JP5342852B2 - Conjugated compound, organic thin film and organic thin film element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound utilizable as an organic n-type semiconductor having excellent electron transport property. <P>SOLUTION: The conjugated compound has two or more groups represented by general formula (I) or groups represented by general formula (II). In the formulas, one of Ar and Ar' is a &ge;6C divalent aromatic hydrocarbon group, and the other is a &ge;4C divalent heterocyclic group (these groups may have substituents, but a fluorine atom is absent in the whole group); R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom, a halogen atom or a monovalent group; Ar" is a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group; with the proviso that when the conjugated compound has two or more groups represented by general formula (I), the part except the groups is free from a fluorine atom. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a conjugated compound, an organic thin film using the same, and an organic thin film element.

Various conjugated compounds, which are organic n-type semiconductors, have been developed as materials for organic thin film elements such as organic transistors, organic solar cells, and optical sensors. As specific examples thereof, compounds in which a fluoroalkyl group is introduced into oligothiophene have been proposed (Patent Documents 1 to 4).
US Patent Application Publication No. 2004/186266 US Patent Application Publication No. 2004/183068 International Publication No. 2003/010778 Pamphlet European Patent Application No. 12799689

  However, the above-described compounds are not usable as organic n-type semiconductors having sufficient electron transport properties.

  Then, the objective of this invention is providing the novel conjugated compound which can be utilized as an organic n-type semiconductor excellent in electron transport property. Another object of the present invention is to provide an organic thin film containing the novel conjugated compound, and an organic thin film element comprising the organic thin film.

In order to achieve the above object, the present invention provides a conjugated compound having two or more groups represented by the following general formula (I) or the following general formula (II).

Here, one of Ar and Ar ′ is a divalent aromatic hydrocarbon group having 6 or more carbon atoms, and the other is a divalent heterocyclic group having 4 or more carbon atoms (these groups have a substituent). Provided that R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent group, and Ar ″ is a trivalent aromatic carbonization. Each represents a hydrogen group or a trivalent heterocyclic group (these groups may have a substituent). However, when the said conjugated compound has 2 or more groups represented by general formula (I), parts other than the said group do not contain a fluorine atom.

  The conjugated compound having such a skeleton is excellent in packing property between molecules, and exhibits a sufficiently low LUMO by introducing an α-fluoroketone structure (—C (═O) —C (F) <). be able to. Therefore, the conjugated compound is sufficiently suitable as an n-type semiconductor excellent in electron injection and electron transport properties. In addition, since these compounds are chemically stable and have excellent solubility in solvents, organic thin film elements with excellent performance can be manufactured by forming thin films using the conjugated compounds. It becomes.

  The present invention provides an organic thin film containing the above conjugated compound. The present invention further provides an organic thin film element, an organic thin film transistor, an organic solar cell, and an optical sensor each having the organic thin film.

  Such an organic thin film, an organic thin film element, an organic thin film transistor, an organic solar cell, and a photosensor are formed using the conjugated compound of the present invention having a sufficiently low LUMO and excellent charge transportability as described above. Therefore, excellent performance can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the novel conjugated compound which can be utilized as an organic n-type semiconductor excellent in electron transport property can be provided. Moreover, the organic thin film containing this novel conjugated compound and an organic thin film element provided with this organic thin film can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  The conjugated compound of the present invention has two or more groups represented by the above general formula (I) or (II). Here, the conjugated compound in the present invention includes a structure in which a single bond and an unsaturated bond, a lone electron pair, a radical, or a nonbonding orbital are alternately connected in the main skeleton of the compound, and a π orbital or nonbonding property. This means that delocalization of electrons due to orbital interaction occurs in part or all of the main skeleton. Among the conjugated compounds, π conjugated compounds based on π orbital interaction are preferable.

  When the said conjugated compound has 2 or more groups represented by general formula (I), parts other than the said group do not contain a fluorine atom. Such a conjugated compound has a sufficiently high packing property between molecules, and is sufficiently suitable as an n-type semiconductor excellent in electron injection and electron transport properties.

  In the conjugated compound, a plurality of groups represented by the general formula (I) or (II) may be the same or different, but are more preferably the same.

In General Formula (I), any one of Ar and Ar ′ represents a divalent aromatic hydrocarbon group having 6 or more carbon atoms, and the other represents a divalent heterocyclic group having 4 or more carbon atoms. Although these groups may have a substituent, the whole group does not contain a fluorine atom. Ar is preferably a divalent heterocyclic group having 4 or more carbon atoms, and Ar ′ is preferably a divalent aromatic hydrocarbon group having 6 or more carbon atoms. R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a monovalent group.

  Here, the divalent aromatic hydrocarbon group means an atomic group remaining after removing two hydrogen atoms from a benzene ring or condensed ring. The carbon number of the divalent aromatic hydrocarbon group is preferably 6 to 60, and more preferably 6 to 20. Examples of the condensed ring include naphthalene, anthracene, tetracene, pentacene, pyrene, perylene, and fluorene. Among these, the remaining atomic group obtained by removing two hydrogen atoms from a benzene ring, pentacene or pyrene is particularly preferable. In addition, you may have a substituent on the aromatic hydrocarbon group. Here, the carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent. In addition, examples of the substituent include a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an arylalkyl group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group. .

  The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The carbon number of the divalent heterocyclic group is preferably 4 to 60, and more preferably 4 to 20. In addition, you may have a substituent on a bivalent heterocyclic group, and carbon number of a substituent is not contained in carbon number of a bivalent heterocyclic group. In addition, examples of the substituent include a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an arylalkyl group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group. . Examples of the divalent heterocyclic group include the remaining atomic groups obtained by removing two hydrogen atoms from a thiophene ring, thienothiophene ring, furan ring, pyrrole ring, and pyridine ring, and in particular, a thiophene ring, a thienothiophene ring to a hydrogen atom. The remaining atomic groups except the two exhibit characteristic electrical properties, and can be expected to exhibit new electrical characteristics that have not existed before. The divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of lowering LUMO, R ¹ and R ² are preferably fluorine atoms.

The group represented by the general formula (I) is preferably a group represented by the following general formula (III).

In formula (III), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ⁰ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. A plurality of R ^{0 s} each representing an alkoxy group may be the same or different. One of Z ¹ and Z ¹ ′ represents a group represented by the following formula (i), and the other represents any of the groups represented by the following formulas (ii) to (ix). Z ¹ ′ is a group represented by the following formula (i), and Z ¹ is preferably any one of groups represented by the following formulas (ii) to (ix). R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent group, and R ³ and R ⁴ may be bonded to each other to form a ring.

When the conjugated compound has two or more groups represented by the general formula (I) or (III), it is preferably a compound represented by the following general formula (V).

In the formula (V), R ⁰ , R ¹ , R ² , Z ¹ and Z ¹ ′ are as defined above. Ar ¹ , Ar ² and Ar ³ each independently represent a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms. Although these groups may have a substituent, the whole group does not contain a fluorine atom. Examples of the divalent aromatic hydrocarbon group and the divalent heterocyclic group having 4 or more carbon atoms include the same groups as those exemplified for Ar and Ar ′. At least one of Ar ¹ , Ar ² and Ar ³ is preferably a thienylene group which may have a substituent. However, the whole group does not contain a fluorine atom. m, n and p each independently represent an integer of 0 to 6. A plurality of R ⁰ , R ¹ , R ² , Z ¹ and Z ¹ ′ may be the same or different. From the viewpoint of more effectively exerting the effects of the present invention, R ¹ and R ² are fluorine atoms, Z ¹ ′ is a group represented by formula (i), and Z ¹ is represented by formula (ii). More preferably, it is a group. More preferably, at least one of Ar ¹ , Ar ² and Ar ³ is a thienylene group.

  In the general formula (II), Ar ″ represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group (these groups may have a substituent).

  The trivalent aromatic hydrocarbon group refers to the remaining atomic group obtained by removing three hydrogen atoms from a benzene ring or condensed ring. The carbon number of the trivalent aromatic hydrocarbon group is preferably 6 to 60, and more preferably 6 to 20. Examples of the condensed ring include naphthalene, anthracene, tetracene, pentacene, pyrene, perylene, and fluorene. Among these, the remaining atomic group obtained by removing three hydrogen atoms from the benzene ring is particularly preferable. In addition, you may have a substituent on the aromatic hydrocarbon group. The carbon number of the trivalent aromatic hydrocarbon group does not include the carbon number of the substituent.

