TW201240946A - Compound having acceptor groups, and organic thin film and organic thin film element using same - Google Patents

Abstract

A compound provided with: a core part, which is a tetravalent or higher group derived from a cage compound or aliphatic hydrocarbon compound; and four or more side-chain groups bonded to the core part, two or more of the side-chain groups having an acceptor group.

Description

201240946 VI. [Technical Field] The present invention relates to a compound having an acceptor group, an organic film using the same, and an organic film element. [Prior Art] A film containing an organic material having a charge (general charge of electrons and holes) is expected to be applied to a photoelectric conversion element (for example, an organic thin film solar cell, a photosensor), an organic electroluminescence device, Organic thin film transistor. Therefore, various developments have been made in the development of organic P-type semiconductors exhibiting hole transport properties and organic n-type semiconductors exhibiting electron transport properties. As a photoelectric conversion element using an organic material, a structure composed of a combination of an organic p-type semiconductor and an organic n-type semiconductor has been proposed. For example, there are reports of poly[(2-methoxy-5-(2'-ethylhexyloxy)) 4-phenylene vinyl) using a polyphenylene extended vinyl derivative as an organic germanium semiconductor. And an electron-accepting π-conjugated polymer such as polyhexylthiophene, and an electron acceptor-containing fullerene derivative (for example, C60, see Patent Document 1 and Non-Patent Document 1). PRIOR ART DOCUMENT Patent Document Patent Document 1: International Publication No. 94/005045 Non-Patent Document Non-Patent Document 1: G. Yu, Science, No. 270, p. 1789 201240946 (1995) [Summary of the Invention] However, the electron transporting property of the conventional organic n-type semiconductor is not necessarily sufficient as compared with the organic P-type semiconductor, and an organic n-type semiconductor having higher electron transport property is required. An object of the present invention is to provide a compound which can be used as an organic n-type semiconductor having excellent electron transport properties. Further, an object of the present invention is to provide an organic thin film containing the compound and an organic thin film device comprising the organic thin film. Means for Solving the Problem] The present invention relates to a compound comprising: a core having a tetravalent or higher group derived from a cage compound or an aliphatic hydrocarbon compound, and four or more side chain groups bonded to the core 2 or more of the side chain groups have an acceptor group. Since the compound of the present invention has an acceptor group contained in a side chain group, it can exhibit properties as an organic n-type semiconductor (electron acceptor) The function of the organic semiconductor is also three-dimensionally arranged by the side chain system bonded to the core. Therefore, the base of the acceptor is stereoscopically arranged in the film, and it is expected that it is difficult to obtain the molecules in the display plane. The above-described compound of the present invention is excellent in electron transport property and can be used as an organic n-type semiconductor. -6 - 201240946 The above cage compound is preferably adamantane or sesquinal sesquioxane, and the above aliphatic The hydrocarbon compound is preferably methane. Further, the above acceptor group is preferably a group containing a fullerene derivative residue, a group containing a naphthoquinone derivative residue or a residue containing a quinone imide derivative. Base The compound produced is excellent in the interaction between molecules, and the stability of the compound is also excellent. Therefore, the electron transport property is more excellent. On the other hand, the present invention provides an organic film containing the above compound of the present invention, and The organic thin film device, the organic thin film transistor, the organic thin film solar cell, and the photosensor of the present invention. The organic thin film device, the organic thin film transistor, the organic thin film solar cell, and the photo sensor of the present invention have a display capable of exhibiting The organic thin film of the compound of the present invention having excellent electron transport properties can exhibit excellent performance. According to the present invention, a novel compound which can be used as an organic semiconductor excellent in charge transport property can be provided. Further, according to the present invention, an organic thin film containing the compound and an organic thin film device comprising the organic thin film can be provided. This organic thin film element can be excellent in stability. In the preferred embodiment, the compound of the present invention is excellent in stability and solubility in an organic solvent, so that an organic thin film element having excellent performance can be easily produced by forming an organic film using a solution. [Embodiment] In the following, a preferred embodiment of the present invention will be described in detail with reference to the drawings. In the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. The positional relationship such as up, down, left, and right is based on the positional relationship shown on the drawing as long as it is not specified in advance. The dimensional ratio of the drawings is not limited by the ratios shown. 1. Compound having an accepting group The compound of the present embodiment is a core having a tetravalent or higher group derived from a cage compound or an aliphatic hydrocarbon compound, and four or more side chains bonded to the core. The basis of the composition. Two or more of the four or more side chain groups have an acceptor group. Hereinafter, the compound having such a constitution is referred to as an "acceptor compound" as the case may be. The core has four or more atoms to which a side chain group is bonded as a bonding portion. When three atoms bonded to the bonding portion of the core are arbitrarily selected from the atoms constituting the side chain group, bonds bonded to the core are disposed outside the plane formed by the three atoms (outside surface) At least one of the other atoms in the junction is present in the atoms constituting the side chain group. It is preferable that the core portion having such a configuration has a vertex, a regular tetrahedron, a regular hexahedron, or the like, which is disposed at the apex of the polygonal pyramid such as a triangular pyramid, a quadrangular pyramid, and a pentagonal pyramid, a triangular prism, a quadrangular prism, and a pentagonal column. The bonding portion of the apex of the regular polyhedron such as a regular octahedron, a regular dodecahedron, and an icosahedron. In the apex of a skewed structure of a polygonal pyramid, a polygonal column, or a regular polyhedron or a vertice of a structure that is partially defective at the apex of a structure from a polygonal pyramid, a polygonal prism, or a regular polyhedron, the key of the core may also be configured -8-201240946 Knot part. The tetravalent group of the core may be a residue obtained by removing four or more hydrogen atoms from the aliphatic hydrocarbon compound. This aliphatic hydrocarbon compound is preferably methane. The tetravalent group of the core may be a residue obtained by removing four or more hydrogen atoms or substituents from the cage compound. Preferably, the cage compound is selected from the group consisting of cubane, adamantane, sesquioxanes and the like. Among these, sesquisesquioxane is preferred. The core may be composed of a plurality of residues derived from the same or different cage compounds, and the plural residues may be bonded to each other as adamantane and the like, and the adamantane represented by the following structural formula may be exemplified. (1 〇〇), diadamantane (1 〇 1 ), diamantane (1 02 ), triamantane (1 03 ), tetramantane (1 04 ) and isotetramantane (1 05 ). Among these, adamantane is preferred.

The caged oxime oxane is generally obtained by partially hydrolyzing and condensing a trifunctional decane to have the formula: (RSi03/2) n (R represents a hydrogen atom or a substituent, and η represents a positive integer) The polyhedral cluster of the configuration shown. The structure of the completely condensed η = 8, 10 or 12 sesquisesquioxane, each of 201240946, is represented by the following structural formula (200), (201) or (2〇2). Incompletely condensed sesquisesquioxanes can also be used. The core portion derived from sesquioxanes is a residue obtained by removing four or more Rs. The core portion is preferably a residue obtained by removing four or more Rs from a sesquioxane having n = 8. -10- 201240946 [Chemical 2] RSi / Ο

Ο——SiR / Ο I n=8 -——SiR (200) RSi^—5-0——SiR° Ο Ο

RSi-Ο-SiR

(201) η=10

RSi - Ο - SiR RSi:

.SiR O' Ο 〇 RSi——r 尸卜 Ο ;i——Ο——SiR V I , 〇,

.Ο Ο-SiR o

SiR^ SiR n=12 (202)

The side chain group in which RSi-0-SiR is bonded to the core is a group represented by the following formula (10). -L-T (10) -11 - 201240946 In the formula (10), L represents a single bond or a divalent organic group, a hydrazine, a halogen atom or a monovalent organic group. In two or more of the side chain groups of the above-mentioned acceptor compound, the plural L and oxime in the same molecule of the lanthanide acceptor group may be the same or the phase is easy to manufacture and the intermolecular The interaction is easy and L and Τ are preferably the same. The acceptor-based group may be selected from the group consisting of a function as an electron acceptor with a donor group. Receptor group, for example, a diazole derivative residue, a quinodimethane derivative residue, a benzoinyl group, a naphthoquinone derivative residue, an anthracene derivative residue, a tetracyanoalkane derivative residue , anthracene derivative residue, diphenyldicyanate residue, terephthalamide derivative residue, 8-hydroxyquinoline-derived fullerene derivative residue such as C60 and C7G, naphthoquinone imine a group comprising a residue of a residue containing a quinone imine derivative, a residue of a residue containing a triphenyl pentanthene terryleneimide derivative, a residue of a residue containing a quinone tribenzo amide derivative, and a quinone-containing imine The residue of the residue of the derivative hexenyleneimine derivative and the group containing the heptene quinone residue. Among these, a fullerene derivative, a group containing a naphthoquinone derivative residue, and a quinone imine-derived group are preferable. Further, the acceptor group is more preferably a group containing a residue of a naphthoquinone derivative or a quinone imine derivative containing a fullerene derivative. Since it is easy to synthesize, it is particularly preferred to contain a residue of a naphthoquinone imine derivative, and since the electron attracting property of the acceptor group is increased, the acceptor contains a fluorine atom. The table does not contain nitrogen. Occurs in a different, but by, a combination of plural, and is selected from the residue of an anthracene derivative residue, a residue of a dimethicone derivative, a living residue of a quinone imine (a group of a pentaphene group, an amine-containing derivative residue) The group of the base of the residue of the substrate, the group of the group of the residue. The group is preferably -12 - 201240946. The group containing the residue of the derivative is represented by the following structural formula, for example.

