JP2013166743A - Fulvalene compound and method for producing the same, and solar cell material and organic transistor material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of synthesizing compounds of various structures having a fulvalene backbone; and to provide a compound that has a fulvalene backbone having a novel structure.SOLUTION: This invention relates to a fulvalene compound configured to have a fulvalene-derived backbone, to have four specific ring structures formed together with part of the backbone moiety of the five-membered ring that forms the fulvalene backbone, and to have a specific monovalent substituent that serves as a substituent of the respective hydrogen atoms or ring structures in these four ring structures.

Description

The present invention relates to a fulvalene compound and a method for producing the same, and a solar cell material and an organic transistor material. More specifically, a fulvalene compound that can be suitably used as a functional electronic element material such as an organic semiconductor material used in an organic thin film solar cell, an organic transistor, etc., and a light emitting device such as an organic EL element, a method for producing the same, and a solar The present invention relates to a battery material and an organic transistor material.

In recent years, electronic control has been introduced not only to conventional electrical products but also to various products such as automobiles and other transportation equipment, and the performance required for electronic components such as semiconductors used for such electronic control is also available. It is getting higher and higher. In such electronic parts, in addition to inorganic materials such as inorganic semiconductors made of transition metals such as silicon and germanium, organic materials are also used, and have electrical characteristics that can be used as materials for electronic parts. Research has been conducted on organic compounds.
In the field of organic semiconductors, many materials have been proposed and developed for p-type organic semiconductors, including poly (3-hexylthiophene) (P3HT). On the other hand, development of n-type organic semiconductors typified by fullerene derivatives has been delayed for various reasons. In particular, since few polymer n-type organic semiconductors suitable for the coating process are known, rapid development is desired. Since materials used as such organic semiconductor materials are required to have low LUMO energy levels, research and development have been conducted on compounds having low LUMO energy levels.

In fluorenylidene, steric repulsion occurs in the molecule due to a central double bond. It is not aromatic because it does not satisfy the Hückel rule, but it satisfies the Hückel rule by receiving π electrons. From this, it is considered that the acceptor property is strong, but it has been reported by a paper that the LUMO energy level is actually lowered (see Non-Patent Document 1). Among such compounds having a fluorenylidene structure, research and development examples of compounds having a bifluorenylidene structure have been reported. Synthesis of compounds having a bifluorenylidene structure, evaluation of electrical properties, bifluorenyl The use of a compound having a redene structure as an electroluminescent element is disclosed (see Patent Documents 1 and 2). Furthermore, a compound having a bifluorenylidene structure and a compound having a bifluorenylidene-like structure have been reported (see Non-Patent Documents 2 to 10).

Japanese Patent Laid-Open No. 11-54284 International Publication No. 2010/038251

F. Gee. Four people from FG Brunetti, “Angevante Chemie International Edition”, 2010, No. 49, p. 532-536 George R. One outside of George R. Newkome, “Journal of Organic Chemistry”, 1979, Vol. 44, No. 4, p. 502-505 Yu Chi Yip and five others, “Journal of Organic Chemistry”, 1990, Vol. 55, p. 1881-1889 Three people outside of Piotr PIOTROWIAK, “Bulletin of the Polish Academy of Science”, 1994, Vol. 42, No. 4, p. 445-453 Marianne Riklin and one other person, “Helvetica Chema Acta”, 1999, Vol. 82, p. 1666-1680 Two others, Lam Lung Yeung, “Journal of Organic Chemistry”, 1990, Vol. 55, p. 1874-1881 Two others, Lam Lung Yeung, “Journal of the Chemical Society, Chemical Communications”, 1987, p. 981-983 Jing Luo and 6 others, “Organic Letters”, 2010, Vol. 12, No. 24, p. 5660-5663 Three people from Elise Molins, “Journal of Organic Chemistry”, 2002, Vol. 67, p. 7175-7178 Masahiro Minabe, “Bulletin of the Chemical Society of Japan”, 1975, Vol. 48, No. 2, p. 586-590

As described above, a compound having a fluorenylidene structure is expected to be developed as an electronic device material such as an organic semiconductor material, and the development of a compound more suitable for use in the electronic device material is required. Among them, compounds having a bifluorenylidene structure have been reported. However, the synthesis methods of compounds having a bifluorenylidene structure that have been reported so far have limited the structures of derivatives that can be synthesized. . In order to develop a compound that is more suitable for electronic device material applications, it is essential to be able to synthesize more various derivatives of compounds having a bifluorenylidene structure. Furthermore, if it is possible to synthesize not only bifluorenylidene in which the benzene ring is fused to the fulvalene skeleton but also compounds in which the ring structure condensed to the fulvalene skeleton is changed to various ones, the development of compounds that are more suitable for electronic device material applications It is more preferable when recommending. For this reason, there is a demand for the development of compounds having various structures having a fulvalene skeleton, and the development of compounds having a fulvalene skeleton having a new structure.

The present invention has been made in view of the above situation, and has a new compound having a full valvalene skeleton that can be suitably used as a material for an n-type organic semiconductor, an organic EL element, and the like, and various structures having a fulvalene skeleton. It is an object of the present invention to provide a production method capable of synthesizing the above compound.

The present inventor has studied a production method that enables synthesis of compounds having various structures having a fulvalene skeleton, and a compound having a fulvalene skeleton having a new structure. A manufacturing method was developed.
The conventional method for producing a bifluorenylidene compound was based on a fluorene derivative, but the new production method developed by the present inventor is a ring structure having a conjugated diene structure and a triple bond in the basic skeleton. A compound having a fulvalene skeleton is produced by a coupling reaction between the containing compound and a ring structure-containing compound having a conjugated diene structure in the basic skeleton. According to the method of the present invention, a compound having a fulvalene skeleton of various structures can be synthesized by changing the ring structure condensed to the basic skeleton of the compound as a raw material and the substituent bonded to the ring structure to various ones. Is possible. Furthermore, this inventor discovered another manufacturing method which can manufacture the compound which has a fulvalene skeleton with a high yield. The inventors have synthesized a compound having a novel fulvalene skeleton by such a production method, and the compound having a fulvalene skeleton has a low LUMO energy level, and is an organic semiconductor material, particularly an organic thin film solar cell material, an organic The inventors have found that it can be suitably used as a material for a light emitting device such as a transistor material or an organic EL element, and have conceived that the above-mentioned problems can be solved brilliantly, and have reached the present invention.

