacting strong acid with acrylamide and then reacting biaryl. The method of making it preferable is.

The temperature at which the strong acid and acrylamide are reacted is preferably -50 ° C to 100 ° C, more preferably -10 ° C to 50 ° C.
The temperature at which biaryl is reacted with a reaction product obtained by reacting a strong acid and acrylamide is preferably 0 ° C to 150 ° C, more preferably 20 ° C to 100 ° C.

  When a strong acid and acrylamide are reacted, a solvent-free may be used, but a solvent can also be used. Solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane, bromopentane, Halogenated saturated hydrocarbons such as chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, 1,1,2,2-tetrachloroethane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, methanol, ethanol, Alcohols such as propanol, isopropanol, butanol and tert-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether Le, methyl -tert- butyl ether, tetrahydrofuran, tetrahydropyran, but ethers such as dioxane and the like, preferably halogenated saturated hydrocarbons.

  A well-known method can be used for the Wittig reaction. For example, in the presence of a Wittig reagent, in a solvent such as aromatic hydrocarbons, ethers, halogenated hydrocarbons, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, The reaction can be carried out under cooling or heating. The Wittig reagent can be obtained, for example, by reacting the corresponding phosphonium salt with a base such as alkyllithium such as potassium carbonate, tert-butoxypotassium, sodium hydride, or n-butyllithium.

The compound of the present invention may be used for the composition, thin film, ink, and device of the present invention. When the compound of the present invention is a polymer compound, the production method of the polymer compound is not particularly limited, but from the viewpoint of ease of synthesis of the polymer compound, a Suzuki coupling reaction or a Stille coupling reaction The method using is preferable.
From the viewpoint of polymerizing the compound represented by the formula (1-2) by Suzuki coupling reaction, W ¹ and W ² in the formula (1-2) are a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, An arylalkyl sulfonate group, a boric acid ester residue, and a boronic acid residue are preferable. From the viewpoint of ease of production, a halogen atom is more preferable. Examples of the halogen atom include a chlorine atom, a bromine primitive atom, and an iodine atom, and a bromine atom is preferable from the viewpoint of reactivity and ease of handling.

When W ¹ and W ² in Formula (1-2) are hydrogen atoms, a bromine atom can be introduced by contacting the compound represented by Formula (1-2) with a brominating agent. Examples of the brominating agent include bromine and N-bromosuccinimide. The brominating agent is preferably used in an amount of 2 equivalents or more relative to the compound represented by Formula (1-2) in which W ¹ and W ² are hydrogen atoms. These can be reacted in the absence of a solvent, but are preferably reacted in a solvent.
Examples of the solvent include hydrocarbon solvents, halogen solvents, N, N-dimethylformamide and the like. The reaction temperature depends on the type of solvent, but is usually −50 ° C. to 100 ° C., preferably −30 ° C. to 50 ° C. The reaction time is usually 1 minute to 20 hours, preferably 10 minutes to 5 hours.

As a method using the Suzuki coupling reaction, for example, the formula (100):
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (100)
[Wherein E ¹ represents a divalent group containing an aromatic ring. Q ¹⁰⁰ and Q ²⁰⁰ are the same or different and represent a boronic acid residue or a boric acid ester residue. ]
One or more compounds represented by formula (200):
T ¹ -E ² -T ² (200)
Wherein, E ² represents a structural unit containing a group represented by the formula (1). T ¹ and T ² are the same or different and each represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an arylalkyl sulfonate group. ]
The manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned. E ¹ is preferably a divalent aromatic group, and more preferably a group represented by the above-mentioned formulas 1 to 141.
In this case, the total number of moles of one or more compounds represented by formula (200) used in the reaction is excessive with respect to the total number of moles of one or more compounds represented by formula (100). Is preferred. When the total number of moles of one or more compounds represented by formula (200) used in the reaction is 1 mole, the total number of moles of one or more compounds represented by formula (100) is 0.6 to 0.00. It is preferably 99 mol, and more preferably 0.7 to 0.95 mol.