[Chemical 5]

-13- 201240946 [Chem. 6]

The base of the residue containing a quinone imine derivative is represented by the following structural formula, for example.

-14- 201240946 [化9]

[化10]

[化11]

[化 12]

-15- 201240946 [Chem. 13]

[Chem. 14]

[化15]

(A) e A group containing a residue of a tribenzopentanthmine derivative, for example, represented by the following structural formula. -16- 201240946 [Chem. 16]

In the formula, rM represents a monovalent organic group and represents a divalent organic group, and RQ3 represents a trivalent organic group, and when RQ1, RQ2 and RG3 are plural in the same formula, they may be the same or different, and A represents an alkyl group. An alkoxy group, a sulfonyl group, an amine group, an ammonium group, a hydroxyl group, a nitro group or a halogen atom, e represents an integer of 0 to 4, f represents an integer of 〇~12, and g represents an integer of 〇~8. The monovalent organic group shown may, for example, be a linear, branched or cyclic alkyl group, an alkoxy group, an aryl group, a monovalent heterocyclic group, an amine group, a nitro group or a cyano group. The alkyl group may have a carbon number of 1 to 20, the alkoxy group may have a carbon number of 1 to 20, and the aryl group may have a carbon number of 6 to 60. The monovalent heterocyclic group is, for example, self-selected from furan, thiophene, and thiophene. Residues of thiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyridinium, pyrimidine, hydrazine, triterpenoid heterocyclic compound after removal of one hydrogen atom base. The aryl group and the monovalent heterocyclic group may have a substituent such as a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amine group, a cyano group or a nitro group. The divalent organic group represented by RW may, for example, be an alkyl group, a vinyl group, an oxy group (-〇-), a thio group (-S-), a carbonyl group, a thiocarbonyl group, a sulfenyl group or a sulfonyl group. A monosubstituted amino group and a residue having a ring structure after removing two hydrogen atoms from a cyclic compound such as a benzene, a condensed ring compound or a heterocyclic compound. The alkyl group may have a carbon number of from 1 to 2 0. The monosubstituted amino group is an amine group substituted with one substituent such as an alkyl group having 1 to 12 carbon atoms of carbon-17 to 201240946 and an aryl group having 6 to 20 carbon atoms. Among these, it is particularly preferred to extend the alkyl group and remove the residue from the hydrogen atom from the benzene. The residue having a ring structure may also have a substituent. The substituent may, for example, be a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group 'amino group, a nitro group or a fluorenyl group. The 'saturated or unsaturated aliphatic hydrocarbon group may have a carbon number of 1 to 20' aryl group and may have a carbon number of 6 to 60, and the alkoxy group may have a carbon number of 1 to 20 'aryloxy group. The carbon number may be 7 to 80. The monovalent heterocyclic group is, for example, self-selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazepine, benzothiazepine, beer, and The residue of the heterocyclic compound of Mi Mi, Di Ding, Shame, Pyrimidine, Anthracene and Triterpenoids after removing one hydrogen atom. The trivalent organic group represented by RU may, for example, be a residue having a ring structure after removing three hydrogen atoms from a cyclic compound such as a benzene, a condensed ring compound or a heterocyclic compound. Among them, the residue after removing three hydrogen atoms from benzene is particularly preferred. The residue having a ring structure may also have a substituent. The substituent '' may, for example, be a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amine group, a nitro group or a cyano group. Among these, the saturated or unsaturated aliphatic hydrocarbon group may have a carbon number of 1 to 20' aryl groups and may have a carbon number of 6 to 60, and the alkoxy group may have a carbon number of 1 to 20 'aryloxy group. The carbon number may be 7 to 80. The monovalent heterocyclic group is, for example, self-selected from furan, thiophene 'thienothiophene, benzothiophene' thiazide, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole. A residue in which one hydrogen atom is removed from a heterocyclic compound of pyridine, pyridinium, pyrimidine, pyrene, and tri-n. The acceptor compound of the present embodiment has two or more side chain groups having a substituent of the group -18 - 201240946. Since the electron transporting property of the acceptor compound of the present embodiment is higher, the number of acceptor groups is preferably 4 or more, more preferably 6 or more. Further, the electron transporting property of the acceptor compound of the present embodiment is further high. All of the side chain groups bonded to the core are particularly reactive groups. The acceptor group is preferably disposed at the end of the side chain group. The acceptor group is preferably arranged as spatially as possible as possible. Therefore, two or more side chain groups having an accepting group are preferably bonded to a bonding site having a symmetric arrangement. T in the side chain group having no acceptor group is preferably a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a substituted phenyl group. The substituent ' of the substituted phenyl group may, for example, be a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amine group, a nitro group or a cyano group. Among these, the saturated or unsaturated aliphatic hydrocarbon group may have a carbon number of 1 to 20, the aryl group may have a carbon number of 6 to 60, and the alkoxy group may have a carbon number of 1 to 20, and an aryloxy group. The carbon number may be 7 to 80. The monovalent heterocyclic group is, for example, self-selected from furan, thiophene, thienothiophene, benzoparaphene, thiazole, benzothiazole, benzothiadiazole, azole, pyrrole, imidazole , pyridine, pyridinium, pyrimidine, sorghum, three-ploughed heterocyclic compound, the residue after removing one hydrogen atom. A part or all of the hydrogen atoms in the substituent may be substituted by a fluorine atom. Since the stability of the acceptor compound is increased, the phenyl group and the substituted phenyl group are particularly preferred, and the phenyl group is more preferred. L in the formula (10) is preferably a group represented by the following formula (11). Thus, the interaction between the acceptor groups disposed at the ends of the side chain groups is -19-201240946, and charge transportability is particularly high. q In the formula (11), Q represents an ester bond (-C(=0)0- or -0C(=0)-, a carbonate bond (-〇c(=o)o-), an oxy group (-0-), thiol (-S-), guanamine bond (-C(=0)NH-, -NHC(C=0)-, or a group in which these hydrogen atoms are substituted), quinone imine a bond (-NHC(=0)NH-, or a group in which the hydrogen atom is substituted), an alkylene group which may have a substituent, a vinyl group which may have a substituent, a subethylidene group which may have a substituent, a divalent aromatic hydrocarbon group having a substituent or a divalent heterocyclic group which may have a substituent, when Q is a plural, they may be the same or different, and q represents an integer of from 1 to 10, and Q preferably has The alkyl group of the substituent or the aryl group which may have a substituent. q is preferably an integer of 1 to 6. The alkyl group of Q: -CnH2n- (wherein η is an integer of 1 or more) is shown. The divalent saturated hydrocarbon group preferably has a carbon number of from 1 to 12, more preferably from 1 to 6. The alkylene group is, for example, selected from the group consisting of methylene, ethyl, propyl, and butyl. a pentyl group and a hexanyl group. A part or all of the hydrogen atom of the alkyl group may be substituted by a halogen atom, and the halogen atom is preferably a fluorine atom. The divalent aromatic hydrocarbon group of Q is a residue obtained by removing two hydrogen atoms from a benzene or a condensed ring compound. The carbon number of the aromatic hydrocarbon group is usually from 6 to 60, preferably from 6 to 20. As the condensed ring, for example, The naphthalene ring, the anthracene ring, and the anthracene ring are preferred. The divalent aromatic hydrocarbon group is preferably a residue obtained by removing two hydrogen atoms from benzene. The divalent aromatic hydrocarbon group may have a substituent. -20- 201240946 The carbon number of the substituent does not include the carbon number of the substituent. As the substituted halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl aryloxy group, a monovalent heterocyclic group, an amine group, a nitro group and The cyano group may have a carbon number of from 1 to 20 in the saturated or unsaturated aliphatic hydrocarbon group of from 6 to 60, an alkoxy group having a carbon number of from 1 to 20, and an aromatic group of from 7 to 80. The base is, for example, a residue obtained by removing one hydrogen atom from a compound selected from the group consisting of furan thiophene, benzothiophene, thiazole, benzothiazole, benzoxazole, pyrrole, imidazole, pyridine, pyridinium, pyrimidine, hydrazine, and a compound of the formula The divalent heterocyclic group of Q is a residue of 2 which is removed from the heterocyclic compound, and has a carbon number of usually 3 to 60, preferably 3 to 20. For example, it is selected from the group consisting of thiophene, thienothiophene, dithiophene, pyridine, pyrimidine, pyridinium and triterpene. The residue after removing two hydrogen atoms from the thiophene or thienothiophene as a divalent heterocyclic ring may have a substituent. The carbon number of the group in the carbon number of the divalent heterocyclic group. Examples of the substituent include a halogen atom, a saturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent group, and a nitro group. And a cyano group. Among these, the saturated or unsaturated group may have a carbon number of 1 to 20, the aryl group may have a carbon number of 6 to 60, the carbon number may be 1 to 20, and the aryloxy group may have a carbon number of 7 to 80. For example, it is a heterocyclic ring selected from furan, thiophene, thienothiophene, benzoxazole, benzothiadiazole, oxazole, pyrrole, pyridinium, pyrimidine, pyrene, and triterpenoid. The residue after removal of the compound. Examples of the group include an alkoxy group, a carbon number of the aryl group, a thiophene, a thiadiazole, and a heterocyclic hydrogen atom. Heterocyclic and thiophene, pyridyl, preferably. The divalent heterocyclic ring does not contain a substituted or unsaturated heterocyclic group, an aliphatic hydrocarbon of an amine, a monovalent heterocyclic thiophene of an alkoxy group, a thiazole, a pyridine, or a hydrogen atom - 21 - 201240946 Suitable examples of the compound of the formula are compounds represented by the following formula (a), (b), (c), (d), (e), (f) or (g). [Chem. 18]