That is, the present invention is a compound having a fulvalene-derived skeleton, wherein the compound is represented by the following formula (1);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Alternatively, differently, a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure may be represented, and a plurality of each may be bonded to a ring structure forming a dotted arc portion. When all the ring structures are benzene rings, X ^{1 to} X ⁴ are not bonded to each other, and all of X ^{1 to} X ⁴ are not the same structure, and X ^{1 to} X ⁴ When a halogen atom is contained, at least one of X ^{1 to} X ⁴ is a monovalent substituent other than a halogen atom, and all four ring structures represented by dotted arcs are benzene rings. , ^X 1, ^{X 3} is the same monovalent substituents a ^{and,, X} 2, X ⁴ If a hydrogen atom or X ^1, X ³ is different from the same monovalent substituent B, or, a four ring structure are all benzene ring represented by the dotted arcs, X ^1, X ⁴ is When the same monovalent substituent A and X ² and X ³ are a hydrogen atom or the same monovalent substituent B different from X ¹ and X ⁴ , the monovalent substituent A is bromine X is a substituent other than an atom, a methoxy group, a carboxyl group, a —CO ₂ CH ₃ group, a —CH ₂ OH group, a —CONHR group (R represents a hydrocarbon group containing a phenyl group in the structure). ¹ and X ² are both bonded to a naphthalene ring, and X ³ and X ⁴ are all bonded to a benzene ring, at least one of X ³ and X ⁴ is It is a monovalent substituent other than a methoxy group, and there is no ring structure to which X ¹ and X ² are bonded. This is also a pyridine ring, and when the ring structure to which X ³ and X ⁴ are bonded is a benzene ring or both are pyridine rings, at least one of X ^{1 to} X ⁴ is monovalent. The four ring structures represented by dotted arcs are all thiophene rings, and the sulfur atom of the thiophene ring to which X ¹ is bonded and the sulfur atom of the thiophene ring to which X ² is bonded Has a structure in which X is bonded through two carbon atoms, and the sulfur atom of the thiophene ring to which X ³ is bonded and the sulfur atom of the thiophene ring to which X ⁴ is bonded are bonded through two carbon atoms. In this case, at least one of X ^{1 to} X ⁴ is formed from a hydrogen atom, a bromine atom, a 2-thiophene group, a 5-bromo-2-thiophene group, one or two thiophene rings and an alkyl group. Monovalent substituents other than groups It is. It is a fulvalene compound characterized by being represented by this.

The present invention also provides the following formula (1 ″);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or differently, a hydrogen atom or a monovalent substituent which is a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part). A method of manufacturing comprising:
The above production method is represented by the following formula (2);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ¹ and X ² are the same or different and represent a hydrogen atom or A monovalent substituent serving as a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part, and Y represents a hydrogen atom or a monovalent substituent. An unsaturated bond-containing compound (I) represented by the following formula (3);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ³ and X ⁴ are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ¹ and R ² may be bonded to the ring structure forming the dotted arc portion. A process for reacting the unsaturated bond-containing compound (II) represented by the formula (II).

The present invention further includes the following formula (1 ″);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or differently, a hydrogen atom or a monovalent substituent which is a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part). A method of manufacturing comprising:
The above production method has the following formula (3 ′);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ³ and X ⁴ are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ¹ ′ and R ² ′ may be the same or different and may be bonded to a ring structure forming a dotted arc portion. An unsaturated bond-containing compound (II ′) represented by the following formula (4):

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ¹ and X ² are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ³ and R ⁴ may be bonded to the ring structure forming the dotted arc portion. A process for reacting with the unsaturated bond-containing compound (III) represented by the formula (1).
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The fulvalene compound of the present invention has the following formula (1);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Alternatively, differently, a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure may be represented, and a plurality of each may be bonded to a ring structure forming a dotted arc portion. When all the ring structures are benzene rings, X ^{1 to} X ⁴ are not bonded to each other, and all of X ^{1 to} X ⁴ are not the same structure, and X ^{1 to} X ⁴ When a halogen atom is contained, at least one of X ^{1 to} X ⁴ is a monovalent substituent other than a halogen atom, and all four ring structures represented by dotted arcs are benzene rings. , ^X 1, ^{X 3} is the same monovalent substituents a ^{and,, X} 2, X ⁴ If a hydrogen atom or X ^1, X ³ is different from the same monovalent substituent B, or, a four ring structure are all benzene ring represented by the dotted arcs, X ^1, X ⁴ is When the same monovalent substituent A and X ² and X ³ are a hydrogen atom or the same monovalent substituent B different from X ¹ and X ⁴ , the monovalent substituent A is bromine X is a substituent other than an atom, a methoxy group, a carboxyl group, a —CO ₂ CH ₃ group, a —CH ₂ OH group, a —CONHR group (R represents a hydrocarbon group containing a phenyl group in the structure). ¹ and X ² are both bonded to a naphthalene ring, and X ³ and X ⁴ are all bonded to a benzene ring, at least one of X ³ and X ⁴ is It is a monovalent substituent other than a methoxy group, and there is no ring structure to which X ¹ and X ² are bonded. This is also a pyridine ring, and when the ring structure to which X ³ and X ⁴ are bonded is a benzene ring or both are pyridine rings, at least one of X ^{1 to} X ⁴ is monovalent. The four ring structures represented by dotted arcs are all thiophene rings, and the sulfur atom of the thiophene ring to which X ¹ is bonded and the sulfur atom of the thiophene ring to which X ² is bonded Has a structure in which X is bonded through two carbon atoms, and the sulfur atom of the thiophene ring to which X ³ is bonded and the sulfur atom of the thiophene ring to which X ⁴ is bonded are bonded through two carbon atoms. In this case, at least one of X ^{1 to} X ⁴ is formed from a hydrogen atom, a bromine atom, a 2-thiophene group, a 5-bromo-2-thiophene group, one or two thiophene rings and an alkyl group. Monovalent substituents other than groups It is. ).
The fulvalene compound of the present invention is a compound having a fulvalene structure as a basic skeleton and four ring structures formed together with a part of a carbon five-membered skeleton forming the fulvalene skeleton.
It is known that polyfluorene obtained by polymerizing fluorene having a structure in which two benzene ring structures are formed together with a carbon 5-membered ring can be used as a light-emitting agent for organic EL. The fulvalene compound of the present invention can be suitably used as a material for a light-emitting device, but it contains only a structural part in which two ring structures are formed together with a carbon five-membered ring similar to fluorene. The fulvalene compound of the present invention has a low LUMO energy level due to its structure, and the fulvalene compound of the present invention has a structure derived from fluorene. It is a compound that can exhibit characteristics that cannot be expressed by a compound that only contains a site.

In the above formula (1), X ^{1 to} X ⁴ are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and each of the ring structures forming the dotted arc portion is plural. It may be bonded. That is, when X ¹ is a hydrogen atom, the ring structure having X ¹ does not have a substituent. Similarly, when X ^{2 to} X ⁴ are hydrogen atoms, the ring structure having each of X ^{2 to} X ⁴ does not have a substituent.
In the present specification, the substituent means a group including an organic group containing carbon and a group not containing carbon such as a halogen atom and a hydroxy group.

In the fulvalene compound represented by the above formula (1), any one of X ^{1 to} X ⁴ is a monovalent substituent, the remaining three are hydrogen atoms, and X ¹ and X ² are monovalent substitutions. X ³ and X ⁴ are hydrogen atoms, X ² and X ⁴ are monovalent substituents, X ¹ and X ³ are hydrogen atoms, X ¹ and X ⁴ are monovalent Any one of X ² and X ³ is a hydrogen atom, X ^{1 to} X ⁴ are all hydrogen atoms, and X ^{1 to} X ⁴ are all monovalent substituents. Is preferred. More preferably, X ² and X ⁴ are monovalent substituents, X ¹ and X ³ are hydrogen atoms, X ¹ and X ² are monovalent substituents, and X ³ and X ⁴ are Any one of which is a hydrogen atom, X ¹ and X ⁴ are monovalent substituents, X ² and X ³ are hydrogen atoms, and all of X ^{1 to} X ⁴ are monovalent substituents It is.