  The trivalent heterocyclic group refers to the remaining atomic group obtained by removing three hydrogen atoms from the heterocyclic compound. The carbon number of the trivalent heterocyclic group is preferably 4 to 60, and more preferably 4 to 20. In addition, you may have a substituent on a trivalent heterocyclic group, and carbon number of a substituent is not contained in carbon number of a trivalent heterocyclic group. Examples of the trivalent heterocyclic group include the remaining atomic groups obtained by removing three hydrogen atoms from a thiophene ring, thienothiophene ring, furan ring, pyrrole ring, and pyridine ring, and in particular, a thiophene ring, a thienothiophene ring to a hydrogen atom. The remaining atomic groups other than three exhibit characteristic electrical properties, and can be expected to exhibit new electrical characteristics that have not existed before. The trivalent heterocyclic group is preferably a trivalent aromatic heterocyclic group.

The group represented by the general formula (II) is preferably a group represented by the following general formula (IV).

In the formula (IV), R ¹⁰ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Represents a fluoroalkoxy group, and Z ² represents any one of groups represented by the following formulas (xi) to (xix). Z ² is preferably a group represented by the following formula (xii). R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. .

When the conjugated compound has two or more groups represented by the general formula (II) or (IV), it is preferably a compound represented by the following general formula (VI).

In formula (VI), R ¹⁰ and Z ² have the same meanings as described above, and a plurality of R ¹⁰ and Z ² may be the same or different. Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms (these groups have a substituent). May be). Examples of the divalent aromatic hydrocarbon group and the divalent heterocyclic group having 4 or more carbon atoms include the same groups as those exemplified for Ar and Ar ′. More preferably, at least one of Ar ⁴ , Ar ⁵ and Ar ⁶ is a thienylene group which may have a substituent. q, r and s each independently represent an integer of 0 to 6. From the viewpoint of more effectively exerting the effects of the present invention, Z ² is preferably a group represented by the formula (xii).

Examples of the alkyl group in R ⁰ and R ¹⁰ include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms can be used. preferable. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, 3-methylbutyl group, pentyl group, hexyl group, 2 -Ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclododecyl group. As an alkoxy group, the C1-C20 alkoxy group which contains the said alkyl group in the structure is mentioned. Examples of the alkoxy group include linear, branched, or cyclic alkoxy groups having 1 to 20 carbon atoms that include the alkyl group in the structure, and include linear, branched, or cyclic groups having 1 to 12 carbon atoms. Those containing an alkyl group are preferred. Examples of the fluoroalkyl group in R ¹⁰ include groups in which part or all of the hydrogen atoms of the above alkyl group are replaced by fluorine atoms, and linear, branched or cyclic fluoroalkyl groups having 1 to 12 carbon atoms are preferable. Examples of the fluoroalkoxy group include C1-C20 fluoroalkoxy groups containing the above-mentioned fluoroalkyl group in the structure thereof, and those containing a linear, branched or cyclic fluoroalkyl group having 1 to 12 carbon atoms Is preferred.

Examples of the monovalent group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ include, for example, a linear or branched low molecule Chain, monovalent cyclic group having 3 to 60 carbon atoms (monocyclic or condensed ring, carbocyclic or heterocyclic ring, which may be saturated or unsaturated, may have a substituent), saturated or unsaturated Hydrocarbon group, hydroxyl group, alkoxy group, alkanoyloxy group, amino group, oxyamino group, alkylamino group, dialkylamino group, alkanoylamino group, cyano group, nitro group, sulfo group, alkyl group substituted by halogen atom An alkoxysulfonyl group (wherein the alkoxy group may be substituted with a halogen atom), an alkylsulfonyl group (wherein the alkyl group may be substituted with a halogen atom), Rufamoiru group, alkylsulfamoyl group, a carboxyl group, a carbamoyl group, an alkylcarbamoyl group include an alkanoyl group and an alkoxycarbonyl group

  As an alkyl group, a C1-C20 linear, branched or cyclic alkyl group is mentioned, A C1-C12 linear, branched or cyclic alkyl group is preferable. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, 3-methylbutyl group, pentyl group, hexyl group, 2- Examples include ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclododecyl group. The same applies to a group containing an alkyl group in its structure (for example, an alkoxy group, an alkylamino group, or an alkoxycarbonyl group).

  Although it does not specifically limit as an unsaturated hydrocarbon group, For example, a vinyl group, 1-propenyl group, an allyl group, a propargyl group, an isopropenyl group, 1-butenyl group, and 2-butenyl group are mentioned.

  The alkanoyl group is not particularly limited, and examples thereof include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, and an isovaleryl group. The same applies to a group containing an alkanoyl group in its structure (for example, an alkanoyloxy group or an alkanoylamino group). Further, the alkanoyl group having 1 carbon atom means a formyl group, and the same applies to a group containing an alkanoyl group in its structure.

The conjugated compound of the present invention is expected to have a high electron transport property as an organic n-type semiconductor. In order to enhance this effect, it is preferable to enhance the planarity of the π-conjugated structure other than the group represented by the general formula (I) or (II) so that a π-π stack structure can be easily formed. From such a viewpoint, Ar ¹ , Ar ² and Ar ³ in the general formula (V) and Ar ⁴ , Ar ⁵ and Ar ⁶ in (VI) preferably have a structure containing a condensed ring or a thiophene ring. A structure including a thiophene skeleton is particularly preferable because the plane spacing of the π-π stack structure can be reduced. Further, from the viewpoints of improving the solubility in organic solvents and maintaining π-conjugated planarity, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ preferably have a substituent. However, it is preferable that the whole group does not contain a fluorine atom.

The conjugated compound of the present invention has two or more groups represented by general formula (I), (II), (III) or (IV). From the viewpoint of enhancing the electron transport property, the conjugated compound is preferably a compound represented by the general formula (V) or (VI). Specific examples of the compound represented by the formula (V) or (VI) include compounds represented by the following general formulas (1) to (20).

Here, R shows a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group. R ^* , R ′ and R ″ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Of the fluoroalkoxy group. A plurality of R, R ^* , R ′ and R ″ may be the same or different. Among them, R, R ^* and R ′ are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ″ is preferably a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms. .

  The conjugated compound of the present invention preferably has a reduction potential of −2.0 V to +0.5 V based on ferrocene measured by an electrochemical measurement (cyclic voltammetry) method, and is −1.8 V to +0. More preferably, it is 2V. When the reduction potential has the above-described numerical range, the conjugated compound is sufficiently suitable as an n-type semiconductor having excellent electron injection and excellent electron transport properties. The reduction potential can be measured by the method described below. The supporting electrolyte, the solvent, and the electrode used for the measurement are not limited to the exemplified materials shown below, and any materials can be used as long as the same level of measurement is possible.

  As a supporting electrolyte, for example, about 0.1 to 2 mM of the measurement target material is dissolved in an organic solvent containing about 0.1 mol / L of tetrabutylammonium perchlorate and tetrabutylammonium hexafluorophosphate. After removing oxygen from the solution thus obtained by techniques such as dry nitrogen bubbling, vacuum degassing, and ultrasonic irradiation, a platinum electrode or a glassy carbon electrode is used as a working electrode, and a platinum electrode is used as a counter electrode, for example. Electrolytic reduction from an electrically neutral state at a sweep rate of 100 mV / sec. By comparing the potential of the first peak value detected at the time of electrolytic reduction with the oxidation-reduction potential of a reference substance such as ferrocene, the oxidation (or reduction) potential of the material to be measured is obtained. A value obtained by converting the oxidation (or reduction) potential thus obtained with reference to ferrocene is the reduction potential in the present invention.

Next, the manufacturing method of the conjugated compound of this invention is demonstrated. Conjugated compounds include, for example, the following general formulas (VIIa), (VIIb), (VIIIa) (VIIIb), (IX), (IX ′), (X), (X ′), (XIa), (XIb) , (XIIa) and (XIIb) (hereinafter abbreviated as “(VIIa) to (XIIb)”) as a raw material.

In formulas (VIIa) to (XIIb), Ar, Ar ′, Ar ″, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Z ¹ , Z ¹ ′, Z ² , R ⁰ , R ¹⁰ , R ¹ , R ² , m, n, p, q, r and s are as defined above. W ¹ and W ² each independently represent 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 monohalogenated methyl group, A boric acid residue (-B (OH) ₂ ), a formyl group, a trialkylstannyl group or a vinyl group is shown. Specific examples of the boric acid ester residue include dimethyl boric acid, diisopropyl boric acid, 1,3,2-dioxaborolane, 4,4,5,5-tetraethyl-1,3,2-dioxaborolane, 1,3,2- Dioxaboroan is mentioned.

From the viewpoint of the synthesis of the compounds represented by the general formulas (VIIa) to (XIIb) and the ease of reaction, W ¹ and W ² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an arylalkyl. A sulfonate group, a boric acid ester residue, a boric acid residue or a trialkylstannyl group is preferred. When the compound represented by the general formula (IX) or (X) is used as a raw material and the reaction is difficult due to strong electron withdrawing property, the general formula (IX ′) or ( The compound represented by X ′) may be reacted as an intermediate, and the alkylenedioxy group may be converted to a carbonyl group after the reaction.