L——T

L——T (8)

L——T

[Chem. 19]

(b)

L——T

[Chem. 20]

(C) -22- 201240946

L-T

[Chem. 21]

(d) [Chem. 22]

T—L L—T \ /

Si-O-Si 4-0—

x-T

T—L •Si T—L— o 0

Si-O-——Si ^ 〇 / τ P L-T

Si-0-Si

T (e)

L——T

[Chem. 23]

L-T

-23- 201240946 [Chem. 24]

Τ—L L—Τ τ-τ L,

L -Si--〇--Sj Ο -L—Τ τ

Si Ο V τ I Ο , Si--〇-Si 1/ L——Τ (g) Τ L—Τ (a) , . ( b) , ( c) , ( d) , ( e) , ( f And L and T in (g) are synonymous with L and T of formula (10). The complex numbers L and T in the same molecule may each be the same or different. Two or more of the plural T are acceptor groups. The acceptor compound is excellent in charge transport property and excellent in stability, and is preferably a compound represented by the following formula (h), (i) or (j). [Chem. 25]

-24- 201240946 [Chem. 26]

[化27]

In the formulae (h), (i) and (j), X represents a single bond or -(Q)q-, and the Q and q are synonymous with Q and q in the formula (11), and the complex Q in the same molecule q Each may be the same or different. Ac represents an acceptor group, a hydrogen atom or a phenyl group, and the plural Ac groups in the same molecule may be the same or different, and two or more of the plural Ac in the same molecule are an acceptor group. The acceptor compound of the present embodiment, for example, when X represents -(Q)q--25-201240946, can be produced by the method of Scheme A or Scheme B described below. In the case of the method of the scheme A shown below, the compound (50), the compound (51) and the compound (53) are used as a monomer to produce an acceptor compound (5 4 ). [化 28]

(50)

(52)

- (54)

In Scheme A, Q, Ac, and q are synonymous with Q, Ac, and q in equations (h), (i), and (j). Td represents the number of the bonding portions of the core portion and the h-based core portion, and represents an integer of 4 or more. V and W each independently represent a reactive functional group which is bonded to each other and bonded. When V is a complex number, they may be the same or different. s represents an integer of 0 to q. When s = q, the compound (50) is reacted with the compound (53). When the method of the scheme B shown below is used, the compound (56) and the compound (5 5 ) are used as a monomer to produce a receptor. The core of the compound (5 8 ) $ acceptor compound (5 8 ) is a tetravalent or higher group derived from sesquioxanes. -26- 201240946 [化29] -U4rSi multi ..., OR,

q, OR_ (57)

(58)

Scheme B Scheme Q, Q, Ac, V, W, q, and h are synonymous with Q, Ac, V, W, q, and h of Scheme A. R' represents a hydrogen atom or an alkyl group, and the plural R's may be the same or different. In Scheme A and Scheme B, the reaction of the reactive functional group V with the reactive functional group W to form a chemical bond is, for example, a Suzuki coupling reaction, a Grignard reaction, a Stille reaction or a dehalogenation reaction. Among them, the Suzuki coupling reaction and the Stille reaction are preferred because the raw material is easily obtained and the reaction operation is simple.

Suzuki coupling reaction, for example, using palladium [tetrakis(triphenylphosphine)] or palladium acetate as a catalyst, using potassium carbonate, sodium carbonate and hydroxide in an amount of more than equivalent, preferably 1 to 10 equivalents, per equivalent of the monomer. It is carried out by an inorganic base such as hydrazine or an organic base such as triethylamine or an fluorinated inorganic salt. It is also possible to carry out the reaction in a two-phase system using an aqueous solution of an inorganic salt. The solvent is, for example, selected from the group consisting of N,N-dimethylformamide (hereinafter referred to as "DMF"), toluene, dimethoxyethane and tetrahydrofuran. The reaction temperature also depends on the solvent to be used, but is preferably 50 to 160 °C. It can also be heated to near the boiling point of the solvent to reflux 201240946. The reaction time is usually from 1 to 200 hours. The Suzuki coupling reaction is described, for example, in Chem. Rev., Vol. 95, p. 2457 (1995).

The Stille reaction is carried out, for example, using palladium [tetrakis(triphenylphosphine)] or palladium acetate as a catalyst, using an organotin compound as a monomer. The solvent is, for example, selected from the group consisting of DMF, toluene, dimethoxyethane and tetrahydrofuran. The reaction temperature depends on the solvent to be used, but is preferably 50 to 1 60 t. It is also possible to raise the temperature to the vicinity of the boiling point of the solvent to reflux. The reaction time is usually from 1 to 200 hours. V and W are each selected, for example, from a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, a boronic acid ester residue, a fluorenylmethyl 'scale methyl' phosphate. Methyl, monohalogenated methyl, boronic acid residues, methylidene, alkylstannyl and vinyl. The combination of V and W is selected according to the reaction used. Examples of the boronic acid ester residue include a group represented by the following formula (300), (301), (302) or (303). [化30]