When X ^{1 to} X ⁴ are monovalent substituents, examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, a halogen atom of an iodine atom; a methyl chloride group, a methyl bromide group, a methyl iodide group, A haloalkyl group such as a fluoromethyl group, a difluoromethyl group and a trifluoromethyl group; a carbon number of 1 to 1 such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group 4 linear or branched alkyl groups; C5-C7 cyclic alkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy Group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc. A linear or branched alkoxy group of ~ 8; hydroxyl group; thiol group; epoxy group; nitro group; azo group; allyl group; cyano group; amino group; methylamino group, ethylamino group, dimethylamino group, diethylamino group Mono- or dialkylamino groups having an alkyl group of 1 to 4 carbon atoms such as a group; amino groups such as diphenylamino group and carbazolyl group; acyl groups such as acetyl group, propionyl group and butyryl group; vinyl group and 1-propenyl group An alkynyl group having 2 to 8 carbon atoms such as allyl group, butenyl group and styryl group; an alkynyl group having 2 to 8 carbon atoms such as ethynyl group, 1-propynyl group, propargyl group and phenylacetylin; vinyloxy group and allyloxy group Alkenyloxy groups such as ethynyloxy groups and phenylacetyloxy groups Aryloxy groups such as phenoxy group, naphthoxy group, biphenyloxy group, pyrenyloxy group; perfluoro groups such as trifluoromethyl group, trifluoromethoxy group, pentafluoroethoxy group, and further long-chain perfluoro groups; diphenylboryl group, Boryl groups such as dimesitylboryl group, bis (perfluorophenyl) boryl group and diboronic acid ester group; carbonyl groups such as acetyl group and benzoyl group; carbonyloxy groups such as acetoxy group and benzoyloxy group; methoxycarbonyl group and ethoxycarbonyl group , Alkoxycarbonyl groups such as phenoxycarbonyl group; sulfinyl groups such as methylsulfinyl group and phenylsulfinyl group; trimethylsilyl group, triisopropylsilyl group, dimethyl-tert-butylsilyl group, trimethoxy Silyl groups such as silyl groups and triphenylsilyl groups; phenyl groups optionally substituted by halogen atoms, alkyl groups, alkoxy groups, 2,6-xylyl groups, mesityl groups, duryl groups, biphenyl groups, terphenyl groups Aryl groups such as naphthyl group, anthryl group, pyrenyl group, toluyl group, anisyl group, fluorophenyl group, diphenylaminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, phenanthrenyl group; oligoaryl group; thienyl group, furyl group , Silacyclopentadienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridinyl group, quinolyl group, quinoxaloyl group, phenanthrolyl group, benzothienyl group, benzothiazolyl group, indolyl group, carbazolyl group, pyridyl , Pyrrolyl group, benzoxazolyl group, pyrimidyl group, imidazolyl group, etc .; oligo heterocyclic group; carboxyl group; carboxylate ester; epoxy group; isocyano group; cyanate group; isocyanate group; thiocyanate group; Carbamoyl group; N, N-dicarbcarbamoyl group such as N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group; formyl group; nitroso group; formyloxy group; stannyl group; phosphino group; silyloxy group; Oxy group; alkylsulfonyloxy group; arylthio group; arylalkyl group; arylalkenyl group; arylalkynyl group; arylalkoxy group; arylalkylthio group; These substituents may be substituted with a reactive group.

X ^{1 to} X ⁴ are preferably a hydrogen atom or, among the above substituents, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom of an iodine atom; a methyl chloride group, a methyl bromide group, a methyl iodide group, Haloalkyl groups such as fluoromethyl group, difluoromethyl group and trifluoromethyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and phenoxycarbonyl group; carboxyl group, hydroxyl group, thiol group, epoxy group, isocyanate group, amino group Group, azo group, acyl group, allyl group, nitro group, alkoxycarbonyl group, formyl group, cyano group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkylsulfonyloxy group, etc. Reactive group: straight or straight chain having 1 to 4 carbon atoms Is a branched alkyl group or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the reactive group; a linear or branched alkoxy group having 1 to 8 carbon atoms or the reactivity A linear or branched alkoxy group having 1 to 8 carbon atoms substituted with a group; an aryl group or an aryl group substituted with the reactive group; an oligoaryl group or an oligoaryl group substituted with the reactive group A monovalent heterocyclic group or a monovalent heterocyclic group substituted with the reactive group; a monovalent oligo heterocyclic group or a monovalent oligo heterocyclic group substituted with the reactive group; an alkylthio group; Aryloxy group; arylthio group; arylalkyl group; arylalkenyl group; arylalkynyl group; arylalkoxy group; arylalkylthio group; alkenyl group or alkenyl group substituted by the reactive group Alkynyl group substituted with an alkynyl group or the reactive group is preferable. More preferably, a hydrogen atom, a bromine atom, an iodine atom, a boryl group, an alkyl group, an alkynyl group, an alkenyl group, an alkoxycarbonyl group, a formyl group, a stannyl group, a phosphino group, an aryl group substituted with the reactive group, An oligoaryl group substituted with a reactive group, a monovalent heterocyclic group such as a group represented by the following formula (5), or a monovalent heterocyclic group substituted with the reactive group, the reactive group A substituted monovalent oligoheterocyclic group, an alkenyl group, an alkenyl group substituted with the reactive group, an alkynyl group, or an alkynyl group substituted with the reactive group.
In the fulvalene compound of the present invention, when X ^{1 to} X ⁴ are monovalent substituents, the bonding position and the number of bonds of X ^{1 to} X ⁴ with respect to the ring structure are not particularly limited.

In the present invention, at least one of X ¹ to X ⁴ in the formula (1), it is also one of the preferred embodiments of the present invention is a substituent having a reactive group. When at least one of the X ^{1 to} X ⁴ is a substituent having a reactive group among those described above, examples of such a substituent include a halogen atom, a carboxyl group, a hydroxyl group, a thiol group, Epoxy group, isocyanate group, amino group, azo group, acyl group, allyl group, nitro group, alkoxycarbonyl group, formyl group, cyano group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group A reactive group such as an alkylsulfonyloxy group; a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the reactive group; a straight chain having 1 to 8 carbon atoms substituted with the reactive group; Linear or branched alkoxy group; aryl group substituted with the reactive group; oligoaryl group substituted with the reactive group; substituted with the reactive group Monovalent heterocyclic group substituted with the reactive group; alkenyl group or alkenyl group substituted with the reactive group; alkynyl group or alkynyl substituted with the reactive group Groups are preferred. More preferably, a bromine atom, an iodine atom, a boryl group, a formyl group, a stannyl group, a phosphino group, an aryl group substituted with the reactive group, an oligoaryl group substituted with the reactive group, or the reactive group Substituted with a substituted monovalent heterocyclic group, monovalent oligoheterocyclic group substituted with the reactive group, alkenyl group or alkenyl group substituted with the reactive group, alkynyl group or reactive group An alkynyl group. More preferably, a bromine atom, a boryl group, a formyl group, a stannyl group, a phosphino group, an aryl group substituted with the reactive group, an oligoaryl group substituted with the reactive group, or a substituted with the reactive group A monovalent heterocyclic group, a monovalent oligoheterocyclic group substituted with the reactive group, an alkenyl group, an alkenyl group substituted with the reactive group, an alkynyl group, or an alkynyl group substituted with the reactive group It is.