For example, a compound represented by the following general formula (XIII) is produced as an intermediate by reacting a compound represented by the general formula (X ′) with a compound represented by the general formula (XIIb). The compound of the above general formula (VI) can be produced by converting an alkylenedioxy group into a carbonyl group.

In formula (XIII), Ar ⁴ , Ar ⁵ , Ar ⁶ , Z ² , R ¹⁰ , q, r and s have the same meanings as described above.

Examples of the method for producing the conjugated compound include a method using a Suzuki coupling reaction, a method using a Grignard reaction, a method using a Stille reaction, a method using a Ni (0) catalyst, and an oxidizing agent such as FeCl _3. , A method using an anion oxidation reaction, a method using palladium acetate and an organic base, a method of using α-substitution or preparing a thiothio compound from a halogen compound and oxidative coupling, a method using an electrochemical oxidation reaction, and Examples thereof include a method by decomposition of an intermediate compound having an appropriate leaving group.

  Among these, there are a method using a Suzuki coupling reaction, a method using a Grignard reaction, a method using a Stille reaction, a method using a Ni (0) catalyst, a method using an anion oxidation reaction, and a method using palladium acetate and an organic base. It is preferable from the viewpoint of easy structure control, availability of raw materials, and simplicity of reaction operation.

  In the case of the Suzuki coupling reaction, for example, tetrakis (triphenylphosphine) palladium, palladium acetates are used as a catalyst, an inorganic base such as potassium carbonate, sodium carbonate, barium hydroxide, an organic base such as triethylamine, cesium fluoride, etc. The inorganic salt such as is added in an equivalent amount or more, preferably 1 to 10 equivalents with respect to the monomer. Moreover, you may make it react by a two-phase system by making inorganic salt into aqueous solution. Examples of the solvent used in this reaction include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. The reaction temperature is preferably about 50 to 160 ° C. although it depends on the solvent used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours. The Suzuki coupling reaction is described in, for example, Chemical Review (Chem. Rev.), 95, 2457 (1995).

  In the case of a reaction using a Ni (0) catalyst, a method using a zero-valent nickel complex as a Ni (0) catalyst, a method of reacting a nickel salt in the presence of a reducing agent, and generating zero-valent nickel in the system There is. Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost.

  Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand to the said reaction. Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. And nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, and triphenoxyphosphine. Among these, a nitrogen-containing ligand is preferable from the viewpoint of versatility and low cost, and 2,2'-bipyridyl is particularly preferable from the viewpoint of high reactivity and high yield. In particular, a system in which 2,2′-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable from the viewpoint of improving the yield of a conjugated compound. . In the method for producing zero-valent nickel in the system, nickel chloride or nickel acetate can be used as the nickel salt. Examples of the reducing agent include zinc, sodium hydride, hydrazine and derivatives thereof, and lithium aluminum hydride. Moreover, you may use together ammonium iodide, lithium iodide, potassium iodide etc. as an additive as needed.

  In the Stille reaction, for example, tetrakis (triphenylphosphine) palladium or palladium acetate is used as a catalyst, and an organotin compound is reacted as a monomer. Examples of the solvent used in this reaction include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. Although reaction temperature is based on the solvent to be used, about 50-160 degreeC is preferable. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

  In the case of a method using an anion oxidation reaction, a halogen or hydrogen substitution product is used as a monomer to prepare a thio compound by reaction with n-butyllithium, and copper (II) bromide, copper (II) chloride, acetylacetonate Treat with an oxidizing agent such as iron (III). Examples of the solvent used in this reaction include toluene, dimethoxyethane, tetrahydrofuran, hexane, heptane, and octane. The reaction temperature depends on the solvent used, but is preferably about 50 to 160 ° C. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 5 minutes to 200 hours.

  In the case of a method using palladium acetate and an organic base, palladium (II) acetate and an organic base such as diisopropylamine or triethylamine are added and reacted using a halogen-substituted product as a monomer. Examples of the solvent used in this reaction include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. The reaction temperature depends on the solvent used, but is preferably about 50 to 160 ° C. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 5 minutes to 200 hours.

  When the conjugated compound of the present invention is used as a material for an organic thin film device, the purity affects the device characteristics. Therefore, it is preferable to perform a purification treatment by a method such as sublimation purification or recrystallization.

  Next, the organic thin film of the present invention will be described. The organic thin film of the present invention contains the above conjugated compound.

  The organic thin film may contain one kind of the conjugated compound alone or may contain two or more kinds of the conjugated compound. Moreover, in order to improve the electron transport property or hole transport property of an organic thin film, the low molecular weight compound or polymer compound (electron transport material, hole transport material) which had electron transport property or hole transport property other than the said conjugated compound. Can also be used in combination.

  As the hole transporting material, known materials can be used, for example, pyrazoline, arylamine, stilbene, triaryldiamine, oligothiophene, polyvinylcarbazole, polysilane, polysiloxane having aromatic amine in the side chain or main chain, polyaniline , Polythiophene, polypyrrole, polyarylene vinylene, polythienylene vinylene, and derivatives thereof.

As the electron transporting material, known materials can be used. For example, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene, diphenoquinone, 8-hydroxyquinoline. , metal complexes, polyquinoline of polyquinoxaline, polyfluorenes, fullerenes such as C _60, and derivatives thereof.

Further, the organic thin film of the present invention may contain a charge generating material in order to generate a charge by light absorbed in the organic thin film. As the charge generation material, known materials can be used. For example, azo compounds, diazo compounds, metal-free phthalocyanine compounds, metal phthalocyanine compounds, perylene compounds, polycyclic quinone compounds, squarylium compounds, azurenium compounds, thiapyrylium compounds, and C _60. And fullerenes.

  Furthermore, the organic thin film of the present invention may contain materials necessary for developing various functions. Examples of such materials include sensitizers for sensitizing the function of generating charges by absorbed light, stabilizers for increasing stability, and UV absorbers for absorbing UV light. Can be mentioned.

  In addition, the organic thin film of the present invention may contain a polymer compound material other than the above compound as a polymer binder in order to improve mechanical properties. As the polymer binder, those that do not extremely inhibit the electron transport property or hole transport property are preferable, and those that do not strongly absorb visible light are preferable.

  Examples of such a polymer binder include poly (N-vinylcarbazole), polyaniline, polythiophene, poly (p-phenylene vinylene), poly (2,5-thienylene vinylene), polycarbonate, polyacrylate, polymethyl acrylate, Examples include polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and derivatives thereof.

  The method for producing the organic thin film of the present invention is not particularly limited. For example, the film is formed from a solution containing the conjugated compound, an electron transporting material or hole transporting material mixed as necessary, a polymer binder, and a solvent. Can be used. Moreover, when a conjugated compound has sublimation property, it can also form in a thin film by a vacuum evaporation method.

  The solvent is not particularly limited as long as it dissolves the conjugated compound, the electron transporting material or hole transporting material to be mixed, and the polymer binder.

  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 and bromocyclohexane, and halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene , Ether solvents such as tetrahydrofuran and tetrahydropyran can be used. Although the conjugated compound of the present invention depends on the structure and molecular weight of the compound, it can be usually dissolved in these solvents in an amount of 0.1% by mass or more.

  Film formation methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing. Application methods such as offset printing, ink jet printing, dispenser printing, nozzle coating and capillary coating can be used. Of these, spin coating, flexographic printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating are preferred.

  The thickness of the organic thin film is preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

  The step of producing the organic thin film of the present invention may include a step of orienting the conjugated compound. In the organic thin film in which the conjugated compound is oriented by this step, the main chain molecules or the side chain molecules are arranged in one direction, so that the electron mobility or the hole mobility is improved.

  As a method of aligning the conjugated compound, a method known as a liquid crystal alignment method can be used. Among them, the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are preferable.

  Since the organic thin film of the present invention has an electron transport property or a hole transport property, by controlling the transport of electrons or holes injected from the electrode or charges generated by light absorption, an organic thin film transistor, an organic photoelectric conversion element ( It can be used for organic thin film elements such as organic solar cells and optical sensors. When the organic thin film of the present invention is used for these organic thin film elements, it is preferable to use the organic thin film by orientation treatment because the electron transport property or hole transport property is further improved.

  Next, application of the organic thin film of the present invention to an organic thin film transistor will be described. The organic thin film transistor has a structure including a source electrode and a drain electrode, an organic thin film layer (active layer) containing a conjugated compound of the present invention as a current path between them, and a gate electrode for controlling the amount of current passing through the current path. The field effect type, the electrostatic induction type, and the like are exemplified.