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。）
で表される基等が例示される。 As the borate ester residue, the following formula:

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

Examples of the halogen atom represented by T ¹ and T ² in Formula (200) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of ease of synthesis of the polymer compound, a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.

Examples of the alkyl sulfonate group represented by T ¹ and T ² in Formula (200) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. A benzyl sulfonate group is illustrated as an arylalkyl sulfonate group.

  Specifically, the method for carrying out the Suzuki coupling reaction includes a method in which a palladium catalyst is used as a catalyst in an arbitrary solvent and the reaction is performed in the presence of a base.

Examples of the palladium catalyst used in the Suzuki coupling reaction include Pd (0) catalyst, Pd (II) catalyst, and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium can be mentioned, and from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, dichlorobis (Triphenylphosphine) palladium, 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 0.0003 mol, relative to 1 mol of the compound represented by the formula (100). ~ 0.1 mol.

  When using palladium acetate as the palladium catalyst used in the Suzuki coupling reaction, for example, phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine are added as ligands can do. 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, barium hydroxide and the like. Examples of the organic base include triethylamine and tributylamine. Examples of the inorganic salt include 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 (100).

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

  The temperature at which the Suzuki coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the target degree of polymerization is reached, but is usually about 0.1 hour 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 inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the compound represented by the formula (100), the compound represented by the formula (200), Dichlorobis (triphenylphosphine) palladium (II) was charged, the polymerization vessel was sufficiently replaced with nitrogen gas, degassed, and then degassed by adding a degassed solvent such as toluene by bubbling with nitrogen gas in advance. Thereafter, a base degassed by bubbling with nitrogen gas in advance, for example, an aqueous sodium carbonate solution, is dropped into this solution, and then heated and heated, for example, while maintaining an inert atmosphere at the reflux temperature for 8 hours. Polymerize.

As a method using Stille coupling reaction, for example, formula (300):
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (300)
[Wherein E ³ represents a divalent group containing an aromatic ring. Q ³⁰⁰ and Q ⁴⁰⁰ are the same or different and represent an organotin residue. ]
The manufacturing method which has a process with which the 1 or more types of compound represented by this, and the 1 or more types of compound represented by the said Formula (200) are made to react in presence of a palladium catalyst is mentioned. E ³ is preferably a divalent aromatic group, and more preferably a group represented by the above-mentioned formulas 1 to 141.

Examples of the organic tin residue 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.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, n-pentyl group, isopentyl group, 2-methylbutyl group, 1 -Methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, Examples include chain alkyl groups such as 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. Examples of the aryl group include a phenyl group and a naphthyl group. Preferably -SnMe ₃ as organotin residue, -SnEt _3, -SnBu _3, an -SnPh _3, more preferably -SnMe _3, -SnEt _3, 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.

Examples of the halogen atom represented by T ¹ and T ² in Formula (200) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of ease of synthesis of the polymer compound, a bromine atom and an iodine atom are preferable.

Examples of the alkyl sulfonate group represented by T ¹ and T ² in Formula (200) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. A benzyl sulfonate group is illustrated as an aryl sulfonate 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, a Pd (II) catalyst, and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium can be mentioned, and from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, palladium [Tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst used for the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 1 mol of the compound represented by the formula (100). 0.5 mol, preferably 0.0003 mol to 0.2 mol.

Further, in the Stille coupling reaction, a ligand or a cocatalyst can be used as necessary. Examples of the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, and tris (2-furyl) phosphine, and triphenylarsine and triphenoxyarsine. Examples include arsenic compounds. Examples of the cocatalyst 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, tetrahydrofuran and the like. From the viewpoint of solubility of the polymer 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 about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for carrying out the reaction (reaction time) may be the end point when the target degree of polymerization 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 polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the polymerization vessel is charged with a compound represented by the formula (300), a compound represented by the formula (200), A palladium catalyst is charged, and the polymerization vessel is sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent, for example, toluene, and then coordinate as necessary. After adding the catalyst and the cocatalyst, the mixture is heated and heated, for example, and polymerized while maintaining an inert atmosphere at the reflux temperature for 8 hours.