When at least one of X ^{1 to} X ⁴ in the above formula (1) is a substituent having a reactive group, (i) a reactivity capable of polymerizing at least one of X ^{1 to} X ⁴ alone. Or (ii) at least two of X ^{1 to} X ⁴ as a substituent having a reactive group, and one kind of fulvalene compound as a combination of reacting the at least two reactive groups is Or (iii) containing two or more fulvalene compounds represented by formula (1) and having a combination of reactive groups such that these fulvalene compounds can be copolymerized; Or (iv) Reactivity such that one or more fulvalene compounds represented by formula (1) can be copolymerized with another compound having at least one reactive group Combination of groups By so comes to have, it can be suitably used as a raw material of the polymer.
In the above (iii) and (iv), the copolymerization includes polycondensation. That is, (iii) includes those having a combination of reactive groups containing two or more fulvalene compounds represented by the formula (1) and capable of polycondensation of these fulvalene compounds, (iv) Includes those having a combination of reactive groups such that one or more fulvalene compounds represented by formula (1) can be polycondensed with another compound having at least one reactive group It is.
Among these, the fulvalene compound of the present invention preferably has a substituent that can be polycondensed alone or with one or more other monomers other than the fulvalene compound represented by the formula (1).
A polymer obtained from such a fulvalene compound can be suitably used as a polymer n-type organic semiconductor suitable for a coating process.

In the above formula (1), the ring structure formed by the dotted arc and a part of the skeleton portion of the five-membered ring forming the fulvalene skeleton is not particularly limited as long as it is a cyclic structure. Cyclohexane ring, thiophene ring, benzothiophene ring, thiazole ring, oxazole ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyridazine ring, pyrazine ring, pyrimidine ring, indole A ring, an isoindole ring, a quinoline ring, an isoquinoline ring, and a phenanthridine ring, which are represented by the following formulas (6-1) to (6-22), respectively. Further, a fulvalene skeleton such as (8-6), (8-12), (8-14), (8-15), (8-18) and (8-23) to (8-25) described later. It may be a ring structure including a 5-membered skeleton portion forming Among these, a benzene ring, a naphthalene ring, a cyclohexane ring, a thiophene ring, and a pyridine ring are preferable.

The fulvalene compound of the present invention has a structure represented by the above formula (1). When all four ring structures represented by dotted arcs in the above formula (1) are benzene rings, X ¹ ˜X ⁴ are not bonded to each other, and all of X ^{1 to} X ⁴ are not the same structure. Further, when all of the four ring structures represented by dotted arcs are benzene rings and X ^{1 to} X ⁴ contain a halogen atom, at least one of X ^{1 to} X ⁴ Is a monovalent substituent other than a halogen atom. That is, when all of the four ring structures represented by dotted arcs in the above formula (1) are benzene rings, none of X ^{1 to} X ⁴ forms a bond, and X ^{1 to} X ⁴ Are present independently and at least one of X ^{1 to} X ⁴ is a monovalent substituent, and all ^four of X ^{1 to} X ⁴ are monovalent substituents, X ^{1 to} X ⁴ contain at least two types of monovalent substituents. Further, if it contains a halogen atom in X ¹ to X ⁴ is at least one of X ¹ to X ⁴ is a monovalent substituent other than a halogen atom. In this case, a monovalent substituent other than a halogen atom is preferably a monovalent substituent in the case where X ^{1 to} X ⁴ are monovalent substituents, and a halogen atom is removed from the preferred monovalent substituent. It is.

In the fulvalene compound represented by the above formula (1), all of the four ring structures represented by dotted arcs are benzene rings, and X ¹ and X ³ are the same monovalent substituent A, and X ² , X ⁴ is a hydrogen atom or the same monovalent substituent B different from X ¹ , X ³ , or four ring structures represented by dotted arcs are all benzene rings, ¹ and X ⁴ are the same monovalent substituent A and X ² and X ³ are a hydrogen atom or the same monovalent substituent B different from X ¹ and X ⁴ , the monovalent substitution The group A is a substituent other than a bromine atom, a methoxy group, a carboxyl group, a —CO ₂ CH ₃ group, a —CH ₂ OH group, and a —CONHR group (R represents a hydrocarbon group containing a phenyl group in the structure). It is a group. Preferred examples of the monovalent substituent A in this case include a bromine atom, a methoxy group, a carboxyl group, and a preferable monovalent substituent when X ^{1 to} X ⁴ described above are monovalent substituents. It excludes the —CO ₂ CH ₃ group, —CH ₂ OH group, and —CONHR group.

In the fulvalene compound represented by the above formula (1), the ring structures to which X ¹ and X ² are bonded are both naphthalene rings, and the ring structures to which X ³ and X ⁴ are bonded are all benzene. When it is a ring, at least one of X ³ and X ⁴ is a monovalent substituent other than a methoxy group. If either X ³ or X ^{4 is} a monovalent substituent other than a methoxy group, the other may be a hydrogen atom, a methoxy group, or a monovalent substituent other than a methoxy group It may be.
Among X ³ and X ⁴ , those preferable as the monovalent substituent other than the methoxy group are preferable from those preferable as the monovalent substituent when X ^{1 to} X ⁴ described above are monovalent substituents. Excluding the group.

Furthermore, in the fulvalene compound represented by the above formula (1), the ring structures to which X ¹ and X ² are bonded are all pyridine rings, and the ring structures to which X ³ and X ⁴ are bonded are all benzene. When it is a ring or both are pyridine rings, at least one of X ^{1 to} X ⁴ is a monovalent substituent. That is, when the ring structures to which X ¹ and X ² are bonded are all pyridine rings, the ring structures to which X ³ and X ⁴ are bonded are all benzene rings, or both are pyridine rings. , X ^{1 to} X ⁴ are not all hydrogen atoms. As long as at least one of X ^{1 to} X ⁴ is a monovalent substituent, two may be a monovalent substituent, a trivalent or a monovalent substituent, and all of X ^{1 to} X ⁴ May be a monovalent substituent. In this case, what is preferable as the monovalent substituent is the same as in the case where X ^{1 to} X ⁴ described above are monovalent substituents.

Furthermore, in the fulvalene compound represented by the above formula (1), all four ring structures represented by dotted arcs are thiophene rings, and X ² is bonded to the sulfur atom of the thiophene ring to which X ¹ is bonded. and has a structure bonded through to the sulfur atom of the thiophene ring and the two carbon atoms, and sulfur atoms thiophene ring sulfur atom and X ⁴ of the thiophene ring to which X ³ is bonded is bonded Has a structure bonded via two carbon atoms, at least one of X ^{1 to} X ⁴ is a hydrogen atom, a bromine atom, a 2-thiophene group, a 5-bromo-2-thiophene group, a thiophene ring 1 or It is a monovalent substituent other than a group formed from two and an alkyl group.
In the fulvalene compound represented by the above formula (1), all four ring structures represented by dotted arcs are thiophene rings, and the sulfur atom of the thiophene ring to which X ¹ is bonded and X ² are bonded. The sulfur atom of the thiophene ring to which the sulfur atom of the thiophene ring to which X ³ is bonded is bonded to the sulfur atom of the thiophene ring to which X ⁴ is bonded. The case of having a structure bonded through two carbon atoms is a case where the fulvalene compound has a structure represented by the following formula (7-1). In the structure represented by the following formula (7-2), the sulfur atom of the thiophene ring to which X ¹ is bonded and the sulfur atom of the thiophene ring to which X ² is bonded are bonded via three carbon atoms. Since this is a structure, this structure is not included in this case.

When the fulvalene compound of the present invention has a structure represented by the above formula (7-1), at least one of X ^{1 to} X ⁴ is a hydrogen atom, a bromine atom, a 2-thiophene group, 5-bromo-2- It is a monovalent substituent other than a thiophene group, a group formed from one or two thiophene rings and an alkyl group. The group formed from one or two thiophene rings and an alkyl group is a group having a structure in which an alkyl group is bonded to one or two thiophene rings bonded to each other.
When the fulvalene compound has a structure represented by the above formula (7-1), a preferable monovalent substituent is a bromine atom, a 2-thiophene group, a 5-bromo-2-thiophene group, a thiophene ring 1 or Except for the group formed from two and an alkyl group, it is the same as that preferable as the monovalent substituent when X ^{1 to} X ⁴ described above are monovalent substituents.