  A field-effect organic thin film transistor includes a source electrode and a drain electrode, an organic thin film layer (active layer) containing a conjugated compound of the present invention that is a current path between them, a gate electrode that controls the amount of current passing through the current path, and It is preferable to provide an insulating layer disposed between the active layer and the gate electrode. In particular, a source electrode and a drain electrode are provided in contact with an organic thin film layer (active layer) containing the conjugated compound of the present invention, and a gate electrode is provided with an insulating layer in contact with the organic thin film layer interposed therebetween. Preferably it is.

  The electrostatic induction type organic thin film transistor has a source electrode and a drain electrode, an organic thin film layer containing a conjugated compound of the present invention that becomes a current path between them, and a gate electrode that controls the amount of current passing through the current path, The gate electrode is preferably provided in the organic thin film layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic thin film layer are preferably provided in contact with the organic thin film layer containing the conjugated compound of the present invention. The structure of the gate electrode may be any structure as long as 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. It is done.

  FIG. 1 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a first embodiment. An organic thin film transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 with a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 between the source electrode 5 and the drain electrode 6, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 formed between the source electrode 5 and the drain electrode 6. And a gate electrode 4.

  FIG. 2 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a second embodiment. An organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5 and a predetermined electrode. Of the drain electrode 6 formed on the active layer 2 with an interval of, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the insulating layer 3 between the source electrode 5 and the drain electrode 6. And a gate electrode 4 formed on the insulating layer 3 so as to cover the region.

  FIG. 3 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a third embodiment. The organic thin film transistor 120 shown in FIG. 3 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval, and a source electrode. 5 and the drain electrode 6 so as to partially cover the insulating layer 3 formed on the active layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below. And a gate electrode 4 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3.

  FIG. 4 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fourth embodiment. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The source electrode 5 and the drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to partially cover the region of the insulating layer 3 formed on the substrate, and the source electrode 5 and the drain electrode 6 are partially covered. Thus, the active layer 2 formed on the insulating layer 3 is provided.

  FIG. 5 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fifth embodiment. An organic thin film transistor 140 shown in FIG. 5 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3 formed on the active layer 2 and an active layer 2 formed on the insulating layer 3 so as to partially cover the source electrode 5. And a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to partially cover the region of the active layer 2 formed below the gate electrode 4 It is.

  FIG. 6 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a sixth embodiment. An organic thin film transistor 150 shown in FIG. 6 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The active layer 2 is formed on the insulating layer 3 so as to partially cover the region of the active layer 2 formed under the active layer 2 and the gate electrode 4 formed below. The source electrode 5 and the drain electrode 6 formed on the insulating layer 3 with a predetermined distance from the source electrode 5 so as to partially cover the region of the active layer 2 where the gate electrode 4 is formed below. , Are provided.

  FIG. 7 is a schematic cross-sectional view of an organic thin film transistor (static induction organic thin film transistor) according to a seventh embodiment. The organic thin film transistor 160 shown in FIG. 7 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality on the active layer 2 with a predetermined interval. The formed gate electrode 4 and the active layer 2a formed on the active layer 2 so as to cover the gate electrode 4 (the material constituting the active layer 2a may be the same as or different from that of the active layer 2). And a drain electrode 6 formed on the active layer 2a.

  In the organic thin film transistors according to the first to seventh embodiments, the active layer 2 and / or the active layer 2a contains the conjugated compound of the present invention, and a current path between the source electrode 5 and the drain electrode 6 ( Channel). The gate electrode 4 controls the amount of current passing through the current path (channel) in the active layer 2 and / or the active layer 2a by applying a voltage.

  Such a field effect organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic thin film transistor can be produced by a known method, for example, a method described in JP-A-2004-006476.

  The material of the substrate 1 is not particularly limited as long as the characteristics as an organic thin film transistor are not impaired. As the substrate 1, a glass substrate, a flexible film substrate, and a plastic substrate can be used.

  When forming the active layer 2, it is very advantageous and preferable to use a conjugated compound soluble in an organic solvent, so that the active layer 2 can be formed using the organic thin film manufacturing method of the present invention described above. An organic thin film can be formed.

The insulating layer 3 in contact with the active layer 2 is not particularly limited as long as it is a material having high electrical insulation, and a known material can be used. For _{example, SiOx, SiNx, Ta 2 O} 5, polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass and photoresists. From the viewpoint of lowering the voltage, the insulating layer 3 is preferably a material having a high dielectric constant.

When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification. Examples of the surface treatment agent include silylamine compounds such as long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, and hexamethyldisilazane. Prior to the treatment with the surface treatment agent, the surface of the insulating layer can be treated with ozone UV or O ₂ plasma.

  Moreover, it is preferable to form a protective film on the organic thin film transistor after the organic thin film transistor is manufactured in order to protect the element. Thereby, an organic thin-film transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic thin-film transistor can be suppressed. Moreover, the influence from the process of forming the display device driven on an organic thin-film transistor with a protective film can be reduced.

  Examples of the method for forming the protective film include a method of covering with a UV curable resin, a thermosetting resin, or an inorganic SiONx film. In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the preparation of the organic thin film transistor to the formation of the protective film without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  Next, application of the organic thin film of the present invention to a photoelectric conversion element will be described. As typical photoelectric conversion elements, there are solar cells and optical sensors. FIG. 8 is a schematic cross-sectional view of the solar cell according to the embodiment. A solar cell 200 shown in FIG. 8 includes a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing the conjugated compound of the present invention formed on the first electrode 7a. The active layer 2 and the second electrode 7b formed on the active layer 2 are provided.

  In the solar cell 200, a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In order to obtain a high open circuit voltage, each electrode is preferably selected so that the difference in work function is large. In the active layer 2 (organic thin film), a charge generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity. As the substrate 1, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

  FIG. 9 is a schematic cross-sectional view of the photosensor according to the first embodiment. An optical sensor 300 shown in FIG. 9 includes a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing the conjugated compound of the present invention formed on the first electrode 7a. The active layer 2, the charge generation layer 8 formed on the active layer 2, and the second electrode 7b formed on the charge generation layer 8 are provided.

  FIG. 10 is a schematic cross-sectional view of an optical sensor according to the second embodiment. An optical sensor 310 illustrated in FIG. 10 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the charge generation layer 8 formed on the first electrode 7a, and the charge generation layer 8. An active layer 2 made of an organic thin film containing the conjugated compound of the present invention, and a second electrode 7b formed on the active layer 2 are provided.

  FIG. 11 is a schematic cross-sectional view of an optical sensor according to the third embodiment. An optical sensor 320 shown in FIG. 11 includes a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing the conjugated compound of the present invention formed on the first electrode 7a. The active layer 2 and the second electrode 7b formed on the active layer 2 are provided.

  In the optical sensor according to the first to third embodiments, a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b. The charge generation layer 8 is a layer that absorbs light and generates charges. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In the active layer 2 (organic thin film), a carrier generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity. Moreover, as the base material 1, a silicon substrate, a glass substrate, a plastic substrate, etc. can be used.

  The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the gist thereof.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Measurement conditions, etc.)
The nuclear magnetic resonance (NMR) spectrum is a product name “JMN-270” (270 MHz at ¹ H measurement) manufactured by JEOL (JEOL Ltd.) or a product name “JMNLA-600” (600 MHz at ¹⁹ F measurement) manufactured by the same company. ). Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used for the internal standard of 0 ppm. The coupling constant (J) is shown in hertz, and the abbreviations s, d, t, q, m, and br are singlet, doublet, triplet, quadruple, respectively. Represents a line, a multiplet, and a broad line. Mass spectrometry (MS) was measured by an electron ionization (EI) method and a direct sample introduction (DI) method using a trade name “GCMS-QP5050A” manufactured by Shimadzu Corporation. As the silica gel in the column chromatography separation, trade name “silica gel 60N” (40-50 μm) manufactured by Kanto Chemical Co., Ltd. was used. All chemical substances are reagent grade and purchased from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Kanto Chemical Co., Ltd., Nacalai Tesque Co., Ltd., Sigma Aldrich Japan Co., Ltd.

Cyclic voltammetry uses the product name “CV-50W” manufactured by BAS Co., Ltd. (BAS) as a measuring device, a Pt electrode manufactured by BAS as a working electrode, a Pt wire as a counter electrode, and a reference electrode It measured using the Ag line. The sweep rate during this measurement was 100 mV / sec, and the scanning potential region was −2.0 V to 1.6 V. Reduction potential and oxidation potential were measured by completely dissolving 1 × 10 ⁻³ mol / L of the conjugated compound and 0.1 mol / L of tetrabutylammonium hexafluorophosphate (TBAPF6) as a supporting electrolyte in a monofluorobenzene solvent. .