The number average molecular weight in terms of polystyrene of the polymer compound is preferably 1 × 10 ³ to 1 × 10 ⁸ . When the number average molecular weight in terms of polystyrene is 1 × 10 ³ or more, a tough thin film is easily obtained. On the other hand, when it is 1 × 10 ⁸ or less, the solubility is high and the production of the thin film is easy.

  The terminal group of the polymer compound that can be used in the present invention is stable because if the polymerization active group remains as it is, there is a possibility that the characteristics and life of the element obtained when used for the preparation of the element may be reduced. It may be protected with any group. The stable group is preferably a group having a conjugated bond continuous with the conjugated structure of the main chain. The structure of the stable group may be, for example, a structure bonded to an aryl group or a heterocyclic group via a vinylene group.

The polymer compound that can be used in the present invention preferably has a long light absorption terminal wavelength. The light absorption terminal wavelength can be determined by the following method.
For the measurement, a spectrophotometer (for example, JASCO-V670, made by JASCO Corporation) that operates in the wavelength region of ultraviolet, visible, and near infrared is used. When JASCO-V670 is used, since the measurable wavelength range is 200 to 1500 nm, the measurement is performed in the wavelength range. First, the absorption spectrum of the substrate used for measurement is measured. As the substrate, a quartz substrate, a glass substrate, or the like is used. Next, a thin film containing the first compound is formed on the substrate from a solution containing the first compound or a melt containing the first compound. In film formation from a solution, drying is performed after film formation. Thereafter, an absorption spectrum of the laminate of the thin film and the substrate is obtained. The difference between the absorption spectrum of the laminate of the thin film and the substrate and the absorption spectrum of the substrate is obtained as the absorption spectrum of the thin film.
In the absorption spectrum of the thin film, the vertical axis represents the absorbance of the first compound, and the horizontal axis represents the wavelength. It is desirable to adjust the thickness of the thin film so that the absorbance at the largest absorption peak is about 0.5 to 2. The absorbance of the absorption peak with the longest wavelength among the absorption peaks is defined as 100%, and the intersection of the absorption peak and a straight line parallel to the horizontal axis (wavelength axis) including the absorbance of 50% of the absorption peak. The intersection point that is longer than the peak wavelength is taken as the first point. The intersection point between the absorption peak and a straight line parallel to the wavelength axis containing 25% of the absorbance, which is longer than the peak wavelength of the absorption peak, is defined as a second point. The intersection of the straight line connecting the first point and the second point and the reference line is defined as the light absorption terminal wavelength. Here, the reference line is the intersection of the absorption peak and the straight line parallel to the wavelength axis including the absorbance of 10% at the absorption peak of the longest wavelength, where the absorbance of the absorption peak is 100%. The third point on the absorption spectrum that is 100 nm longer than the reference wavelength and the absorption spectrum that is 150 nm longer than the reference wavelength with reference to the wavelength of the intersection that is longer than the peak wavelength of the absorption peak A straight line connecting the top and the fourth point.

  Since the compound of the present invention can exhibit high electron and / or hole transport properties, when an organic thin film containing the compound is used in a device, it is generated by electrons or holes injected from an electrode or light absorption. Charge can be transported. Taking advantage of these characteristics, it can be suitably used for various 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 having the compound of the present invention has one or more active layers containing the compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent.
As a preferable form of the photoelectric conversion element having the compound of the present invention, an activity formed from a pair of electrodes, at least one of which is transparent or translucent, and an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. Has a layer. The compound of the present invention is preferably used as a p-type organic semiconductor. The operation mechanism of the photoelectric conversion element of this embodiment will be described. Light energy incident from a transparent or translucent electrode is absorbed by an electron-accepting compound (n-type organic semiconductor) such as a fullerene derivative and / or an electron-donating compound (p-type organic semiconductor) such as the compound of the present invention. Generates excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface, Electric charges (electrons and holes) that can move independently are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.
The photoelectric conversion element manufactured using the compound of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

  In another aspect of the photoelectric conversion element having the compound 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 the first active layer. Adjacent to the photoelectric conversion element is a second active layer containing an electron-accepting compound such as a fullerene derivative.