(302 ) ( 303 ) /0CH3 0C2H5

A'-B och3 , oc2h5 (300) (301 ) When it is a Suzuki coupling reaction, as a combination of V and W, a combination of a halogen atom and a boronic acid ester residue or a boronic acid residue is preferred. When it is a stille reaction, 'as a combination of V and W, a combination of a halogen atom and an alkyl tin -28-201240946 fluorenyl group is preferred. When an acceptor compound is synthesized, it is protected by a protecting group in the monomer as needed. This protecting group is selected according to the reaction to be protected. Preferred are the protective groups described in Protective Groupes S yntehesis, 3rd ed. T. W. Greene and P.G. M.. John Willey & Sons. Inc. When the site to be protected is an alkyl group, an aryldialkylalkylene group such as a trialkyldecanedimethylalkyl group such as a trimethylsulfanylalkyl group or a tert-butyldimethylmethylalkyl group may be mentioned. 2-Hydroxypropyl is trimethyldecylalkyl. The monomer to be reacted may be dissolved in an organic solvent. The reaction may be carried out above the melting point of the organic solvent using a base or a suitable catalyst. The base or the catalyst is preferably sufficiently dissolved in the reaction. The organic solvent is also used in accordance with the compound or reaction to be used in order to suppress side reactions, and it is preferred to sufficiently perform deoxidation. The reaction is carried out in a sexual environment. Similarly, it is preferred to carry out the two-phase case of dehydrating the water layer and the organic layer in a Suzuki coupling reaction or the like without this limitation. The solvent used for the reaction is, for example, a saturated hydrocarbon selected from the group consisting of pentane, hexane, and cyclohexane, benzene, toluene, ethylbenzene, and an unsaturated hydrocarbon, carbon tetrachloride, chloroform, dichloromethane, and chloroprene. Functional groups such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, etc., functional groups such as chlorobenzene, dichlorobenzene and trichlorobenzene, and in Organic Wuts, 1999 , when the 'triethyl fluorenyl, biphenyl group and the like. Very good. It may be the same as the solvent below the boiling point, but it is generally preferred to be inert. However, the reaction of hydrazine, Gengyuan, xylene and other alkane, bromobutane and bromocyclohexane halogenated not enough -29-201240946 and hydrocarbons, methanol, ethanol, propanol, isopropanol, butanol and Carboxylic acids, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, tetrahydropyran and two, hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid and nitric acid The solvent-free system may be used alone or in combination of two or more. When the acceptor compound of the present embodiment is used as a useful material, the purity thereof affects the device characteristics. Therefore, the purification reaction by distillation, sublimation purification, recrystallization, or the like is preferably carried out by sublimation, re-refining, and fractionation by chromatography. After the reaction, for example, the reaction is stopped with water, and the product is obtained by a general operation such as distilling off the solvent organically. The post-removal and refining can be carried out by separation or re-processing of the tomography. 2. Organic film The organic film of the present embodiment contains one or two kinds of acceptor compounds in a suitable embodiment. The thickness of the organic thin film is preferably from 1 nm to ΙΟΟμηι, more preferably 100 nm, more preferably from 5 nm to 500 nm, particularly preferably from 20 nm. In order to improve the electron transportability of the organic thin film or the electron transporting film, in addition to the acceptor compound of the present embodiment, It is also possible to use a low- or high-molecular compound having an electron transporting property different from the acceptor compound (hereinafter referred to as an etheroic acid such as diethyl ether decane such as an electron transporting material such as tributyl alcohol. Preferably, the thin film element is prepared by the purification, re-solvent extraction, single crystal of the product, or the like. [Guide is 2 nm to 2 0 0 nm, and the organic compound and the present molecule are contained. Compound "), a low molecular compound or a polymer compound having a hole transporting property of -30 to 201240946 (hereinafter referred to as "hole transporting material"). The hole transporting material can be selected from well known ones. For example, a pyrazoline derivative, an arylamine derivative, an anthracene derivative, a triaryldiamine derivative, an oligothiophene and a derivative thereof, a polyvinylcarbazole and a derivative thereof, a polydecane, and a derivative thereof may be mentioned. , polyoxyalkylene derivatives having an aromatic amine structure in a side chain or a main chain, polyaniline and its derivatives 'polythiophene and its derivatives, polypyrrole and its derivatives, poly(arylene) and its derivatives Derivatives, polythiophene-based vinyl and derivatives thereof. Electron transporting materials can also be selected from among the well-known ones. For example, Df diazole derivatives, quinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, hydrazine and its derivatives, tetracyanoquinodimethane and its Derivatives, anthrone derivatives, diphenyldicyanoethylene and its derivatives, terephthalamide derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinolines and derivatives thereof, Polyporphyrin and its derivatives, burial and its derivatives, fullerenes such as C6Q and its derivatives. In order to generate electric charges by light absorbed in the organic thin film, the organic thin film may also contain a charge generating material. The charge generating material can be selected from a person skilled in the art. Examples thereof include azo compounds and derivatives thereof, diazonium compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, hydrazine compounds and derivatives thereof, and the like. Cycloheximide compounds and derivatives thereof, square quinone compounds and derivatives thereof, hydrazine compounds and derivatives thereof, hydrazone compounds and derivatives thereof, fullerenes such as C6Q and derivatives thereof. -31 - 201240946 Organic films may also contain other materials in order to exhibit various functions. Other materials include, for example, a sensitizer for functional sensitization to generate electric charge by absorbed light, a stabilizer for increasing stability, and a UV absorber for absorbing ultraviolet (UV) light. The organic film may contain a polymer material other than the acceptor compound of the present embodiment as a polymer binder in order to improve the mechanical properties. As the polymer binder, those which do not extremely impede charge transport are preferably used, and those which do not absorb visible light are preferably used. As the polymer binder, poly(N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly(p-phenylenevinyl) and derivatives thereof, poly(2) can be exemplified. , 5-polythiophene extended vinyl) and derivatives thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polyoxyalkylene. The organic thin film of the present embodiment can be formed, for example, by a solution containing an acceptor compound of the present embodiment, an optional electron transporting material, a hole transporting material, a polymer binder, or the like, and a solvent. 'Manufactured from the method of removing the solvent from the film formed solution. When the acceptor compound has sublimation properties, the organic film can be formed by a vacuum evaporation method. The solvent of the above solution may be any one that dissolves the acceptor compound and other materials. For example, toluene, xylene, 1,3,5-trimethylbenzene, tetrahydronaphthalene, decahydronaphthalene, dicyclohexane, n-butylbenzene, t-butylbenzene, and t-butylbenzene can be used. Unsaturated hydrocarbon solvent, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane Halogenated saturated hydrocarbon solvent such as alkane and bromocyclohexane - 32-201240946, halogenated unsaturated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or trichlorobenzene, and ether solvent such as tetrahydrofuran or tetrahydropyran . The acceptor compound of the present embodiment is also dependent on its structure or molecular weight, but it is usually dissolved in a solvent of such a solvent at a concentration of 0.1% by mass or more. As a film forming method using a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a rod coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, or a screen printing method can be used. Coating methods such as printing, offset printing, lithography, inkjet printing, dispenser printing, nozzle coating, and capillary coating. Among these, spin coating, offset printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating are preferred. The method of producing an organic film may also include the step of aligning the acceptor compound. By this step, the main chain and/or the side chain are arranged in a certain direction to further increase the charge mobility of the organic film. As a method of aligning the acceptor compound, a method known as an alignment method of liquid crystal can be used. Among them, the rubbing method, the photo-alignment method, the shearing method (shear stress applying method), and the hoisting coating method are simple, useful, and easy to use as an alignment method. In particular, a rubbing method and a shearing method are preferred. The method of producing an organic film also includes the step of annealing the film after removing the solvent. By annealing, the interaction between the acceptor compounds is promoted, the film quality of the organic film is improved, and the charge mobility is further improved. The annealing temperature is preferably from 50 ° C to the temperature between the glass transition temperature (Tg) of the acceptor compound, more preferably between (Tg - 30 ° C) and Tg. The annealing time is preferably from 1 minute to 10 hours, more preferably from 10 minutes - 33 to 201240946 to 1 hour. The annealed environment is preferably in a vacuum or an inert gas atmosphere. The organic thin film of the present embodiment can be used for organic thin film transistors, organic thin film solar cells, photosensors, etc. by transporting charges controlled by electric charges or generated by light absorption by transporting charge. A variety of organic film components. When an organic thin film element such as an organic thin film is used, the acceptor compound is aligned by the alignment treatment, which is more preferable from the viewpoint of obtaining high charge transport properties. 3. Organic thin film device The organic thin film of the above-described preferred embodiment has excellent charge transport properties because it contains the acceptor compound of the present embodiment. Therefore, the organic thin film can efficiently transport charges injected from an electrode or the like, charges generated by light absorption, and the like. The acceptor compound of the present embodiment is excellent in environmental stability, and by using these to form a film, an organic thin film element having stable performance can be obtained even in a normal atmosphere. Hereinafter, suitable embodiments of various organic thin film elements will be described. (Organic thin film transistor) The organic thin film electromorphic system is composed of a source electrode and a germanium electrode, an active layer functioning as a current path between the electrodes, and a germanium electrode for controlling the amount of current passing through the current path. As the organic thin film transistor, an electric field effect type or an electrostatic induction type can be exemplified. As the active layer, an organic thin film containing the acceptor compound of the above embodiment is used. The electric field effect type organic thin film transistor is preferably an active layer having a source electrode and a current path between the electrodes 34-201240946, a current path between the electrodes, a gate electrode for controlling a current amount passing through the current path, and an organic thin film. An insulating layer between the gate electrode and the gate electrode. Preferably, the source electrode and the ruthenium electrode are connected to the organic thin film, and further, a gate electrode is provided, which is sandwiched between the insulating layers of the organic thin film. The static-inducing organic thin film transistor is preferably an active layer having a source electrode and a germanium electrode, a current path between the electrodes, and a gate electrode for controlling a current amount passing through the current path, the gate electrode being disposed in the organic thin film . The source electrode, the germanium electrode and the gate electrode are preferably provided in contact with the active layer. The gate electrode may have a structure in which a current flowing from the source electrode to the cathode electrode is formed, and the amount of current flowing in the current path can be controlled by a voltage applied to the gate electrode. The gate electrode is, for example, a comb electrode. Fig. 1 is a schematic cross-sectional view showing an organic thin film transistor (electric field effect type organic thin film transistor) of the first embodiment. The organic thin film transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a germanium electrode 6 formed at a predetermined interval on the substrate 1, and is formed on the substrate 1 so as to cover the source electrode 5 and the germanium electrode 6. The active layer 2, the insulating layer 3 formed on the active layer 2, and the gate electrode 4 formed on the insulating layer 3 so as to cover the region of the insulating layer 3 between the source electrode 5 and the germanium electrode 6. Fig. 2 is a schematic cross-sectional view showing an organic thin film transistor (electric field effect type organic thin film transistor) of the second embodiment. The organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, and an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, and the source electrode 5 is vacated. a tantalum electrode 6 formed on the active layer 2, an insulating layer 3 formed on the active layer 2 and the tantalum electrode 6, to cover an area of the insulating layer 3 between the source electrode 5 - 35 - 201240946 and the tantalum electrode 6 The gate electrode 4 is formed on the insulating layer 3. Fig. 3 is a schematic cross-sectional view showing an organic thin film transistor (electric field effect type 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 germanium electrode 6 formed by vacating a predetermined interval on the active layer 2, and partially covering the source electrode. 