Example 1
<Synthesis of Compound A>
In a test tube with a lid dried by heating, 5,5′-ditributylstannyl-2,2′-bithiophene (1.49 g, 2.00 mmol), 4′-bromo-2,2,2-trifluoroacetophenone (1 .27 g, 5.00 mmol), tetrakis (triphenylphosphine) palladium (0) (100 mg, 0.05 mmol) and toluene (20 mL) were added, and the reaction was carried out at 120 ° C. with nitrogen substitution. After 19 hours, water was added and the mixture was extracted with chloroform. The organic phase was dried over magnesium sulfate and concentrated under reduced pressure. The obtained concentrate was washed with methanol and ether, and purified by sublimation in vacuo to obtain compound A (863 mg, yield 85%) represented by the following formula (21) as a red solid. The reduction potential of Compound A was -1.70V.

TLC R _f = 0.2 (hexane); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 8.10 (m, 2H), 7.77 (m, 2H), 7.47 (d, 2H, J = 3.9 Hz), 7.30 (d , 2H, J = 3.9Hz); GC-MS (DI) m / z = 510 (M ⁺ )

Comparative Example 1
<Synthesis of Compound B>
In a test tube with a lid dried by heating, 5,5′-dibromo-2,2′-bithiophene (242 mg, 0.75 mmol), 4-acetylphenylboronic acid (366 mg, 2.23 mmol), tetrakis (triphenylphosphine) palladium (0) (40 mg, 0.05 mmol), sodium hydrogen carbonate (438 mg, 5.21 mmol), dimethoxyethane (DME) / water mixed solvent (7 mL) were added, and the reaction was carried out at 100 ° C. with nitrogen substitution. After 14 hours, the mixture was concentrated under reduced pressure to obtain a concentrate. The obtained concentrate was washed with methanol and ether, and then purified by sublimation in vacuo to obtain Compound B (205 mg, 83% yield) represented by the following formula (22) as a pale yellow solid. The reduction potential of Compound B could not be measured because it was insoluble in monofluorobenzene.

TLC R _f = 0.0 (chloroform); ¹ H-NMR (400 MHz, CDCl ₃ ); δ 7.96 (m, 2H), 7.68 (m, 2H), 7.36 (m, 2H), 7.23 (m, 2H), 2.60 (s, 3H); GC-MS (DI) m / z = 402 (M ⁺ )

Example 2
An intermediate serving as a starting material for the target compound was synthesized according to Scheme 1 below using compound (23a) as a starting material. Details will be described below.

<Synthesis of Compound D>
Compound C-1 represented by the above formula (23a) was synthesized by the method described in the literature (J. Chem. Soc. Perkin Trans 1. Organic and Bio-Organic Chemistry 1992, 21, 2985-2988). Next, Compound C-1 (1.00 g, 6.58 mol) and the fluorinating agent “Selectfluor ^™ (registered trademark)” (5.60 g, 15.8 mol) were placed in a 300 mL three-necked flask, and THF (65 mL) was added. Melted. Tetrabutylammonium hydroxide (TBAH) (10% methanol solution) (3.76 g, 14.5 mol) was added thereto, and the mixture was stirred at 0 ° C. for 12 hours. The solvent was removed under reduced pressure, then water was added, the aqueous phase was extracted with ethyl acetate, the organic phase was dried over magnesium sulfate and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1), and compound C-2 (0.934 g, 75%) represented by the above formula (23b) was obtained as a pale yellow solid. Obtained.

mp 156-158 ° C .; TLC R _f = 0.29 (2: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.60 (d, 1 H, J = 4.8 Hz), 8.28 (d, 1H, J = 4.8Hz); MS (EI) m / z = 188 (M +)

Compound C-2 (1.97 g, 10.48 mmol) was placed in a 200 mL three-necked flask, dissolved by adding N, N′-dimethylformamide (DMF) (50 mL), and further 2-chloromethanol (3.37 g, 41). .91 mmol) was added. To the solution, potassium tert-butoxide dissolved in DMF (50 mL) was added dropwise at -60 ° C. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and water was added to stop the reaction. Next, the aqueous phase was extracted with ethyl acetate and washed with water, and then the organic phase was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1) to obtain compound D (1.58 g, yield 55%) represented by the above formula (24) as a white solid. It was.

mp 117-122 ° C .; TLC R _f = 0.34 (2: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.26 (s, 8H), 7.02 (d, 1H, J = 4.8 Hz), 7.51 (d, 1H, J = 5.1 Hz); MS (EI) m / z = 276 (M ⁺ )

<Synthesis of Compound E>
Compound D (500 mg, 1.81 mmol) was placed in a 50 mL three-necked flask and dissolved by adding THF (18 mL). N-Butyllithium (1.58M, 2.29mL, 3.62mmol) was added thereto at -78 ° C. After stirring for 0.5 hour, tributyltin chloride (1.09 mL, 3.98 mmol) was added, and the temperature was gradually raised to room temperature. After 1 hour, water was added to stop the reaction. The aqueous phase was extracted with ethyl acetate and washed with water, then the organic phase was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained concentrate was purified by alumina column chromatography (hexane / ethyl acetate = 10: 1) to obtain compound E (1.02 g, yield 99%) represented by the above formula (25) as a colorless liquid. It was.

TLC R _f = 0.30 (hexane); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.89 (t, 9H, J = 7.2 Hz), 1.08-1.13 (m, 6H), 1.24-1.38 (m, 6H) , 1.49-1.60 (m, 6H), 4.23-4.28 (m, 8H), 7.03 (s, 1H); MS (EI) m / z = 566 (M ⁺ )

<Synthesis of Compound F>
Compound D (1.00 g, 3.62 mmol) was placed in a 100 mL three-necked flask and dissolved by adding THF (30 mL). Thereto was added n-butyllithium (1.58M, 2.75 mL, 4.34 mmol) at -78 ° C. After stirring for 0.5 hour, bromine (0.29 mL, 5.43 mmol) was added and the temperature was gradually raised to room temperature. After 1 hour, water was added to stop the reaction. The aqueous phase was extracted with ethyl acetate, washed with saturated aqueous sodium thiosulfate solution, washed with water, and the organic phase was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the crude product was passed through silica gel column chromatography (hexane / ethyl acetate = 3: 1) to obtain a crude product of the intermediate compound represented by the above formula (26a). This was put into a 100 mL eggplant flask and dissolved in THF (30 mL). Concentrated sulfuric acid (30 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured onto ice and extracted with water. The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate) to obtain Compound F (877 mg, 91% in 2steps) represented by the above formula (26b) as a brown solid.

TLC R _f = 0.21 (3: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.60 (s, 1H); MS (EI) m / z = 266 (M ⁺ )

<Synthesis of Compound G>
2,5-dibromothiophene (18 mg, 0.0738 mmol), compound E (100 mg, 0.177 mmol), tetrakis (triphenylphosphine) palladium (0) (17 mg, 0.0148 mmol) were placed in a test tube and toluene (1 mL ) Was added and dissolved. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Next, the solvent was distilled off under reduced pressure, and the crude product was passed through alumina column chromatography (hexane / ethyl acetate = 3: 1) and then purified by GPC (chloroform). The compound represented by the following formula (27) G (35 mg, 74%) was obtained as a pale yellow solid.

mp 273-275 ° C .; TLC R _f = 0.68 (1: 2 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.25-4.29 (m, 16H), 7.06 (s, 2H), 7.11 (s, 2H); MS (EI) m / z = 632 (M ⁺ )

<Synthesis of Compound H>
Compound G (35 mg, 0.0550 mmol) was placed in a test tube and dissolved in THF (3 mL). Concentrated sulfuric acid (3 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured onto ice and extracted with water. The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained concentrate was washed with diethyl ether to obtain Compound H (18 mg, 72%) represented by the following formula (28) as a red solid. The reduction potential of Compound H was −1.24V.

TLC R _f = 0.62 (1: 2 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.56 (s, 2H), 7.63 (s, 2H); MS (EI) m / z = 456 (M ⁺ )

Example 3
<Synthesis of Compound I>
1,3-dibromo-5,5-difluoro-4H-cyclopenta [c] thiophene-4,6 (5H) -dione (26 mg, 0.0738 mmol), compound E (100 mg, 0.177 mmol), tetrakis (triphenyl) Phosphine) palladium (0) (17 mg, 0.0148 mmol) was placed in a test tube and dissolved by adding toluene (1 mL). This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Next, the solvent was distilled off under reduced pressure, and the crude product was passed through alumina column chromatography (chloroform) and then purified by GPC (chloroform) to obtain Compound I (33 mg, 61%) represented by the following formula (29). Obtained as a yellow solid.

TLC R _f = 0.59 (1: 2 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.28-4.31 (m, 16H), 8.00 (s, 2H); MS (EI) m / z = 736 (M ⁺ )

<Synthesis of Compound J>
Compound I (72 mg, 0.0978 mmol) was placed in a test tube and dissolved in THF (7 mL). Concentrated sulfuric acid (7 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured into ice and extracted with water. The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained concentrate was recrystallized from hexane / chloroform to obtain Compound J (21 mg, 38%) represented by the following formula (30) as a dark yellow solid. The reduction potential of Compound J was −0.66V.