  Examples of the transparent or translucent electrode material 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, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  One electrode may not be transparent, and a metal, a conductive polymer, etc. can be used as an electrode material of the electrode. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. 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.

  An additional intermediate layer other than the active layer may be used as a means for improving the photoelectric conversion efficiency. Examples of the material used for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).

<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 Phenanthrene derivatives such as polyfluorene and derivatives thereof, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocuproin), fullerenes, and fullerene derivatives are preferred. 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.

（２） （３） （４） （５）

（式（２）〜（５）中、Ｒ^ａは、アルキル基、アリール基、ヘテロアリール基又はエステル構造を有する基である。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はアルキル基又はアリール基を表す。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 the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), and a compound represented by the formula (5).

(2) (3) (4) (5)

(In the formulas (2) to (5), R ^a is an alkyl group, an aryl group, a heteroaryl group or a group having an ester structure. A plurality of R ^a may be the same or different. R ^b represents an alkyl group or an aryl group, and a plurality of R ^b may be the same or different.)

The definitions and specific examples of the alkyl group and aryl group represented by R ^a and R ^b are the same as the definitions and specific examples of the alkyl group and aryl group represented by X ¹ .

The heteroaryl group represented by ^Ra usually has 3 to 60 carbon atoms, and examples thereof include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.

（６）
（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、アルキル基、アリール基又は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 (6).

(6)
(In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c represents an alkyl group, an aryl group, or a heteroaryl group.)

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^a .

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

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

  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] Examples thereof include C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).

  When the active layer contains the compound of the present invention and a fullerene derivative, the ratio of the fullerene derivative 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. More preferably.

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

  The method for producing the active layer may be produced by any method, and examples thereof include film formation from a solution containing a compound and film formation 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 containing the polymer 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 unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane. , Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, and halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene Examples of the solvent include 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 ink jet coating method, and a spin coating method are preferable.
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.

  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 organic semiconductor layer (active layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path. The organic semiconductor layer is constituted by the organic thin film described above. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.

A field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active 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 organic semiconductor layer (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 organic semiconductor layer is constituted by an organic thin film containing the compound of the present invention.

  The static induction organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, and a gate electrode that controls the amount of current passing through the current path. It is preferable to be provided in the organic semiconductor layer. In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor 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 organic semiconductor layer is constituted by an organic thin film containing the compound of the present invention.

<Application of device>
The photoelectric conversion element using the compound of the present invention can be operated as an organic thin film solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. . 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 applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, 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.
The above-mentioned organic thin film transistor can be used as a pixel driving element used for controlling the uniformity of screen brightness and the screen rewriting speed of an electrophoretic display, a liquid crystal display, an organic electroluminescence display, and the like.

<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. 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 a filling resin depending on the purpose 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.

  The compound of this invention can also be used for an organic electroluminescent element (organic EL element). An organic EL element has a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent. 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.

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

(NMR measurement)
The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).

(Measurement of number average molecular weight and weight average molecular weight)
Regarding the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 30 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

アルゴン置換した（以下、フラスコ内の気体をアルゴンで置換したことを「アルゴン置換した」と記載する場合がある。）２００ｍＬのフラスコにＮ，Ｎ−ジメチルアクリルアミド１．９８ｇ（２０ｍｍｏｌ）、１,１,２,２−テトラクロロエタンを入れて均一な溶液とした。反応液を０℃に保ち、無水トリフルオロスルホン酸５．６４ｇ（２０ｍｍｏｌ）を１，１，２，２−テトラクロロエタン２０ｍＬに溶かした溶液を、１０分かけて滴下した。次いで、５，５’−ビチオフェン６．４８ｇ（２０ｍｍｏｌ）を１，１，２，２−テトラクロロエタン１２０ｍｌに溶かした溶液を、０℃で滴下し、その後、１００℃で８時間反応を行った。反応系を室温（２５℃）まで冷却し、炭酸ナトリウム水溶液を用いてｐＨが９になるまで中和した。その後、クロロホルムで油層を抽出し、油層を硫酸マグネシウムで乾燥し、ろ過した。ろ液を濃縮し、クロロホルムを展開溶媒としたシリカゲルカラムで精製して化合物１を２．１ｇ得た。 Reference example 1
(Synthesis of Compound 1)