Furthermore, in the fulvalene compound represented by the above formula (1), 1 to 3 of X ^{1 to} X ⁴ in the formula (1) are monovalent substituents containing a carbon-carbon double bond or triple bond. Some are also one preferred embodiment of the fulvalene compound of the present invention.
That is, at least one of X ^{1 to} X ⁴ in Formula (1) is a monovalent substituent containing a carbon-carbon double bond or triple bond, but all of X ^{1 to} X ⁴ are carbon-carbon. A monovalent substituent containing an intervening double bond or triple bond, and a monovalent substituent containing a hydrogen atom or a carbon-carbon double bond or triple bond in X ^{1 to} X ⁴ A fulvalene compound containing at least one monovalent substituent that is not a substituent is also one preferred embodiment of the fulvalene compound of the present invention.
The monovalent substituent containing a carbon-carbon double bond or triple bond is not particularly limited as long as it contains a carbon-carbon double bond or triple bond, but the above-mentioned X ^{1 to} X ⁴ are 1 Among those preferable as the monovalent substituent in the case of the valent substituent, those having a carbon-carbon double bond or triple bond are preferable. More preferably, it is a substituent having a cyclic structure, and a carbon-carbon double bond or triple bond constituting a part of the cyclic structure.
In the fulvalene compound represented by the above formula (1), when at least one of X ^{1 to} X ^{4 is} a monovalent substituent containing a carbon-carbon double bond or triple bond, Among the substituents that are not monovalent substituents containing a heavy bond or a triple bond, among the preferable monovalent substituents when X ^{1 to} X ⁴ described above are monovalent substituents, carbon-carbon Those not containing double bonds or triple bonds are preferred.

In the above formula (1), there are four ring structures formed by the dotted arc and a part of the skeleton portion of the five-membered ring that forms the fulvalene skeleton. Of these four ring structures, X ¹ , X ² is preferably a benzene ring, naphthalene ring, thiophene ring, pyridine ring, or benzothiophene ring, and the two ring structures to which X ³ and X ⁴ are bonded are: A benzene ring, naphthalene ring, thiophene ring, pyridine ring, or benzothiophene ring is preferred.
Moreover, it is one of the suitable embodiment of the fulvalene compound of this invention that 1-3 are thiophene rings among the four ring structures represented by the dotted-line arc in the said Formula (1).

In the fulvalene compound of the present invention, the four ring structures are composed of two types of ring structures, and the ring structures in which X ¹ and X ² , X ³ and X ⁴ are bonded are the same ring structure. This is one of the preferred embodiments. That is, in the above formula (1), the ring structure to which X ¹ is bonded and the ring structure to which X ² are bonded are the same, and the ring structure to which X ³ is bonded and the ring structure to which X ⁴ is bonded A fulvalene compound having the same ring structure in which a ring structure to which X ¹ and X ² are bonded and a ring structure to which X ³ and X ⁴ are bonded is a preferred embodiment of the present invention. It is.
Further, among the four ring structures to which X ^{1 to} X ⁴ are bonded in the above formula (1), a fulvalene compound in which three are the same ring structure and only one is a ring structure different from the other three, 1 is one of the preferred embodiments of the present invention.
Further, all of the ring structures to which X ^{1 to} X ⁴ are bonded are the same ring structure, X ¹ and X ² are the same monovalent substituent, and both X ³ and X ⁴ are hydrogen. It is one of the preferred embodiments of the present invention that they are atoms or the same substituent and are different from X ¹ and X ² .
Further, all of the ring structures to which X ^{1 to} X ⁴ are bonded are the same ring structure, and any one of X ^{1 to} X ⁴ is a monovalent substituent, and the other three are hydrogen atoms. Or any three of X ^{1 to} X ⁴ are the same or different and are monovalent substituents, and the remaining one is a hydrogen atom, which is another preferred embodiment of the present invention. It is.

Thus, the fulvalene compound of the present invention is constituted by the structural part constituted by the ring structure in which X ¹ and X ¹ are bonded in the above formula (1), and the ring structure in which X ² and X ² are bonded. At least four structural sites of a structural site composed of a ring structure to which X ³ and X ³ bind, and a structural site composed of a ring structure to which X ⁴ and X ⁴ bind One is preferably different from at least one of the other three structural sites.

As a preferable fulvalene compound of this invention, the compound of a structure like following formula (8-1)-(8-31) is mentioned, for example. Among these, (8-1) to (8-3), (8-6), (8-8) to (8-13), (8-16), (8-17), (8-20) ) To (8-31) are more preferable. More preferably, it has a reactive group capable of polycondensation reaction, (8-1), (8-2), (8-10) to (8-13), (8-16) (8-20) to (8-23).

Since the fulvalene compound of the present invention has a low LUMO energy level, it can be suitably used as a material for an n-type semiconductor or an organic EL device. The energy level of LUMO is preferably 3.0 eV to 5.2 eV, for example. In such a range, when used as an n-type semiconductor material or an organic EL element material, the performance can be sufficiently exhibited. The energy level of LUMO is more preferably 3.0 eV to 5.1 eV, and still more preferably 3.2 eV to 5.0 eV.
The LUMO energy level can be obtained as follows.
<LUMO energy levels>
A p-doped silicon substrate (manufactured by Furuuchi Chemical Co., Ltd.) is cut into 25 mm square, and ultrasonically washed in acetone and isopropyl alcohol for 10 minutes, respectively, and then subjected to UV ozone treatment for 20 minutes. Then, this board | substrate was fixed to the board | substrate holder of the vacuum evaporation apparatus (made by ULVAC) connected with the glove box of argon atmosphere. A sample to be measured is put in a quartz crucible, and the pressure is reduced to about 1 × 10 ⁻³ Pa. For the created measurement sample, an ionization potential is measured using an ultraviolet photoelectron spectrometer (manufactured by Kobelco Kaken Co., Ltd.), and the measured value is set as the energy level of the highest occupied orbit (HOMO) of the sample.
At the same time, the absorption spectrum of another sample thin film prepared in the same manner as described above is measured using an ultraviolet-visible spectrophotometer (product name “Agilent 8453”, manufactured by Agilent Technologies). A long wavelength side absorption edge λ (unit: nm) of an absorption peak is read from the obtained spectrum, and a HOMO-LUMO gap (B.G.) is obtained by the following formula (1).

Furthermore, from the HOMO energy level obtained using the composite electron spectrometer as described above and the HOMO-LUMO gap (BG) obtained from the above equation (1), the following equation (2) is obtained. Obtain the LUMO energy level.