5 and the insulating layer 3 formed on the active layer 2 in such a manner as to cover the region of the insulating layer 3 in which the active electrode 5 is formed in the lower portion and the insulating layer 3 in which the germanium electrode 6 is formed in the lower portion. The gate electrode 4 is formed on the insulating layer 3. Fig. 4 is a schematic cross-sectional view showing an organic thin film transistor (electric field effect type organic thin film transistor) of the fourth embodiment. The organic thin film transistor 130 shown in FIG. 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 a portion covered in a lower portion. The source electrode 5 and the germanium electrode 6 formed by vacating a predetermined interval on the insulating layer 3 in a region having the region of the insulating layer 3 of the gate electrode 4, and partially covering the source electrode 5 and the germanium electrode 6 are formed on the insulating layer 3. Active layer 2. Fig. 5 is a schematic cross-sectional view showing an organic thin film transistor (electric field effect type organic thin film transistor) of the fifth embodiment. The organic thin film transistor 14 shown in FIG. 5 is provided with 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 a gate formed at a lower portion thereof. The source electrode 5 of the electrode 4 is formed on the insulating layer 3 in a manner to partially cover the source electrode 5 - 36 - 201240946 to form the active layer 2 on the insulating layer 3, partially covering the gate electrode 4 The region of the active layer 2 is spaced apart from the source electrode 5 to form the tantalum electrode 6 on the insulating layer 3. Fig. 6 is a schematic cross-sectional view showing an organic thin film transistor (organic thin film transistor) of a sixth embodiment. The transistor 150 shown in FIG. 6 is provided with a substrate 1 and a gate formed on the substrate 1 to cover the gate electrode 4. The mode layer 2 of the region in which the insulating layer 3 on the substrate 1 is formed with the insulating layer 3 of the gate electrode 4 is formed. a source electrode 5 formed on the insulating layer 3 so as to cover a region where the gate electrode 4 is formed in a lower portion, and a pole 5 covering a region where the active layer 2 of the gate electrode 4 is formed at a lower portion is formed at a predetermined interval. Fig. 7 is a schematic cross-sectional view showing an organic thin film transistor (organic thin film transistor) of the seventh embodiment. The transistor 160 shown in FIG. 7 includes a substrate 1, an active layer 2 formed on the substrate 1 and a source electrode 2 formed on the source electrode 5, and a gate electrode 4 which is formed by being plurally formed on the active layer 2 to cover the gate electrode 4. The active layer 2a formed on the active layer 2 (constituting the active layer 2 may be the same as or different from the active layer 2), and the active layer 2 is formed on the organic thin film transistor 2 of the first to seventh embodiments and/or Or the active layer 2a contains the acceptor wave of the present embodiment as a current path between the source electrode 5 and the ytterbium electrode 6 (the gate electrode 4 is controlled by applying a voltage to control the formation of a predetermined electric field in the lower portion of the active layer 2). The effect type organic thin film electrode 4 is formed so as to cover the living active layer 2 formed in a partial manner with the source electrode 6 and the electrostatic induction type organic thin film electrode 5, and all of the specified forms are formed: a The amount of current flowing in the current path (channel) of the active layer compound, the active channel compound, and/or the active-37-201240946 layer 2 a. Such an electric field effect type organic thin film electromorphic system can be produced by a known method, for example, the method described in JP-A No. Hei 5-119069. Further, the electrostatically inducible organic thin film electrocrystallization system can be produced by a known method, for example, the method described in JP-A-2004-006476. The substrate 1 is selected so as not to impede the characteristics of the organic thin film transistor. As the substrate 1, a glass substrate, a flexible film substrate, and a plastic substrate can be used. The insulating layer 3 can be formed by selecting a well-known insulating material. For example, SiOx, SiNx, Ta2〇5, polyimide, polyvinyl alcohol, polyvinylphenol, organic glass, and photoresist can be given. Since the voltage can be low north, it is preferable to form the insulating layer 3 using a material having a high dielectric constant. When the active layer 2 is formed on the insulating layer 3, in order to improve the interface characteristics of the insulating layer 3 and the active layer 2, the surface of the insulating layer 3 may be treated with a surface treating agent such as a decane coupling agent to be surface-modified. Active layer 2. Examples of the surface treatment agent include long-chain alkylchlorosilanes, long-chain alkyl alkoxy decanes, fluorinated alkylchlorosilanes, fluorinated alkyl alkoxy decanes, and hexamethyldifluorene. A mercaptoalkylamine compound such as a nitrone. The surface of the insulating layer may also be treated with ozone UV, 02 plasma before the surface treatment. After the organic thin film transistor is fabricated, in order to protect the device, it is preferred to form a protective film on the organic thin film transistor. Thereby, the organic thin film electro-crystal system can block the atmosphere and suppress the degradation of the characteristics of the organic thin film transistor. Further, by the protective film, it is possible to form a driving display device on the organic thin film transistor. In the step of -38-201240946, the influence from the outside is reduced. As a method of forming a protective film, for example, a method of covering with a UV, a thermosetting resin or an inorganic SiONx film is effective, and it is preferably not exposed to the atmosphere in a dry nitrogen atmosphere or in a vacuum. The step of making the organic thin film until the protective film is formed is performed. By arranging a plurality of organic thin film transistors, a crystal array can be formed, and a back sheet as a flat panel display can also be used. (Organic thin film solar cell) Fig. 8 is a plan view of an organic thin film solar cell of a suitable embodiment. The organic thin film solar cell 200 shown in Fig. 8 includes a first electrode 7a formed on the substrate 1, and a second electrode 7b formed on the first active layer 2 and formed on the active layer 2. An organic thin film containing the acceptor compound of the present embodiment is contained. At least one of the first electrode 7a and the second electrode 7b is a transparent electrode. As the electrode material, a metal such as aluminum, gold, silver metal or alkaline earth metal or a semitransparent film or film thereof can be used. In order to obtain a high open voltage, the difference in the work function is larger as the respective electrodes. In order to increase the sensitivity, the active layer 2 is a charge generating agent, a sensitizer, or the like. As the substrate 1, a glazing substrate, a plastic substrate or the like can be used. The operating mechanism of the organic thin film solar cell is explained. The light energy incident on the self-transparent electrode is an acceptor compound and/or a hardening resin. In order to have (for example, a thin film substrate of a film transistor machine, the layer 2 on i 7a is transparent or semi-copper, transparent, transparent, preferably also includes a substrate, a glass or a semi-transparent donor. -39-201240946 The compound absorbs and generates excitons formed by electrons and holes. The exciton moves, if it reaches the heterojunction interface between the acceptor compound and the donor compound, The difference between the energy of each compound and the LUMO of the interface, the electrons are separated from the hole, and the active charge is generated. The generated electrons move toward the cathode, and the generated anode moves, and can be taken out as electric energy (current) to the outside. Considering such an action mechanism, in order to obtain a photoelectric conversion effect organic thin film solar cell, it is important to use an acceptor compound and/or a compound having an absorption range of a spectrum of incident light which is efficiently desired; for efficient separation Exciton, organic thin film The sun has many heterojunction interfaces; a material having charge transportability for transporting generated charges to the electrodes is used. In the organic thin film solar cell, an additional layer may be provided between at least one of the first electrode and the second electrode 7b and the active J in the element. Examples of the additional layer include a charge transport layer and a separator electrode. Specifically, the organic thin film solar cell 200 shown in FIG. 8 is preferably one or both of an active layer containing an acceptor compound and a donor compound. The above-mentioned film solar cell having a buffer layer. The organic thin film solar cell system can generate a photoelectromotive force between electrodes by transparently or translucently illuminating light such as sunlight, thereby performing a battery operation by collecting a plurality of organic thin films. Battery, machine. Thin film solar cell module. The adjacent HOMO can be connected to a high-capacity absorber or a donor battery containing a fast 7a and 罾2. Fig. 9 is a schematic cross-sectional view of a photosensor according to the first embodiment. The photo sensor 300 shown in Fig. 9 is provided with a substrate 1 and formed thereon. The first electrode 7a on the board 1, the active layer 2 on the first electrode 7a, the charge generating layer 8 on the active layer 2, and the second electrode 7b formed on the charge generating layer 8. The active layer 2 contains the present Fig. 1 is a schematic cross-sectional view of a photosensor according to a second embodiment of the present invention. The photosensor 310 shown in Fig. 10 includes a substrate 1 and is formed on the substrate 1. The first electrode 7a, the charge generating layer 8 formed on the first electrode 7a, the active layer 2 on the charge generating layer 8, and the second electrode 7b formed on the active layer 2. The active layer 2 contains the present embodiment. An organic thin film of an acceptor compound. The photosensor of the organic thin film of the present embodiment can emit light from a transparent or translucent electrode by applying a voltage between electrodes. Flow, acting as a light sensor. An image sensor can be constructed by collecting a plurality of photo sensors. Fig. 示意 is a schematic cross-sectional view of a photosensor according to a third embodiment. The photo sensor 320 shown in FIG. 11 includes a substrate 1, a first electrode 7a formed on the substrate 1, an active layer 2 formed on the first electrode 7a, and a second electrode 7b formed on the active layer 2. . The active layer 2 is an organic thin film containing the acceptor compound of the present embodiment. In the photosensors of the first to third embodiments, one of the first electrodes 7a to 41 - 201240946 and the second electrode 7b is a transparent or translucent electrode. The charge generating layer 8 is a layer that absorbs light to generate electric charges. As the electrode material, a metal such as aluminum, gold, silver, copper, an alkali metal or an alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. The active layer 2 may also contain a carrier generator, a sensitizer, or the like for improving the photosensitivity. As the substrate 1, a ruthenium substrate, a glass substrate, a plastic substrate or the like can be used. The present invention is not limited to the embodiments described above, and various modifications are possible without departing from the gist of the invention. EXAMPLES Hereinafter, the present invention will be more specifically described based on the examples and comparative examples. However, the invention is not limited at all by the following examples. (Measurement conditions, etc.) The nuclear magnetic resonance (NMR) spectrum is a product name JMN-270 (270 MHz at the time of measurement) manufactured by JEOL (Japan Electronics Co., Ltd.) or JMNLA-600 (150 MHz at the time of 13 C measurement) manufactured by JEOL. Determination. Chemical shifts are expressed in parts per million (ppm). As an internal standard Oppm, tetramethyl decane (TMS) was used. The coupling constant (J) is expressed in Hertz, and the short numbers s, d, t, q, m, and br each represent a single line (singlet), double line (doublet), triple line (triplet), and quadruple line (quartet). ), multiple lines and broad lines. Mass analysis (MS) was performed using Voyager Linear DE-H MALDI-TOF MS (trade name) manufactured by PerSeptive Biosystems, Inc., -42-201240946. Column chromatography The ruthenium gel in the GPC separation was sold under the trade name Silieagel 6〇n (40 to 50 gm) manufactured by Kanto Chemicals Co., Ltd. The oxidation name was obtained by using Merck's trade name aluminum oxide 90 standardized. The chemical substance is a reagent grade, purchased from Wako Pure Chemical Industries Co., Ltd., Tokyo Chemical Industry Co., Ltd., Kanto Chemical Co., Ltd., Nacalai Tesque Co., Ltd. or Sigma-Aldrich Japan Co., Ltd. Cyclic voltammetry (below) The "CV" system was measured using a device manufactured by BAS Corporation using a Pt electrode manufactured by BAS Corporation as a working electrode and a Pt wire as a counter electrode using an A g line as a reference electrode. The scanning speed at this measurement was 1 〇〇mV/sec, and the scanning potential range was -2.8 V, 1.6 V. The measurement of the reduction potential and the oxidation potential was carried out by completely dissolving lxl in dichloromethane (T3 mol/L). A solution of tetrabutylammonium hexafluorophosphate as a supporting electrolyte with a compound of 0.1 mol/L. The absorption spectrum of the solution is automatically recorded by a spectrophotometer (UV-3100PC: manufactured by Shimadzu Corporation) at a groove width of 1 cm. The quartz cell was measured at a slit width of 1 mm. The fluorescence spectrum of the solution was measured using a fluorescence spectrophotometer (FluoroMax-2: manufactured by Horiba, Ltd.) using a photomultiplier tube (R92 8: Hamamatsu PHOTONICS) The system was measured as a detector. The measurement of the fluorescence spectrum was carried out by placing the solution in a quartz cell at a slit width of 1 mm and a cumulative time (1 nm/sec). Example 1 <Compound B Synthesis > -43- 201240946 The compound A used as a raw material was synthesized according to the method described by Toshifumi Dohi et al., J. Org. Chem. 2007, 72, 109. [Chem. 31]