Argon substitution (hereinafter, the fact that the gas in the flask was substituted with argon may be referred to as “argon substitution”.) 1.98 g (20 mmol) of N, N-dimethylacrylamide in a 200 mL flask, 1,1 1,2,2-tetrachloroethane was added to obtain a uniform solution. The reaction solution was kept at 0 ° C., and a solution obtained by dissolving 5.64 g (20 mmol) of trifluorosulfonic anhydride in 20 mL of 1,1,2,2-tetrachloroethane was added dropwise over 10 minutes. Next, a solution prepared by dissolving 6.48 g (20 mmol) of 5,5′-bithiophene in 120 ml of 1,1,2,2-tetrachloroethane was added dropwise at 0 ° C., and then reacted at 100 ° C. for 8 hours. The reaction system was cooled to room temperature (25 ° C.) and neutralized with an aqueous sodium carbonate solution until the pH reached 9. Thereafter, the oil layer was extracted with chloroform, and the oil layer was dried over magnesium sulfate and filtered. The filtrate was concentrated and purified with a silica gel column using chloroform as a developing solvent to obtain 2.1 g of Compound 1.

アルゴン置換した２００ｍＬの４つ口フラスコに、トリフェニル（テトラデシル）ホスホニウムブロミド１．０７ｇ(１．９８ｍｍｏｌ)と脱水テトラヒドロフラン（ＴＨＦ）１０ｍＬを入れて均一な溶液とした。反応系を−７８℃に保ちながら、ｎ−ブチルリチウム（ｎ−ＢｕＬｉ）の２．６Ｍヘキサン溶液を０．７９ｍＬ（１．９８ｍｍｏｌ）加えた。−７８℃で１時間攪拌した後、参考例１で製造した化合物１（０．５００ｇ、１．３２ｍｍｏｌ）をＴＨＦ５ｍＬに溶解した溶液を滴下した。徐々に室温（２５℃）に戻し、そのまま一晩静置した。反応溶液中に水を加えて反応を停止し、クロロホルムで有機層を抽出した。有機層を硫酸マグネシウムで乾燥し、ろ過後、ろ液の溶媒を留去した。シリカゲルカラム（ヘキサン：クロロホルム＝１:１（容積比））で精製して化合物２と化合物３の混合物を合計３９６ｍｇ（合計０．６９２ｍｍｏｌ）得た。化合物２と化合物３の混合比は２：１（モル比）であった。 Example 1
(Synthesis of tetradecylidenecycloheptabithiophene)

A 200 mL four-necked flask purged with argon was charged with 1.07 g (1.98 mmol) of triphenyl (tetradecyl) phosphonium bromide and 10 mL of dehydrated tetrahydrofuran (THF) to obtain a uniform solution. While maintaining the reaction system at −78 ° C., 0.79 mL (1.98 mmol) of a 2.6M hexane solution of n-butyllithium (n-BuLi) was added. After stirring at −78 ° C. for 1 hour, a solution of compound 1 (0.500 g, 1.32 mmol) prepared in Reference Example 1 in 5 mL of THF was added dropwise. The temperature was gradually returned to room temperature (25 ° C.) and allowed to stand overnight. Water was added to the reaction solution to stop the reaction, and the organic layer was extracted with chloroform. The organic layer was dried over magnesium sulfate and filtered, and then the solvent of the filtrate was distilled off. Purification with a silica gel column (hexane: chloroform = 1: 1 (volume ratio)) gave a total of 396 mg (0.692 mmol in total) of the mixture of Compound 2 and Compound 3. The mixing ratio of Compound 2 and Compound 3 was 2: 1 (molar ratio).