（式中、４つの点線の円弧は、同一又は異なって、フルバレン骨格を形成する５員環の骨格部分の一部と共に環構造が形成されていることを表す。Ｘ^１〜Ｘ^４は、同一又は異なって、水素原子又は環構造の置換基となる１価の置換基を表し、点線の円弧部分を形成する環構造にそれぞれ複数個結合していてもよい。点線の円弧で表される４つの環構造が全てベンゼン環である場合、Ｘ^１〜Ｘ^４の全てが同じ構造であることはない。Ｘ^１〜Ｘ^４が結合している環構造が全てナフタレン環である場合、Ｘ^１〜Ｘ^４のうち少なくとも１つは１価の置換基であり、Ｘ^１、Ｘ^２が結合している環構造がいずれもナフタレン環であり、Ｘ^３、Ｘ^４が結合している環構造がいずれもベンゼン環である場合、Ｘ^３、Ｘ^４の少なくとも一方は、メトキシ基以外の１価の置換基である。Ｘ^１〜Ｘ^４が結合している４つの環構造のうちいずれか１つが、フルバレン骨格を形成する５員環の骨格部分と該骨格部分の一部とともに形成される４つの環とから構成され、該４つの環がいずれもベンゼン環又はナフタレン環である構造の場合、Ｘ^１〜Ｘ^４の少なくとも１つがメトキシ基、２−エチルヘプトキシ基以外の１価の置換基であるか、又は、Ｘ^１〜Ｘ^４が全て水素原子である。）で表されるフルバレン化合物である太陽電池用材料でもある。 The present invention is also a solar cell material comprising a compound having a fulvalene-derived skeleton, wherein the compound is represented by the following formula (1 ′);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Alternatively, differently, a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure may be represented, and a plurality of each may be bonded to a ring structure forming a dotted arc portion. When all of the ring structures are benzene rings, X ^{1 to} X ⁴ are not all the same structure, and when all of the ring structures to which X ^{1 to} X ⁴ are bonded are naphthalene rings, X ¹ to X ⁴ At least one of X ⁴ is a monovalent substituent, the ring structure to which X ¹ and X ² are bonded is a naphthalene ring, and the ring structure to which X ³ and X ⁴ are bonded is If also a benzene ^ring, at least one of X 3, ^{X 4,} main Alkoxy is a monovalent substituent other than group .X ¹ to X ⁴ one of the four ring structures are attached, but one backbone moiety and the backbone portion of the 5-membered ring to form a fulvalene skeleton In the case where each of the four rings is a benzene ring or a naphthalene ring, at least one of X ^{1 to} X ⁴ is 1 other than a methoxy group or a 2-ethylheptoxy group. Or a solar cell material that is a fulvalene compound represented by X ^{1 to} X ⁴ are all hydrogen atoms.

In the above formula (1 ′), specific examples and preferred structures of the structures of X ^{1 to} X ⁴ , specific examples and preferred structures of the ring structure represented by dotted arcs, and the ring to which the monovalent substituent is bonded The positions are specific examples and preferred structures of the structures of X ^{1 to} X ⁴ in the above formula (1), specific examples and preferred structures of ring structures represented by dotted arcs, and rings to which a monovalent substituent is bonded. It is the same as the position of.

In the above formula (1 ′), when all four ring structures represented by dotted arcs are benzene rings, X ^{1 to} X ⁴ are not all the same structure. That is, when all of the four ring structures represented by the dotted arc in the formula (1 ′) are benzene rings, at least one of X ^{1 to} X ⁴ is a monovalent substituent, and X ¹ to When all ^four of X ⁴ are monovalent substituents, at least two monovalent substituents are included in X ^{1 to} X ⁴ .

In the above formula (1 ′), any one of four ring structures to which X ^{1 to} X ⁴ are bonded is formed together with a skeleton part of a 5-membered ring forming a fulvalene skeleton and a part of the skeleton part. And the four rings are all benzene rings or naphthalene rings, the structure of the fulvalene compound represented by the above formula (1 ′) is, for example, the following formula (9-1), This is a structure represented by (9-2).

The above formulas (9-1) and (9-2) are structures in which X ^{1 to} X ⁴ are all hydrogen atoms, and the compound having such a structure is fulvalene represented by the above formula (1 ′). Included in compounds. When at least one of X ^{1 to} X ⁴ is a monovalent substituent, at least one of X ^{1 to} X ^{4 is} a monovalent substituent other than a methoxy group and a 2-ethylheptoxy group.

The present invention further relates to an organic transistor material comprising a compound having a fulvalene-derived skeleton, wherein the compound has the following formula (1 ″):

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure, and a plurality of them may be bonded to the ring structure forming the dotted arc portion). It is also a material for some organic transistors.

In the above formula (1 ″), specific examples and preferred structures of the structures of X ^{1 to} X ⁴ , specific examples and preferred structures of ring structures represented by dotted arcs, and rings to which a monovalent substituent is bonded The specific position of X ^{1 to} X ⁴ in the above formula (1) and the preferred structure, the specific example and preferred structure of the ring structure represented by the dotted arc, and the monovalent substituent are bonded to the position of The same as the position of the ring.

Next, the manufacturing method of the fulvalene compound of this invention is described.
There are two different methods for producing the fulvalene compound of the present invention. In the following, these are referred to as the production method of the first fulvalene compound of the present invention and the production method of the second fulvalene compound of the present invention, respectively, and the production method of the first and second fulvalene compounds of the present invention Are collectively described as a method for producing the fulvalene compound of the present invention.
First, the manufacturing method of the 1st fulvalene compound of this invention is described.
The manufacturing method of the 1st fulvalene compound of this invention is following formula (1 '');

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or differently, a hydrogen atom or a monovalent substituent which is a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part). A method of manufacturing comprising:
The production method comprises the following formula (2):

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ¹ and X ² are the same or different and represent a hydrogen atom or A monovalent substituent serving as a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part, and Y represents a hydrogen atom or a monovalent substituent. An unsaturated bond-containing compound (I) represented by the following formula (3);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ³ and X ⁴ are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ¹ and R ² may be bonded to the ring structure forming the dotted arc portion. A process for reacting the unsaturated bond-containing compound (II) represented by the formula (II).

In the first fulvalene compound production method of the present invention, the compound represented by the above formula (2) or the compound represented by the above formula (3) is appropriately selected to form a ring to which X ^{1 to} X ⁴ are bonded. It is possible to produce fulvalene compounds with various structures.
The manufacturing method of the 1st fulvalene compound of this invention includes the process of making the compound represented by the said Formula (2), and the compound represented by the said Formula (3) react. In this reaction step, the compound represented by the above formula (2) and the compound represented by the above formula (3) may each be used alone or in combination of two or more.
Moreover, as long as the manufacturing method of the 1st fulvalene compound of this invention includes the process of reacting the compound represented by the said Formula (2), and the compound represented by the said Formula (3), another process is carried out. May be included.

The dotted circular arc in the compounds represented by the above formulas (2) and (3) indicates that a ring structure is formed with two carbon atoms constituting a double bond between carbon atoms. That is, the compounds represented by the above formula (2) and the above formula (3) each have at least two ring structures in the structure, and in the above formula (2) and the above formula (3) This indicates that a double bond moiety is included as part of the ring structure.
In the above formula (2), X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of a ring structure. In the above formula (3), X ³ and X ⁴ are The same or different and represents a hydrogen atom or a monovalent substituent which is a substituent of the ring structure.
Specific examples and preferred structures of the structures of X ^{1 to} X ⁴ , specific examples and preferred structures of ring structures represented by dotted arcs, and the position of the ring to which the monovalent substituent is bonded are the above formulas (1) Specific examples and preferred structures of the structures of X ^{1 to} X ^{4 in} the formula, specific examples and preferred structures of the ring structure represented by dotted arcs, and the positions of the rings to which a monovalent substituent is bonded.

Y in the above formula (2) represents a hydrogen atom or a monovalent substituent. Any monovalent substituent may be used as long as it generates a terminal alkyne in the reaction system with the compound represented by the above formula (3) and finally generates a copper (I) acetylide intermediate.
Examples of such a monovalent substituent include a trimethylsilyl group, a triethylsilyl group, and a tripropylsilyl group.
Y is preferably a hydrogen atom or a trivalent silyl group among monovalent substituents.