Compound A (258 mg, 0.39 mmol) and 3-aminopropyltriethoxydecane (1 mL) were placed in a 5 mL test tube and stirred at 150 ° C overnight. The obtained product was purified by a hydrazine gel column (chloroform) and GPC to give Compound B (2 1 7 m g, yield: 64%) as a red solid. The analysis results and structural formula of Compound B are as follows. TLC Rf = 0.1 (chloroform) 'H NMR (4 00MHz, CDC13) : 50.8 1 ( m) , 1.2 1 ( m) 1.87 (m) , 2.26 (m, 2H) , 3.84 (m, 6H) , 4.21 (t , 2H) 5.18 ( m, lH ) , 8.69 ( m, 8H ) [32]

Si(OEt)3 <Synthesis of Compound c> -44 - 201240946 In a 50 mL eggplant-shaped flask, Compound B (217 mg '0.252 mmol), chloroform (3 mL), and tetra-n-butyl saddle (O.lmL) were added. ) ' Stir overnight. The resulting product was washed with water and then extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was evaporated, and the residue was evaporated. This was purified by a hydrazine gel column (chloroform) and GPC to give Compound C (177 mg, yield 93%) as a red solid. The analysis results and structural formula of Compound C are as follows. MALDI TOFMS: m/z = 5 998.97 The result of CV measurement is that compound C shows a reduction potential of -1.29V.