¹ HNMR (ppm):
Compound 2: 6.84 (1H), 6.76 (1H), 5.75 (1H), 2.85 (2H), 2.64 (2H), 2.12 (2H), 1.38-1 .24 (22H), 0.88 (3H)
Compound 3: 6.84 (1H), 6.73 (1H), 5.43 (1H), 2.95 (2H), 2.53 (2H), 2.18 (2H), 1.38-1 .24 (22H), 0.88 (3H)

アルゴン置換した１００ｍＬフラスコに、実施例１で合成した化合物２と化合物３の混合物（混合比 ２：１（モル比））１００ｍｇ（０．１７５ｍｍｏｌ）、化合物４（４,７−ｂｉｓ(４,４,５,５−ｔｅｔｒａｍｅｔｈｙｌ−１,３,２−ｄｉｏｘａｂｏｒｏｌａｎ−２−ｙｌ)−２,１,３−ｂｅｎｚｏｔｈｉａｄｉａｚｏｌｅ）（Ａｌｄｒｉｃｈ社製）６７．８ｍｇ（０．１７５ｍｍｏｌ）、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）、アルドリッチ社製）１００ｍｇを加え、トルエン５ｍＬ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２．０ｍｇ、トリス(２−メトキシフェニル)ホスフィン（Ｔｒｉｓ（２−ｍｅｔｈｏｘｙｐｈｅｎｙｌ）ｐｈｏｓｐｈｉｎｅ）１０．０ｍｇ、炭酸ナトリウム水溶液（１６．７ｗｔ％）４．０ｍＬを加え、１００℃で５時間攪拌を行った。その後、フェニルホウ酸３０ｍｇを加え、さらに１００℃で２時間反応させた。その後、ジエチルジチオカルバミン酸ナトリウム１ｇと水１０ｍＬ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、酢酸水溶液（３重量（ｗｔ）％）２０ｍＬで２回、さらに水２０ｍＬで２回洗浄し、有機層をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン５ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通し、精製した。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、ポリマーをろ過後、乾燥し、重合体６０ｍｇを得た。以下、この重合体を重合体Ａと呼称する。ＧＰＣで測定した重合体Ａのポリスチレン換算の分子量は、重量平均分子量（Ｍｗ）が１３０００であり、数平均分子量（Ｍｎ）が４５００であった。重合体Ａの光吸収末端波長を測定したところ、８０５ｎｍであった。 Example 2
(Synthesis of polymer A)

In a 100 mL flask purged with argon, 100 mg (0.175 mmol) of the mixture of compound 2 and compound 3 synthesized in Example 1 (mixing ratio 2: 1 (molar ratio)) and compound 4 (4,7-bis (4,4) were mixed. , 5,5-tetramethyl-1,3,2-dioxaboolalan-2-yl) -2,1,3-benzothiazole) (manufactured by Aldrich) 67.8 mg (0.175 mmol), methyltrialkylammonium chloride (trade name) 100 mg of Aliquat 336 (registered trademark, manufactured by Aldrich) was added and dissolved in 5 mL of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.0 mg of palladium acetate, 10.0 mg of tris (2-methoxyphenyl) phosphine (10.0 mg), 4.0 mL of an aqueous sodium carbonate solution (16.7 wt%) were added, and the mixture was stirred at 100 ° C. for 5 hours. Went. Thereafter, 30 mg of phenylboric acid was added, and the mixture was further reacted at 100 ° C. for 2 hours. Thereafter, 1 g of sodium diethyldithiocarbamate and 10 mL of water were added, and the mixture was stirred under reflux for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 20 ml of water, twice with 20 mL of acetic acid aqueous solution (3 wt.%), And further twice with 20 mL of water. The organic layer was poured into methanol to precipitate the polymer. It was. The polymer was filtered and dried, and the resulting polymer was dissolved again in 5 mL of toluene and purified by passing through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 60 mg of a polymer. Hereinafter, this polymer is referred to as polymer A. Regarding the molecular weight in terms of polystyrene of the polymer A measured by GPC, the weight average molecular weight (Mw) was 13000, and the number average molecular weight (Mn) was 4500. It was 805 nm when the light absorption terminal wavelength of the polymer A was measured.