TLC R _f = 0.32 (1: 2 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 8.40 (s, 2H); MS (EI) m / z = 560 (M ⁺ )

Comparative Example 2
<Synthesis of Compound K>
In a heat-dried test tube with a lid, 1,3-dibromo-5,5-difluoro-4H-cyclopenta [c] thiophene-4,6 (5H) -dione (589 mg, 1.70 mmol), 2-tributylstannylthiophene (1.32 g, 5.10 mmol) and tetrakis (triphenylphosphine) palladium (0) (196 mg, 0.17 mmol) were added.
Toluene (10 mL) was added thereto and reacted at 120 ° C. After 12 hours, the mixture was allowed to cool and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The obtained concentrate is purified by column chromatography (silica gel, chloroform charge) using hexane / ethyl acetate (4/1) as a developing solvent, whereby compound K represented by the following formula (31) (186 mg, 31) %) As a red solid. The reduction potential of Compound K was -1.34V.

TLC R _f = 0.44 (4: 1 = hexane / ethyl acetate); ¹ H-NMR (270 MHz, CDCl ₃ ) δ8.17-8.19 (m, 2H), 7.55-7.57 (m, 2H), 7.18-7.22 ( m, 2H); MS (EI) m / z = 352 (M ⁺ )

Example 4
<Synthesis of Compound L>
5,5′-bis (tributylstannyl) -2,2′-bithiophene (413 mg, 0.555 mmol), compound F (326 mg, 1.22 mmol), tetrakis (triphenylphosphine) palladium (0) (64 mg, 0 0.056 mmol) was placed in a test tube and dissolved in toluene (6 mL). This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. The reaction solution was filtered through Celite and the solvent was distilled off under reduced pressure. The resulting solid was washed with hexane to obtain Compound L (35 mg, 74%) represented by the following formula (32) as a dark purple solid.

mp> 300 ° C .; MS (EI) m / z = 538 (M ⁺ )

Example 5
<Preparation of Organic Thin Film Element 1 and Evaluation of Transistor Characteristics>
A silicon oxide film having a thickness of 300 nm formed as an insulating layer by thermal oxidation was prepared on the surface of a heavily doped p-type silicon substrate serving as a gate electrode. On the substrate, comb source and drain electrodes having a channel width of 38 mm and a channel length of 5 μm were formed by a lift-off method. The substrate with electrodes was ultrasonically cleaned with acetone for 10 minutes and then with isopropyl alcohol for 10 minutes, and then the surface was cleaned by irradiation with ozone UV for 30 minutes. An organic thin film of the compound A synthesized in Example 1 was formed on the cleaned substrate by a vacuum vapor deposition method to produce an organic thin film element 1. When the organic transistor characteristics were measured by changing the gate voltage Vg in the range of 0 to 100 V and the source-drain voltage Vsd in the range of 0 to 100 V in the organic thin film element 1, the Id-Vg of a good n-type semiconductor was measured. Characteristics were obtained. The mobility at this time was as favorable as 3.4 * 10 < ^-3 > cm < ² > / Vs and on / off ratio 10 < ⁴ > -10 < ⁵ >.

Comparative Example 3
<Preparation of organic thin film element 2 and evaluation of transistor characteristics>
In the same manner as in Example 5, an organic thin film of Compound B synthesized in Comparative Example 1 was formed to produce an organic thin film element 2. By changing the gate voltage Vg in the range of 0 to 100 V and the source-drain voltage Vsd in the range of 0 to 100 V in vacuum in the obtained organic thin film element 2 and measuring the organic transistor characteristics, the Id− of the p-type semiconductor is obtained. Vg characteristics were obtained. The mobility at this time was as low as 1.8 × 10 ⁻⁵ cm ² / Vs and an on / off ratio of 10 ² .

Example 6
<Preparation of Organic Thin Film Element 3 and Evaluation of Transistor Characteristics>
In the same manner as in Example 5, an organic thin film of Compound L synthesized in Example 4 was formed to produce an organic thin film element 3. By changing the gate voltage Vg in the range of 0 to 100 V and the source-drain voltage Vsd in the range of 0 to 100 V in vacuum in the obtained organic thin film element 3 and measuring the organic transistor characteristics, a good n-type semiconductor was obtained. Id-Vg characteristics were obtained. The mobility at this time was as favorable as 1.5 × 10 ⁻³ cm ² / Vs and an on / off ratio of 10 ⁴ .

Example 7
<Preparation of Organic Thin Film Element 4 and Evaluation of Transistor Characteristics>
A substrate was prepared in which a silicon oxide film serving as an insulating layer was formed by thermal oxidation on the surface of a heavily doped p-type silicon substrate serving as a gate electrode. This substrate was dipped in hexamethyldisilazane (HMDS, manufactured by Aldrich) at 50 ° C. for 7 hours and surface-treated. Next, an organic thin film of Compound A having a film thickness of 30 nm was deposited on the surface-treated substrate by vacuum evaporation at room temperature. On this organic thin film, Au was vapor-deposited with a thickness of 30 nm through a shadow mask to form a source electrode and a drain electrode having a channel width of 5.5 mm and a channel length of 50 μm, whereby the organic thin film element 4 was produced. When the transistor characteristics of the obtained organic thin film element 4 were measured by changing the gate voltage Vg and the source-drain voltage Vsd in nitrogen, good Id-Vg characteristics were obtained, and Vg = 100V, Vd = 100V. A current of drain current Id = 1.1 × 10 ⁻⁴ A flowed. At this time, the mobility was 0.12 cm ² / Vs, and the threshold voltage at which the current was turned on was Vth = 60V. From this, it was confirmed that the organic thin film element 4 using the compound A functions effectively as an n-type organic transistor.

Example 8
<Preparation of organic thin film element 5 and evaluation of transistor characteristics>
In the same manner as in Example 7, an organic thin film element 5 was produced using an organic thin film of Compound L instead of an organic thin film of Compound A. When the transistor characteristics of the obtained organic thin film element 5 were measured by changing the gate voltage Vg and the source-drain voltage Vsd in nitrogen, good Id-Vg characteristics were obtained. Vg = 80V, Vd = 100V The drain current Id = 1.5 × 10 ⁻⁵ A flowed. Moreover, the mobility of this time is 0.013 cm ² / Vs, an on / off ratio of 10 ^5, the threshold voltage the current is turned on was Vth = 38V. From this, it was confirmed that the organic thin film element 5 using the compound L functions effectively as an n-type organic transistor.

Example 9
<Synthesis of Compound M>
2-Bromo-3-hexylthiophene (600 mg, 2.43 mmol), compound E (1.51 g, 2.67 mmol) synthesized in Example 2 and tetrakis (triphenylphosphine) palladium ( 0) (281 mg, 0.243 mmol) was added, and toluene (25 mL) was added and dissolved. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Next, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 10: 1) to obtain compound M represented by the following formula (33) (960 mg, yield). 81%) was obtained as a yellow liquid.

TLC R _f = 0.46 (5: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.89 (t, 3H, J = 3.6 Hz), 1.23-1.43 (m, 4H), 1.53 -1.69 (m, 4H), 2.72 (t, 2H, J = 8.0Hz), 4.27 (s, 8H), 6.94 (d, 1H, J = 5.4Hz), 6.97 (s, 1H), 7.22 (d, 1H, J = 5.4Hz); MS (EI) m / z442 (M ⁺ ).

<Synthesis of Compound N>
Compound M (300 mg, 0.679 mmol) was placed in a heat-dried 20 mL three-necked flask, and dissolved in THF (7 mL). N-Butyllithium (1.58M, 0.88mL, 1.39mmol) was added thereto at -78 ° C. After stirring for 1 hour, tributyltin chloride (0.221 ml, 0.814 mmol) was added, and the temperature was gradually raised to room temperature. After 0.5 hour, water was added to stop the reaction. The aqueous phase was extracted with ethyl acetate, washed with water and then the organic phase was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the crude product was purified by alumina column chromatography (hexane / ethyl acetate = 10: 1), and compound N (440 mg, yield 89%) represented by the following formula (34) was yellow. Obtained as a liquid.

TLC R _f = 0.67 (5: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ0.85-0.93 (m, 12H), 1.07-1.13 (m, 6H), 1.26-1.40 ( m, 10H), 1.51-1.67 (m, 10H), 2.74 (t, 2H, 8.0Hz), 4.27 (s, 8H), 6.95 (s, 1H), 6.96 (s, 1H); MS (EI) m / z = 732 (M ⁺ ).