Ered (peak). [化33]

PDI

PDI >i-

-OsSi A

^^PDI

,C9H19 c9h19 PDI-

•PDI

C <Measurement of Absorption Spectrum and Fluorescence Spectrum> The absorption spectrum and the fluorescence spectrum were measured using a chloroform solution of Compound C. In the absorption spectrum, peaks were observed at 465 nm, 490 nm and 53011〇 (Fig. 12). In the fluorescence spectrum, a broad fluorescence having a peak near 62 Onm due to the association of the bis(dicarboxylimideimine) groups strongly derived from the terminal groups was observed (Fig. 13). The association of the bis(dicarboxylimideimine) groups with the acceptor group is associated with each other, suggesting that the compound C has a good electron transportability of -45 to 201240946. Example 2 <Synthesis of Compound D> In the test tube attached, phenanthrene 3,4,9,10-tetradecanoic acid dianhydride (550 mg, 1.4 0 mm ο 1 ), ethylhexylamine was placed. (435 mg, 3.37 mmol) and DMF (10 mL), 14 (rc was stirred overnight), and the obtained product was washed with hexane, and purified by a hydrazine gel column (chloroform) to give a red solid compound. D (542 mg, yield 63%). The analysis results and the structural formula of the compound D are as follows. *H NMR (400 MHz, CDCl3): δ θ.91 (m) , 1.41 (m), 4.13 (m), 8.45 (d) , 4H), 8·57 (d, 4H) [34]

D <Synthesis of Compound E> In a 50 mL eggplant-shaped flask, Compound D (73 4 mg, 1.19 mmol), potassium hydroxide (234 mg, 417 mm〇i), and 2-methyl-2-propanol (5) were added. 〇mL) 'At 8〇. (: stirring for 2 hours. After washing the reaction liquid with water and methanol, 'vacuum under vacuum' to obtain a red solid (6 1 3 mg). -46- 201240946 Place red solid (613 mg) and triethylbenzene in the test tube. The oxime propyl propylamine (4 mL) was stirred at 150 ° C overnight, and the obtained product was purified by hydrazine gel column (chloroform) and GPC to give Compound E (304 mg, yield 36%). The analysis results and the structural formula of the compound E are as follows. TLC Rf = 0.1 (chloroform) 'H NMR (400 MHz, CDC13) : δ 0.9 0 (m ), 1.23 (m, 9H ), 1.40 (m) , 3.84 (m, 6H), 4.19 (m), 8.68 (m, 8H) [Chem. 35]

E <Synthesis of Compound F> In a 5 mL test tube, Compound E (87 mg, 〇.123 mmol), chloroform (2 mL) and tetra-n-butylammonium fluoride (0.1 mL) were added and stirred overnight. The resulting product was washed with water and then extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was evaporated, and the residue was evaporated. This was purified by a hydrazine gel column (chloroform) and GPC to give Compound F ( 36 mg, yield %) as a red solid. The analysis results and structural formula of the obtained Compound F are as follows. MALDI TOFMS : m/z = 4765.7 -47- 201240946 [化36]

Example 3 <Synthesis of Compound &> Compound G used as a raw material was synthesized in accordance with the method described by Yutaka Ie et al., Chem. Comm. 2009, 10, 1213. [化37]

In a 5 mL test tube, compound G (lg, 1.16 mmol), PdCl2 (dppf) (95 mg '0.16 mmol), potassium acetate (3 42 mg), bis(pinapol) diboron (44 3 mg) were placed. And dimethyl hydrazine (lmL), the reaction was carried out at 1 l ° ° C. The reaction solution was washed with water and extracted with chloroform. The organic layer was dried with sodium sulfate and the solvent was evaporated to dryness. The product was purified by a hydrazine gel column (chloroform) and GPC to give a compound H as a red solid (21.6 mg, yield 22%). The analysis results and structural formula of the obtained compound hydrazine are as follows. -48- 201240946 *H NMR ( 400MHz, CDClj ) : 50.84 ( t,6H) , 1.26 ( m ), 1.91 (m) , 2.26 (m) , 5.19 (m,lH) , 7.37 (d,2H), 8.03 ( d,2H ) , 8.67 ( m,8H ) [化38]

<Synthesis of Compound J> The compound used as a raw material was synthesized according to the method described by Isabelle Aujard et al., J. Am. Chem. Soc_200 1 123, 8I77.

I

In a test tube of 5 m:L, compound H (130 mg, 0.15 mmol), compound I (28 mg, 〇.〇3 mmol), tetrakis(triphenylphosphine)palladium (7 mg, 0.0060 mmol), potassium carbonate (42 mg) were placed. And a mixture of tetrahydrofuran and water (tetrahydrofuran / water = 1.5 mL / 0.3 mL), reacted at 9 CTC -49 - 201240946 overnight. The resulting product was purified by a silica gel column (chloroform) and GPC to give Compound J (26 mg, yield: 26%) as a red solid. The analysis results and structural formula of the obtained Compound J are as follows. MALDI TOFMS: m/z = 3 3 63.8 The result of the CV measurement was that the compound J showed a reduction potential of _125 V E R e D (peak 値). [40]

Example 4 <Synthesis of Compound L> Compound K used as a raw material was synthesized in accordance with the method described in Lyle D. Wescott and Daniell Lewis Mattern., J. Org. Chem. 2003, 68, 1 005 8. [化41]

-50- 201240946 In a 5 mL test tube, compound H (86 mg, 0.1 Ommol), compound K (16 mg, 0.02 mmol), tetrakis(triphenylene) IE (5 mg, 〇.〇〇43 mmol), carbonic acid were placed. Potassium (28 mg) and a mixture of tetrahydrofuran and water (tetrahydrofuran/water = 1.0 mL / 0.2 mL) were reacted at 90 ° C overnight. The product obtained by purifying the gel column (chloroform) and GPC was used to obtain Compound L (2 mg, yield 30%) as a red solid. The analysis results and structural formula of the obtained compound L are as follows. MALDI TOFMS: m/z = 3243.7 The result of the C V measurement is that the compound L shows a reduction potential of -1 · 2 6 V Ered (peak 値). [化42]

Example 5 <Synthesis of Compound &> Compound N was synthesized as a raw material according to the method described by Michael R. Wasielewski et al., J. Am. Chem. Soc. 2000, 122, 5 563. -51 - 201240946 [化 43]

Compound N (10 mg, 〇.26 mmol) and 3-aminopropyltriethoxy decane (06 mL) were placed in a 5 mL test tube, and stirred at 150 ° C overnight. The resulting product was purified by a hydrazine gel column (chloroform) to afford compound yd (yield: 67%, yield: 30%). The analysis results and structural formula of the obtained compound hydrazine are as follows. 'H NMR (400MHz, CDClj) : 60.77 ( m ) , 〇 · 9 5 ( m ): 1.95 (m) , 3.83 (t,6H) , 4.15 (m,2H) , 8.75 (s,4H) [44 ]

<Synthesis of Compound P> In a 5 mL test tube, a compound hydrazine (86 mg, 0.15 mmol), dichloromethane (3 mL), and tetra-n-butyl pentoxide (0.07 mg) were placed and stirred overnight. The reaction solution was washed with water and extracted with dichloromethane. -52 - 201240946 The organic layer was dried over sodium sulfate, the solvent was evaporated, and the residue was dried in vacuo. This was purified by a hydrazine gel column (chloroform) and GPC to give Compound P (37 mg, yield: 56%) as a white solid. The analysis results and structural formula of the obtained Compound P are as follows. 'H NMR ( 400MHz, CDC13 ) : 50.90 ( m) , 1.34 ( m) 1.85 ( m ) , 4.03 ( m ) , 8.37 ( m,32H) MALDI TOFMS : m/z = 3 708.4