重合体Ｂ Comparative Example 1
(Synthesis of polymer B)
Journal of Materials Chemistry, Vol. The polymer B having the following structure was produced by the method described in 12, 2887-2892 (2002), and the light absorption terminal wavelength was measured and found to be 650 nm. N in the following structure represents the number of repeating units.

Polymer B

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物２と化合物３の混合物（混合比 約２：１（モル比））を５００ｍｇ（０．８９５ｍｍｏｌ）、脱水ＴＨＦを２０ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液１．３５ｍＬ（２．１６ｍｍｏｌ）を５分かけて滴下した。滴下後、反応液を−７８℃で１時間攪拌した。その後、フラスコを−７８℃に保ったまま、反応液にトリ（ｎ−ブチル）スズクロリドを０．７７３ｇ（２．３７ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で６時間攪拌した。その後、水１００ｍｌを加えて反応を停止し、反応液に酢酸エチルを加えて反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、ろ過後、ろ液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ５ｗｔ％のトリエチルアミンを含むヘキサンに５分間浸し、その後、ヘキサンで濯いだシリカゲルを用いた。精製後、化合物５と化合物６の混合物（混合比 約２：１（モル比））を４２０ｍｇ（０．４２９ｍｍｏｌ）得た。 Example 3
(Synthesis of Compound 5 and Compound 6)

A 100 mL flask in which the gas in the flask was replaced with argon was charged with 500 mg (0.895 mmol) of a mixture of Compound 2 and Compound 3 (mixing ratio: about 2: 1 (molar ratio)) and 20 mL of dehydrated THF to obtain a uniform solution. did. The solution was kept at −78 ° C., and 1.35 mL (2.16 mmol) of 1.6 M n-butyllithium in hexane was added dropwise to the solution over 5 minutes. After dropping, the reaction solution was stirred at -78 ° C for 1 hour. Thereafter, 0.773 g (2.37 mmol) of tri (n-butyl) tin chloride was added to the reaction solution while keeping the flask at −78 ° C. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 6 hours. Thereafter, 100 ml of water was added to stop the reaction, and ethyl acetate was added to the reaction solution to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate and filtered, and then the filtrate was concentrated with an evaporator and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 420 mg (0.429 mmol) of a mixture of Compound 5 and Compound 6 (mixing ratio: about 2: 1 (molar ratio)) was obtained.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物５と化合物６の混合物（混合比 約２：１（モル比））を２５０ｍｇ（０．２５５ｍｍｏｌ）、化合物７（４,７−ｄｉｂｒｏｍｏ−２,１,３−ｂｅｎｚｏｔｈｉａｄｉａｚｏｌｅ）（Ａｌｄｒｉｃｈ社製）を７３ｍｇ（０．２４８ｍｍｏｌ）、トルエンを１０ｍｌ入れて均一溶液とした。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３．５１ｍｇ（３．８３μｍｏｌ）、トリス(２−トルイル)ホスフィン７．０ｍｇ（２３．０μｍｏｌ）を加え、１００℃で７時間攪拌した。その後、反応液にフェニルブロミドを５００ｍｇ加え、さらに８時間攪拌した。その後、フラスコを２５℃に冷却し、反応液をメタノール２００ｍＬに注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ５時間抽出した。円筒ろ紙内に残ったポリマーを、ｏ−ジクロロベンゼン１００ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム２ｇと水５０ｍＬを加え、１０時間還流下で攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、次いで、５％フッ化カリウム水溶液５０ｍLで２回洗浄し、次いで、水５０ｍLで２回洗浄し、得られたｏ−ジクロロベンゼンの溶液に無水硫酸ナトリウムを１０ｇ加えて、該溶液を乾燥した。ろ過後、ろ液をアルミナ／シリカゲルカラムに通した。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、ポリマーをろ過後、乾燥し、精製された重合体１１０ｍｇを得た。以下、この重合体を重合体Ｃと呼称する。ＧＰＣで測定した重合体Ｃのポリスチレン換算の分子量は、重量平均分子量（Ｍｗ）が２６０００であり、数平均分子量（Ｍｎ）が１６０００であった。重合体Ｃの光吸収末端波長は８０５ｎｍであった。 Example 4
(Synthesis of polymer C)