<Synthesis of Compound O>
1,3-dibromo-5,5-difluoro-4H-cyclopenta [c] thiophene-4,6 (5H) -dione (93 mg, 0.27 mmol), compound N (435 mg, 0.594 mmol) and tetrakis (triphenyl) Phosphine) palladium (0) (31 mg, 0.027 mmol) was placed in a test tube and dissolved by adding toluene (3 mL). This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Then the solvent was distilled off under reduced pressure, the resulting crude product was purified from through a silica gel column chromatography (CHCl ₃₎ in GPC (CHCl _3), the compound represented by the following formula (35) O (230mg , Yield 80%) as a red solid.

TLC R _f = 0.39 (2: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.90 (t, 6H, J = 7.1 Hz), 1.29-1.46 (m, 12H), 1.65 -1.75 (m, 4H), 2.79 (t, 4H, J = 7.9Hz), 4.30 (s, 16H), 7.13 (s, 2H), 8.03 (s, 2H).

<Synthesis of Compound P>
Compound O (250 mg, 0.234 mmol) was placed in an eggplant flask (30 mL), and THF (3 mL) was added to dissolve it. Concentrated sulfuric acid (10 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. The resulting reaction mixture was poured onto ice and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium bicarbonate solution, then with water and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting solid was purified by GPC (CHCl ₃ ) to obtain compound P (99 mg, yield 47%) represented by the following formula (36) as a red solid.

TLC R _f = 0.57 (2: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.92 (t, 6H, J = 7.1 Hz), 1.23-1.52 (m, 12H), 1.73 -1.83 (m, 4H), 2.91 (t, 4H, J = 7.9Hz), 7.63 (s, 2H), 8.12 (s, 2H); MS (EI) m / z = 892 (M ⁺ ).

Example 10
<Synthesis of Compound Q>
5,5′-Dibromo-4,4′-dihexyl-2,2′-bithiophene (492 mg, 1.00 mmol) was placed in a 20 mL three-necked flask and dissolved by adding THF (10 mL). N-Butyllithium (1.58M, 1.39mL, 2.20mmol) was added thereto at -78 ° C. After stirring for 1 hour, tributyltin chloride (0.543 ml, 2.00 mmol) was added, and the temperature was gradually raised to room temperature. After 2 hours, the reaction was stopped by adding water and a small amount of hydrochloric acid. The aqueous phase was extracted with diethyl ether, washed with water and then the organic phase was dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained liquid was purified by GPC (CHCl ₃ ) to obtain Compound Q (630 mg, yield 69%) represented by the following formula (37) as a yellow liquid.

TLC R _f = 1.0 (hexane); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.84-0.94 (m, 24H), 1.02-1.20 (m, 12H), 1.26-1.39 (m, 24H), 1.46 1.61 (m, 16-H), 2.51 (t, 4H, 8.0 Hz), 7.13 (s, 2H); MS (EI) m / z = 912 (M ⁺ ).

<Synthesis of Compound R>
Compound Q (50 mg, 0.055 mmol), Compound F (32 mg, 0.12 mmol) synthesized in Example 2 and tetrakis (triphenylphosphine) palladium (0) (6 mg, 0.005 mmol) were placed in a test tube with a lid. Toluene (1 mL) was added and dissolved. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. The solvent was then distilled off under reduced pressure, the crude product was purified from through a silica gel column chromatography (CHCl ₃₎ in GPC (CHCl _3), the following equation (38) with a compound represented by R (19 mg, yield: 49%) as an orange solid. Compound R had an oxidation potential of 0.48 V and a reduction potential of −1.87 V. Furthermore, the peak wavelength of the absorption spectrum was 472 nm.

TLC R _f = 0.43 (5: 1 = hexane / ethyl acetate); ¹ H-NMR (400 MHz, CDCl ₃ ) δ0.88-0.96 (m, 6H), 1.28-1.49 (m, 12H), 1.65-1.76 ( m, 4H), 2.85 (t, 4H, J = 7.9Hz), 7.19 (s, 2H), 7.51 (s, 2H); MS (EI) m / z = 706 (M ⁺ ).

Example 11
<Synthesis of Compound S>
2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-di (n-octyl) fluorene, compound F, tetrakis (triphenylphosphine) palladium ( 0), potassium carbonate and tetrahydrofuran (THF) / water mixed solvent are added, and the reaction is carried out at 100 ° C. with nitrogen substitution. After 12 hours, the solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography and then purified by GPC (CHCl ₃ ), whereby the target compound S represented by the following formula (39) was obtained. Can be obtained.

Example 12
<Synthesis of Compound T>
2,7-dibromo-9,9-di (n-octyl) fluorene, compound N and tetrakis (triphenylphosphine) palladium (0) are placed in a test tube with a lid, and toluene is added to dissolve. This is stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. The solvent is distilled off under reduced pressure, and the resulting crude product is passed through silica gel column chromatography and then purified by GPC (CHCl ₃ ). The obtained compound is put into an eggplant flask, dissolved in THF, concentrated sulfuric acid is added thereto, and the mixture is stirred at room temperature for 12 hours. The reaction mixture is subsequently poured onto ice and extracted with ethyl acetate, and the organic layer is washed with saturated aqueous sodium hydrogen carbonate solution and water and then dried over magnesium sulfate. The solvent is distilled off under reduced pressure, and the obtained solid is purified by GPC (CHCl ₃ ) to obtain a compound T represented by the following formula (40).

Example 13
<Synthesis of Compound Ua>
In a test tube with a heat-dried lid, 2,5-dibromothiophene (48 mg, 0.199 mmol), 5-tributyl-3-hexylthiophene (200 mg, 0.437 mmol) and tetrakis (triphenylphosphine) palladium (0) (11 mg , 0.0199 mmol), and toluene (2 mL) was added to dissolve. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Next, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane), and the compound Ua (48 mg, yield 58%) represented by the following formula (41a) was used as a yellow liquid. Obtained.

TLC R _f = 0.75 (hexane); ¹ HNMR (400 MHz, CDCl ₃ ) δ 0.89 (m, 6H), 1.22-1.44 (m, 12H), 1.50-1.72 (m, 4H), 2.58 (t, 4H, J = 7.8Hz), 6.80 (s, 2H), 7.00 (s, 2H), 7.03 (s, 2H); MS (EI) m / z = 416 (M ⁺ ).

<Synthesis of Compound Ub>
Compound Ua (100 mg, 0.240 mmol) and tetramethylethylenediamine (58 mg, 0.504 mmol) were placed in a heat-dried 30 mL two-necked flask, and diethyl ether (3 mL) was added and dissolved. N-Butyllithium (1.58M, 0.319 mL, 0.504 mmol) was slowly added thereto at 0 ° C. After stirring for 2 hours, tributyltin chloride (0.221 ml, 0.814 mmol) was slowly added at −78 ° C., and the temperature was gradually raised to room temperature. Water was added to stop the reaction, the aqueous phase was extracted with diethyl ether, and the organic phase was washed with a saturated aqueous copper sulfate solution and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by alumina column chromatography (hexane) to obtain compound Ub (165 mg, yield 69%) represented by the following formula (41b) as a yellow liquid. It was.

TLC R _f = 1.0 (hexane); ¹ HNMR (400 MHz, CDCl ₃ ) δ0.84-0.96 (m, 24H), 1.05-1.20 (m, 12H), 1.25-1.45 (m, 24H), 1.50-1.70 ( m, 16H), 2.51 (t, 4H, J = 8.0Hz), 7.02 (s, 2H), 7.14 (s, 2H).

<Synthesis of Compound Uc>
Compound Ub (50 mg, 0.050 mmol), compound F (29 mg, 0.11 mmol) synthesized in Example 2 and tetrakis (triphenylphosphine) palladium (0) (6 mg, 0.0050 mmol) were placed in a test tube, and toluene was added. (1 mL) was added and dissolved. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. The solvent was distilled off under reduced pressure, the obtained crude product was purified from through a silica gel column chromatography (CHCl ₃₎ in GPC (CHCl _3), the compound represented by the following formula (41c) Uc (16mg, yield 49%) was obtained as a red solid.

TLC R _f = 0.48 (3: 1 = hexane / ethyl acetate); ¹ HNMR (400 MHz, CDCl ₃ ) δ0.92 (t, 6H, J = 7.1 Hz), 1.29-1.50 (m, 12H), 1.69-1.75 (M, 4H), 2.84 (t, 4H, J = 7.8Hz), 7.14 (s, 2H), 7.23 (s, 2H), 7.48 (s, 2H); MS (EI) m / z = 788 (M ⁺ ).

Example 14
<Synthesis of Compound V>
1,3-dibromo-5,5-difluoro-4H-cyclopenta [c] thiophene-4,6 (5H) -dione (400 mg, 1.16 mmol), 2-bromo-3-hexylthiophene (1.33 g, 2 .90 mmol) and tetrakis (triphenylphosphine) palladium (0) (134 mg, 0.116 mmol) were placed in a test tube and dissolved by adding toluene (12 mL). This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Then the solvent was distilled off under reduced pressure, the resulting crude product was purified from through a silica gel column chromatography (CHCl ₃₎ in GPC (CHCl _3), the compound represented by the following formula (42) V (247mg Yield 41%) as a red solid.