[化45] NDI

Example 6 <Production of Organic Thin Film Element 1 and Evaluation of Transistor Characteristics> On the surface of a p-type germanium substrate doped with a high concentration of a gate electrode, a tantalum oxide film having a diameter of 300 nm was prepared by thermal oxidation. A substrate as an insulating film. On the substrate, a comb-shaped source electrode having a channel width of 38 mm and a channel length of 25 #m and a ruthenium electrode were formed by a lift-off method. The surface of the substrate was washed with ozone for 10 minutes by ultrasonic washing for 1 minute with acetone for 10 minutes, followed by ultrasonic cleaning of the substrate with the electrode. -53-201240946 The compound C synthesized in Example 1 was dissolved in chloroform at a concentration of 1% by mass. As a result, it was confirmed that the compound C was completely dissolved in chloroform, and it was confirmed that it was dissolved in an organic solvent. This solution was applied onto the washed substrate by spin coating at a rotation number of 1 500 rpm for 1 minute while being dried to form an organic film of Compound C. Then, annealing treatment was performed at 200 ° C for 30 minutes in nitrogen gas to obtain an organic thin film device 1. The organic thin film element 1 was measured while changing the range of the surface voltage Vg and the source-to-turn voltage Vsd in the range of 0 to 80 V in a vacuum using a semiconductor parameter analyzer (manufactured by Keithley Co., Ltd., trade name "4200-SCS"). The characteristics of the organic transistor gave a good Id-Vg characteristic of the n-type semiconductor. The mobility at this time was 1.2 x 10 _ 4 cm 2 /Vs, the 闽値 voltage was 59 V, and the on/off ratio was 1 〇 5, which was good. From this, it was confirmed that the organic thin film device 1 effectively functions as an n-type organic electromechanical crystal. Further, it was confirmed that the compound C can be used as an organic n-type semiconductor which is excellent in electron transport property. Example 7 <Production of Organic Thin Film Element 2 and Evaluation of Solar Cell Characteristics> A regioregular poly-3-hexylthiophene as a donor compound was mixed at a ratio of 1:1 (mass ratio) and as an acceptor Compound C of the compound was dissolved in a chloroform solvent to prepare a coating solution. The glass substrate to which the ITO film was attached by sputtering was subjected to surface treatment with ozone UV. Then, the coating solution was applied onto the surface-treated substrate by spin coating to obtain an active layer of the organic thin film solar cell. Then, lithium fluoride was deposited on the active layer by a vacuum evaporation method, and then -54 - 201240946 aluminum was deposited on the lithium fluoride layer to fabricate the organic thin film device 2. In the organic thin film device 2, when the characteristics of the organic thin film solar cell are measured by light irradiation of a solar simulator (AM 1.5G filter, radiation illuminance of 100 mW/cm 2 ), it operates as a solar cell. Example 8 <Production of Organic Thin Film Element 3 and Evaluation of Transistor Properties> The compound P synthesized in Example 5 was added to chloroform at a concentration of 1% by mass, and as a result, the compound P was completely dissolved in chloroform. It was confirmed that it could be dissolved in an organic solvent. An organic thin film device 3 was produced in the same manner as in Example 6 except that the solution thus obtained was used instead of the chloroform solution of the compound c. Then, in the same manner as in Example 6, the organic transistor characteristics of the organic thin film device 3 were measured, and as a result, the Id-V9 characteristics of a good n-type semiconductor were obtained. At this time, the mobility was 1 · 1 X l (T4 cm 2 /Vs, the 闽値 voltage was 14 V, and the on/off ratio was 1 07, which was good. It was confirmed that the organic thin film device 3 effectively functions as an n-type organic transistor. Further, it was confirmed that the compound p can be used as an organic n-type semiconductor excellent in electron transport property. Comparative Example 1 <Synthesis of Compound Q> According to Lyle D. Wescott and Daniell Lewis Mattern at J. 〇rg. C hem. Method described in 2003, 68, 10058, synthetic compound q -55- 201240946 [Chem. 46]

Q <Evaluation of absorption spectrum and fluorescence spectrum> Compound Q was dissolved in chloroform, and an absorption spectrum was measured. In the absorption spectrum, at 460 nm, 490 nm, and 525 nm (Fig. 12). Further, in the egg light spectrum, a peak was observed at 530 nm and 620 nm, and the maximum peak was 530 nm, and the width of the peak near 620 nm caused by the association of the formation was as strong as that (Fig. 13). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an illustration of an organic thin film transistor according to a first embodiment. Fig. 2 is an illustration of an organic thin film transistor according to a second embodiment. Fig. 3 is an illustration of an organic thin film transistor according to a third embodiment. 4 is a view showing an organic thin film transistor according to a fourth embodiment. FIG. 5 is a view showing an organic thin film transistor according to a fifth embodiment, and a fluorescent light seeing a peak of 570 nm and a compound Q and a fluorescent system are not intended. Fig. 6 is a schematic cross-sectional view of an organic thin film transistor of a sixth embodiment. Fig. 7 is a schematic cross section of an organic thin film transistor of a seventh embodiment. Fig. 6 is a schematic cross-sectional view of an organic thin film transistor according to a sixth embodiment. Figure 8 is a schematic cross-sectional view of a solar cell of an embodiment. Fig. 9 is a schematic cross-sectional view showing a photosensor according to the first embodiment. Fig. 10 is a schematic cross-sectional view showing a photosensor of a second embodiment. Fig. 1 is a schematic cross-sectional view of a photosensor according to a third embodiment. Fig. 1 2 is a graph showing the absorption spectra of Compound C and Compound Q. Fig. 1 is a graph showing the fluorescence spectrum of Compound C and Compound Q. [Description of main component symbols] 1 : Substrate 2 : Active layer 2 a : Active layer 3 : Insulating layer 4 : Gate electrode 5 : Source electrode 6 : Bismuth electrode 7 a : First electrode 7 b : Second electrode 8 : Charge generating layer -57- 201240946 160 : Organic thin film electric 100, 110, 120, 130, 140, 150, crystal 200: organic thin film solar cell 300, 310, 320: photo sensor - 58-

Claims (1)

201240946 VII. Patent Application Range: 1. A compound comprising: a core having a tetravalent or higher group derived from a cage compound or an aliphatic hydrocarbon compound, and 4 or more side chains bonded to the core A group in which two or more of the aforementioned side chain groups have an acceptor group. 2. A compound as claimed in claim 1 wherein the formula is represented by the following formula (a), (b), (c), (d), (e), (Ο or (g) - LT is the aforementioned side chain group, and two or more of the plural T in the same molecule are the base of the above acceptor; [Chemical 1] -59- 201240946 [化3] (c) [Chem. 4] L-T (Φ τ—L L——T \ / Si-0-Si Si-O-Si T-L', L-T (e) -60- 201240946 [Chem. 6] L-TT-L, •Sk, 〇, o L——TT-L-Si L-T ·〇- L——T ·〇· (0 T—L [Chemical 7] T—LL—τ T—L T- Λ Si , Si- I of —r〇—,r—c { L——TT—L |i^?* —o—s,〇| I Io--si^ 〇-L-TT, one TJ^Si I/0 XL-TLx 0 1 Si (g) [Formula (a), (b) ' ( c) ' ( d) , ( e) , ( f ) and (g) ' L denotes a single bond or 2 valence The organic group, T represents a substituent of the above-mentioned accepting group 'hydrogen atom, halogen atom, alkyl group, alkoxy group, phenyl group or substituted phenyl group'. The substituent of the above substituted phenyl group is a halogen atom, saturated or unsaturated. One or a part of a hydrogen atom selected from an aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amine group, a nitro group and a cyano group, which may be substituted by a fluorine atom, in the same molecule The plural L and T each may be the same or different. The compound of claim 1 wherein the aforementioned cage compound is adamantane or sesquioxanes, and the aforementioned aliphatic hydrocarbon compound is Methane. 4. The compound according to any one of claims 1 to 3, wherein the aforementioned acceptor is based on the following structural formula: [Chemical 8] [Chemistry 9] -62 - 201240946 [化 10] R01 a group containing a fullerene derivative residue as shown in any one of the following formulas: [Chemical Formula 11] The group containing the residue of the naphthoquinone imide derivative, the following structural formula = [Chemical 12] -63- 201240946 [Chem. 13] [Chem. 14] [化15] [Chemistry 16] -64 201240946 [Chem. 17] R01 [化 18] Or the following formula: [Chem. 19] In the equation, RQI represents a monovalent organic group 'RG2' represents a divalent organic group, R. 3 represents a trivalent organic group, and each of R«n, and rQ3 may be the same or different when it is plural in the same formula, and A represents an alkyl group, an alkoxy group, a sulfonyl group, an amine group, an ammonium group, A hydroxyl group 'nitro group or a halogen atom, e represents an integer of c to 4, f represents an integer of 〇~12, and g represents an integer of 〇~8. The compound according to any one of claims 1 to 3, wherein the acceptor-based group is a group containing a fullerene derivative residue, and a naphthoquinone-containing amine derivative residue a group or a group containing a residue of a quinone imine derivative. An organic film comprising the compound according to any one of claims 1 to 5. 7. An organic film element which has an organic film as in claim 6 of the patent application. 8. An organic thin film transistor having an organic film as in claim 6 of the patent application. 9. An organic thin film solar cell comprising an organic film as in claim 6 of the patent application. 10. A photosensor comprising an organic film as in claim 6 of the patent application. -66-