R ¹ and R ² in the above formula (3) are the same or different and represent a monovalent substituent. The monovalent substituent may be any substituent capable of causing oxidative addition of the Pd (0) species. Examples of such a monovalent substituent include a halogen atom, a triflate group, a tosylate group, and the like. Among these, a bromine atom and an iodine atom are preferable.

In the step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (3), the above formula (3) is used with respect to 1 mol of the compound represented by the above formula (2). The reaction is preferably performed using 0.5 to 1.5 moles of the represented compound. By using at such a ratio, the fulvalene compound represented by the above formula (1) can be produced in high yield. More preferably, 0.7 to 1.3 mol of the compound represented by the above formula (3) is used with respect to 1 mol of the compound represented by the above formula (2).

The step of reacting the compound represented by the formula (2) with the compound represented by the formula (3) is preferably performed using a catalyst. As the catalyst, tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), dichlorobis (triphenylphosphine) palladium (PdCl ₂ (PPh ₃ ) ₂ ), bis (tri-tert-butylphosphine) palladium (Pd ( P ^t Bu ₃ ) ₂ ), tris (dibenzylideneacetone) dipalladium (Pd ₂ dba ₃ ), palladium acetate (Pd (OAc) ₂ ) and other palladium complexes, copper iodide, odor It is preferable to use one or more copper catalysts such as copper chloride and copper chloride. More preferably, Pd (PPh ₃ ) ₄ or Pd (P ^t Bu ₃ ) ₂ and a monovalent copper catalyst such as copper iodide are used.
Moreover, it is preferable to use it as a usage-amount of a catalyst so that the sum total of a palladium complex and a copper catalyst may be 0.001-0.2 mol with respect to 1 mol of compounds represented by the said Formula (2). More preferably, it is used so that it may become 0.01-0.05 mol.

A ligand may be used to increase the reactivity of the catalyst. Examples of the ligand include triphenylphosphine (PPh ₃ ), tri (o-tolyl) phosphine (P (o-tol) 3), tri (2-furyl) phosphine, diphenylphosphinoferrocene, and tri-tert- Butylphosphine, tricyclohexylphosphine, 2- (biphenyl) di-tert-butylphosphine 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-diisopropoxybiphenyl, etc. Of the phosphorus ligand. Of these ligands, triphenylphosphine and tri-tert-butylphosphine are preferable.
As a usage-amount of a ligand, it is preferable to use 0.5-4 mol with respect to 1 mol of palladium catalysts. More preferably, 1 to 2.5 mol is used.
When a catalyst containing a stabilizer such as a phosphine ligand (eg, tetrakis (triphenylphosphine) palladium, bis (tri-tert-butylphosphine) palladium, bis (tricyclohexylphosphine) palladium, etc.) is used. Does not require the use of further ligands.

In the step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (3), it is necessary to add a C—H bond activator. Examples of the activator include amine compounds such as ethyldiisopropylamine (DIPEA), pyridine, triethylamine, and diazabicycloundecene (DBU). These activators may be used alone or in combination of two or more.
As the usage-amount of the said activator, it is preferable that it is 1 mol-10 mol with respect to 1 mol of compounds represented by the said Formula (2). More preferably, it is 1 mol-5 mol, Most preferably, it is 3 mol-5 mol.

The solvent used in the step of reacting the compound represented by the above formula (2) and the compound represented by the above formula (3) is not particularly limited as long as the reaction proceeds, and dimethylformamide (DMF ), Toluene, xylene, dioxane, tetrahydrofuran, dimethyl sulfoxide (DMSO) and the like can be used.

The step of reacting the compound represented by the formula (2) with the compound represented by the formula (3) is preferably performed in an inert gas atmosphere. The inert gas is not particularly limited, and any of nitrogen, argon, helium and the like may be used, but nitrogen and argon are preferable. 1 type (s) or 2 or more types can be used for an inert gas.

The reaction temperature in the step of reacting the compound represented by the formula (2) with the compound represented by the formula (3) is preferably −100 ° C. to 300 ° C. More preferably, it is 0 ° C. to 200 ° C., and particularly preferably 0 ° C. to 150 ° C., although it depends on the solvent.
The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure. The reaction time is preferably 1 to 48 hours. More preferably, it is 10 to 36 hours, and particularly preferably 12 to 30 hours from the viewpoint of industrial and practical use.

Next, the manufacturing method of the 2nd fulvalene compound of this invention is described.
The manufacturing method of the 2nd fulvalene compound of this invention is following formula (1 '');

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or differently, a hydrogen atom or a monovalent substituent which is a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part). A method of manufacturing comprising:
The production method comprises the following formula (3 ′);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ³ and X ⁴ are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ¹ ′ and R ² ′ may be the same or different and may be bonded to a ring structure forming a dotted arc portion. An unsaturated bond-containing compound (II ′) represented by the following formula (4):

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ¹ and X ² are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ³ and R ⁴ may be bonded to the ring structure forming the dotted arc portion. A process for reacting with an unsaturated bond-containing compound (III) represented by the formula (1).

When the fulvalene compound is produced by reacting the compound represented by the above formula (3 ′) and the compound represented by the above formula (4) as in the second fulvalene compound production method of the present invention, the fulvalene compound is produced. Can be produced in higher yields. Another advantage of this method is that a fulvalene compound can be produced without using a highly toxic compound under relatively mild conditions.
The manufacturing method of the 2nd fulvalene compound of this invention includes the process of making the compound represented by the said Formula (3 '), and the compound represented by the said Formula (4) react. In this reaction step, the compound represented by the above formula (3 ′) and the compound represented by the above formula (4) may each be used alone or in combination of two or more.
In addition, the method for producing a fulvalene compound of the present invention includes other steps as long as it includes a step of reacting the compound represented by the above formula (3 ′) with the compound represented by the above formula (4). May be.

The dotted circular arc in the compound represented by the above formula (4) represents that two ring structures are formed together with a part of the skeleton portion of the carbon 5-membered ring. The dotted arc in the compound represented by the above formula (3 ′) is the same as the dotted arc in the compound represented by the above formula (3).
Specific examples and preferred structures of the structures of X ^{1 to} X ⁴ , specific examples and preferred structures of ring structures represented by dotted arcs, and the position of the ring to which the monovalent substituent is bonded are the above formulas (1) Specific examples and preferred structures of the structures of X ^{1 to} X ^{4 in} the formula, specific examples and preferred structures of the ring structure represented by dotted arcs, and the positions of the rings to which a monovalent substituent is bonded.

R ¹ ′ and R ² ′ in the above formula (3 ′) are the same or different and represent a monovalent substituent. Examples of the monovalent substituent include a halogen atom, a triflate group, a tosylate group, and a boryl group. Among these, a bromine atom, an iodine atom, and a boryl group are preferable. R ¹ ′ and R ² ′ are preferably the same substituent.