TLC R _f = 0.39 (3: 1 = hexane / ethyl acetate); ¹ HNMR (400 MHz, CDCl ₃ ) δ0.84-0.93 (m, 6H), 1.23-1.41 (m, 12H), 1.61-1.72 (m, 4H), 2.75 (t, 4H, J = 7.9Hz), 7.09 (d, 2H, J = 5.1Hz), 7.52 (d, 2H, J = 5.1Hz); MS (EI) m / z = 520 (M ⁺ ).

<Synthesis of Compound W>
Under ice-cooling, Compound V (103 mg, 0.198 mmol) was placed in a 20 mL eggplant flask dried by heating, and DMF (2 mL) was added to dissolve. N-bromosuccinimide (NBS) (74 mg, 0.416 mmol) was added thereto, and the temperature was gradually raised to 80 ° C. After stirring for 12 hours, water was added to stop the reaction. The aqueous phase was extracted with ethyl acetate, washed with water and then the organic phase was dried over magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (ethyl acetate), and compound W (125 mg, yield 91%) represented by the following formula (43) was converted to a red solid. Obtained.

TLC R _f = 0.42 (3: 1 = hexane / ethyl acetate); ¹ HNMR (400 MHz, CDCl ₃ ) δ 0.88 (t, 6H, J = 7.1 Hz), 1.20-1.42 (m, 12H), 1.60-1.71 (M, 4H), 2.70 (t, 4H, J = 7.9Hz), 7.22 (s, 2H); MS (EI) m / z = 678 (M ⁺ ).

<Synthesis of Compound X>
Compound W (125 mg, 0.184 mmol), Compound E (240 mg, 0.424 mmol), tetrakis (triphenylphosphine) palladium (0) (21 mg, 0.018 mmol) were placed in a test tube, and toluene (2 mL) was added. Melted. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. The solvent was distilled off under reduced pressure and the resulting crude product was purified from the through alumina column chromatography (CHCl ₃₎ in GPC (CHCl _3). This was put into an eggplant flask (50 mL) and dissolved in THF (1 mL). Concentrated sulfuric acid (20 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured onto ice and extracted with ethyl acetate. The organic phase was washed with a saturated aqueous sodium bicarbonate solution, washed with water and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting solid was purified by GPC (CHCl ₃ ) to obtain Compound X (23 mg, 2 steps yield 14%) represented by the following formula (44) as a red solid.

TLC R _f = 0.51 (2: 1 = hexane / ethyl acetate); ¹ HNMR (400 MHz, CDCl ₃ ) δ 0.86 (t, 6H, J = 7.0 Hz), 1.17-1.41 (m, 12H), 1.69-1.78 (M, 4H), 2.81 (t, 4H, J = 8.0Hz), 7.47 (s, 2H), 7.63 (s, 2H); MS (EI) m / z = 892 (M ⁺ ).

  From the above, the organic thin film element provided with the organic thin film containing the π-conjugated compound of the present invention produced in Examples 5, 6, 7 and 8 has a higher electron mobility than the organic thin film element produced in Comparative Example 3. It was found to be good. From this, it was confirmed that the π-conjugated compound of the present invention can be used as an n-type organic semiconductor having an excellent electron transport property.

It is a schematic cross section of the organic thin-film transistor which concerns on 1st Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 2nd Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 3rd Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 4th Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 5th Embodiment. It is a schematic cross section of the organic thin-film transistor concerning 6th Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 7th Embodiment. It is a schematic cross section of the solar cell according to the embodiment. It is a schematic cross section of the photosensor concerning a 1st embodiment. It is a schematic cross section of the optical sensor which concerns on 2nd Embodiment. It is a schematic cross section of the photosensor concerning a 3rd embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Active layer, 2a ... Active layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode, 6 ... Drain electrode, 7a ... 1st electrode, 7b ... 2nd electrode, 8 ... Charge generation layer, 100 ... organic thin film transistor according to the first embodiment, 110 ... organic thin film transistor according to the second embodiment, 120 ... organic thin film transistor according to the third embodiment, 130 ... organic thin film transistor according to the fourth embodiment, 140 ... Organic thin film transistor according to fifth embodiment, 150... Organic thin film transistor according to sixth embodiment, 160. Organic thin film transistor according to seventh embodiment, 200... Solar cell according to embodiment, 300. , 310... Optical sensor according to the second embodiment, 320... Optical sensor according to the third embodiment.

Claims (9)

Co-role-based compound you express under following general formula (V).

[Wherein, R ⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms , and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, saturated or unsaturated. Hydrocarbon group, hydroxyl group, alkoxy group, alkanoyloxy group, amino group, oxyamino group, alkylamino group, dialkylamino group, alkanoylamino group, cyano group, nitro group, sulfo group, alkyl group substituted by halogen atom An alkoxysulfonyl group (wherein the alkoxy group may be substituted with a halogen atom), an alkylsulfonyl group (wherein the alkyl group may be substituted with a halogen atom), a sulfamoyl group, an alkylsulfamoyl group, Carboxyl group, carbamoyl group, alkylcarbamoyl group, alkanoyl group, or alkoxy Indicates a carbonyl group, ^{Z 1} represents any of the groups represented by the following formula (ii) ~ (ix), Z 1 ' represents a group represented by the following formula ^{(i), Ar 1, Ar} 2 And Ar ³ are each independently a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms (these groups are a halogen atom, a saturated or unsaturated hydrocarbon group) , an aryl group, an alkoxy group, an arylalkyl group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, or a cyano group which may have a substituent. However, a fluorine atom as a whole these groups M, n and p each independently represents an integer of 0 to 6. A plurality of R ⁰ , R ¹ , R ² , Z ¹ and Z ¹ ′ may be the same or different. ]

[Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a saturated or unsaturated hydrocarbon group, a hydroxyl group, an alkoxy group, an alkanoyloxy group, an amino group, an oxyamino group, an alkylamino group. Group, dialkylamino group, alkanoylamino group, cyano group, nitro group, sulfo group, alkyl group substituted by halogen atom, alkoxysulfonyl group (however, the alkoxy group may be substituted by halogen atom), alkylsulfonyl A group (provided that the alkyl group may be substituted with a halogen atom), a sulfamoyl group, an alkylsulfamoyl group, a carboxyl group, a carbamoyl group, an alkylcarbamoyl group, an alkanoyl group, or an alkoxycarbonyl group, and R ³ and R ⁴ may be bonded to each other to form a ring. ] At least one of Ar ¹ , Ar ² and Ar ³ is a halogen atom, saturated or unsaturated hydrocarbon group, aryl group, alkoxy group, arylalkyl group, aryloxy group, monovalent heterocyclic group as a substituent , amino group, a nitro group, or an optionally thienylene group which may have a cyano group (provided that no fluorine atom as a whole group), according to claim 1 conjugated compound according. Co-role-based compound you express under following general formula (VI).

[Wherein, R ¹⁰ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a fluoroalkoxy having 1 to 20 carbon atoms. represents a group, ^{Z 2} represents any of the groups represented by the following formula (xii) ~ (xiii) and (xv) ~ (xix), Ar 4, Ar 5 and Ar ⁶ each independently A divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms (these groups are a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an arylalkyl group) group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, or indicates also may) have a cyano group as a substituent, q, r and s are each independently 0-6 of Indicates an integer. A plurality of R ¹⁰ and Z ² may be the same or different. ]

[Wherein R ¹⁶ represents a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group, a hydroxyl group, an alkoxy group, an alkanoyloxy group, an amino group, an oxyamino group, an alkylamino group, a dialkylamino group, an alkanoylamino group. , A cyano group, a nitro group, a sulfo group, an alkyl group substituted with a halogen atom, an alkoxysulfonyl group (wherein the alkoxy group may be substituted with a halogen atom), an alkylsulfonyl group (wherein the alkyl group is a halogen atom) A sulfamoyl group, an alkylsulfamoyl group, a carboxyl group, a carbamoyl group, an alkylcarbamoyl group, an alkanoyl group, or an alkoxycarbonyl group. ] The conjugated compound according to claim 3 , wherein Z ² is a group represented by the formula (xii). The organic thin film containing the conjugated compound as described in any one of Claims 1-4 . An organic thin film element comprising the organic thin film according to claim 5 . An organic thin film transistor comprising a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between these electrodes, and a gate electrode for controlling a current amount passing through the current path, wherein the organic semiconductor layer is claimed. 5. An organic thin film transistor comprising the organic thin film according to 5 . An organic solar cell comprising the organic thin film according to claim 5 . An optical sensor comprising the organic thin film according to claim 5 .

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