In a 100 mL flask in which the gas in the flask was replaced with argon, 250 mg (0.255 mmol) of a mixture of Compound 5 and Compound 6 (mixing ratio: about 2: 1 (molar ratio)) and Compound 7 (4,7-dibromo-2) were mixed. , 1,3-benzothiadiazole) (manufactured by Aldrich) and 73 ml (0.248 mmol) and 10 ml of toluene to obtain a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.51 mg (3.83 μmol) of tris (dibenzylideneacetone) dipalladium and 7.0 mg (23.0 μmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 7 hours. Thereafter, 500 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 8 hours. Thereafter, the flask was cooled to 25 ° C., and the reaction solution was poured into 200 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of o-dichlorobenzene, 2 g of sodium diethyldithiocarbamate and 50 mL of water were added, and the mixture was stirred for 10 hours under reflux. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and then 50 mL of 5% aqueous potassium fluoride solution. And then twice with 50 mL of water, 10 g of anhydrous sodium sulfate was added to the resulting solution of o-dichlorobenzene, and the solution was dried. After filtration, the filtrate was passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer. The polymer was filtered and then dried to obtain 110 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer C. Regarding the molecular weight in terms of polystyrene of the polymer C measured by GPC, the weight average molecular weight (Mw) was 26000, and the number average molecular weight (Mn) was 16000. The light absorption terminal wavelength of the polymer C was 805 nm.

Claims (17)

The compound containing the structural unit represented by Formula (1).

(1)
[Wherein, Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group. However, at least one of Ar ¹ and Ar ² is a trivalent heterocyclic group. Z ¹ and Z ² are the same or different and are —O—, —S—, —C (R ¹ ) (R ² ) —, —Si (R ³ ) (R ⁴ ) —, —N (R ⁵ ). ^{-, - B (R 6)} -, - P (R 7) -, - P (= O) (R 8) -, - Se (R 9) (R 10) -, - CO -, - SO 2 - Or -C (R < ¹¹ >) = C (R < ¹² >)-is represented. R ^{1 to} R ¹² , X ¹ and X ² are the same or different and are a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyl. Oxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, It represents a heterocyclic oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, or a cyano group. n represents an integer of 1 or more, and m represents an integer of 0 or more. When there are a plurality of Z ¹ , they may be the same or different. When there are a plurality of Z ² , they may be the same or different. ] The compound according to claim 1, wherein Ar ¹ and Ar ² are trivalent heterocyclic groups. The compound according to claim 1 or 2, wherein at least one of Ar ¹ and Ar ² is a group obtained by removing three hydrogen atoms from a thiophene ring. X < ¹ >, X < ² > is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a cyano group, The compound as described in any one of Claims 1-3. The compound according to any one of claims 1 to 4, wherein Z ¹ and Ar ² are bonded to an adjacent position of Ar ¹ , and Z ² and Ar ¹ are bonded to an adjacent position of Ar ² .   The sum of m and n is 2 or more, The compound as described in any one of Claims 1-5.   It is a high molecular compound, The compound as described in any one of Claims 1-6.   The compound according to claim 7, which has a weight average molecular weight of 3000 or more.   The thin film containing the compound as described in any one of Claims 1-8.   The composition containing the compound as described in any one of Claims 1-8.   A thin film comprising the composition according to claim 10.   An ink comprising the composition according to claim 10 and a solvent.   It has a 1st electrode and a 2nd electrode, it has an active layer between this 1st electrode and this 2nd electrode, and this active layer is any one of Claims 1-8. A device comprising the described compound.   The device according to claim 13, which is a photoelectric conversion device.   An image sensor comprising the element according to claim 13.   The device according to claim 13, which is an organic thin film transistor.   The device according to claim 13, which is an organic electroluminescence device.