R ³ and R ⁴ in the above formula (4) are the same or different and represent a monovalent substituent and are different from R ¹ ′ and R ² ′ in the above formula (3 ′). Examples of the monovalent substituent include a halogen atom, a triflate group, a tosylate group, and a boryl group. Among these, a bromine atom, an iodine atom, and a boryl group are preferable. R ³ and R ⁴ are preferably the same substituent.
More preferably, R ¹ ′ and R ² ′ in the formula (3 ′) are both bromine atoms or iodine atoms, and R ³ and R ⁴ in the formula (4) are both boryl groups, or R ¹ ′ and R ² ′ in formula (3 ′) are both boryl groups, and R ³ and R ⁴ in formula (4) are both bromine atoms or iodine atoms. Most preferably, R ¹ ′ and R ² ′ in the above formula (3 ′) are both boryl groups, and R ³ and R ⁴ in the above formula (4) are both bromine atoms or iodine atoms. When R ¹ ′ and R ² ′ in the above formula (3 ′) are both a boryl group, and R ³ and R ⁴ in the above formula (4) are both a bromine atom or an iodine atom, the fulvalene compound can be obtained in a higher yield. Can be manufactured.
The boryl group is a group represented by (RO) ₂ B— (R is the same or different and each represents a hydrogen atom or a hydrocarbon group, and two R may be bonded to each other). .

In the step of reacting the compound represented by the above formula (3 ′) with the compound represented by the above formula (4), the above formula (4) is used with respect to 1 mol of the compound represented by the above formula (3). The reaction is preferably performed using 0.5 to 1.5 moles of the represented compound. By using in such a ratio, the fulvalene compound represented by the above formula (1 ″) can be produced in a high yield. More preferably, 0.7 to 1.3 mol of the compound represented by the above formula (4) is used with respect to 1 mol of the compound represented by the above formula (3 ′).
In addition, when one of the compound represented by the above formula (3 ′) and the compound represented by the above formula (4) has a bromine atom or an iodine atom and the other has a boryl group, the bromine atom or the iodine atom It is more preferable to use 1 to 1.2 mol of the compound having a boryl group with respect to 1 mol of the compound having the compound.

The step of reacting the compound represented by the formula (3 ′) with the compound represented by the formula (4) is preferably performed using a catalyst. As the catalyst, tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), dichlorobis (triphenylphosphine) palladium (PdCl ₂ (PPh ₃ ) ₂ ), bis (tri-tert-butylphosphine) palladium (Pd ( P ^t Bu _{3) 2),} and tris (dibenzylideneacetone) dipalladium _(Pd 2 _dba 3), palladium acetate (Pd _{(OAc) 2)} 1, two or more palladium complexes such as, potassium carbonate, sodium carbonate It is preferable to use 1 type, or 2 or more types of basic compounds, such as cesium carbonate, sodium hydroxide, and potassium hydroxide. More preferably, Pd (PPh ₃ ) ₄ or Pd (P ^t Bu ₃ ) ₂ and potassium carbonate are used.
Moreover, as the usage-amount of a catalyst, it is used so that the sum total of a palladium complex and a basic compound may be 0.001-0.2 mol with respect to 1 mol of compounds represented by the said Formula (3 '). preferable. More preferably, it is used so that it may become 0.01-0.05 mol.

A ligand may be used to increase the reactivity of the catalyst. Examples of the ligand include triphenylphosphine (PPh ₃ ), tri (o-tolyl) phosphine (P (o-tol) ₃ ), tri (2-furyl) phosphine, diphenylphosphinoferrocene, tri-tert- Butylphosphine, tricyclohexylphosphine, 2- (biphenyl) di-tert-butylphosphine 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-diisopropoxybiphenyl, etc. Of the phosphorus ligand. Of these ligands, triphenylphosphine and tri-tert-butylphosphine are preferable.
As a usage-amount of a ligand, it is preferable to use 0.5-4 mol with respect to 1 mol of palladium catalysts. More preferably, 1 to 2.5 mol is used.
When a catalyst containing a stabilizer such as a phosphine ligand (eg, tetrakis (triphenylphosphine) palladium, bis (tri-tert-butylphosphine) palladium, bis (tricyclohexylphosphine) palladium, etc.) is used. Does not require the use of further ligands.

The solvent used in the step of reacting the compound represented by the above formula (3 ′) and the compound represented by the above formula (4) is not particularly limited as long as the reaction proceeds, but tetrahydrofuran. It is preferable to use 1 type, or 2 or more types of ether type | system | group polar solvents, such as diethyl ether and a dioxane. More preferred is tetrahydrfuran.
Furthermore, it is more preferable to use a mixture of water as a solvent. The ratio in the case of using a mixture of an ether polar solvent and water is preferably ether polar solvent: water = 3: 1 to 10: 1. More preferably, it is 4: 1 to 5: 1.

The step of reacting the compound represented by the formula (3 ′) with the compound represented by the formula (4) is preferably performed in an inert gas atmosphere. The inert gas is not particularly limited, and any of nitrogen, argon, helium and the like may be used, but nitrogen and argon are preferable. 1 type (s) or 2 or more types can be used for an inert gas.

The reaction temperature in the step of reacting the compound represented by the above formula (3 ′) with the compound represented by the above formula (4) is preferably 20 ° C. to 100 ° C. More preferably, it is 40 degreeC-80 degreeC.
The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure. The reaction time is preferably 30 hours or longer. More preferably, it is 30 to 48 hours.

In the method for producing the first fulvalene compound of the present invention, after the step of reacting the compound represented by the above formula (2) and the compound represented by the above formula (3) or after the second fulvalene of the present invention After the step of reacting the compound represented by the above formula (3 ′) and the compound represented by the above formula (4) in the compound production method, the compound represented by the above formula (1 ″) is obtained. A step of purifying the fulvalene compound may be included. The purification method is not particularly limited, and an appropriate method may be selected and used from extraction, filtration, silica gel chromatography, column chromatography, recycle preparative gel permeation chromatography, recrystallization, sublimation, and the like. it can. Moreover, any one of these purification methods may be used, and two or more may be used.

The manufacturing method of the fulvalene compound of this invention can be used suitably as a manufacturing method at the time of manufacturing the fulvalene compound of this invention represented by the said Formula (1). That is, it is one of preferred embodiments of the method for producing a fulvalene compound of the present invention to produce the fulvalene compound of the present invention represented by the above formula (1) using the method for producing a fulvalene compound of the present invention. .

As described above, the fulvalene compound having the specific structure represented by the above formula can be suitably used as a material for an n-type semiconductor or an organic EL element. As described above, a solar cell or an organic transistor is used. It is suitable as a material.
Organic EL elements include those having a structure in which an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially laminated, or those having a hole injection layer and an electron injection layer. In these devices, electrons injected from the cathode pass through the electron transport layer and reach the light emitting layer. From the viewpoint of energy efficiency, the minimum empty orbit (LUMO) of the material of the light emitting layer and the electron transport layer is used. ) Preferably has a small energy gap between the LUMO energy level of the electron injection layer material and the valence band of the cathode. As the cathode, metals such as aluminum, magnesium, calcium, and alloys thereof are used. Of these, those having a high valence band energy are easily oxidized, so use a low energy one. Is preferred. By using a fulvalene compound having a low energy level of the lowest vacant orbit (LUMO), it is possible to use, as the cathode, a material that has a low valence band energy and is difficult to oxidize. Can be spread.
Therefore, from such a point, the fulvalene compound of the present invention can be suitably used as a material for an n-type semiconductor or an organic EL element. Thus, it is also one of the present invention that the fulvalene compound of the present invention is used for forming a light emitting device. Such a light-emitting device formed using the fulvalene compound of the present invention is also one aspect of the present invention.
Furthermore, the fulvalene compound having the specific structure represented by the above formula includes, in addition, materials for telecommunications equipment, materials for electrochromics, materials for thermochromics, materials for field effect transistors, materials for integrated circuits, and for gas sensors. It can be suitably used as a material for various applications such as materials, materials for electrochemical cells, materials for organic laser diodes, materials for spin valves, materials for light receiving elements, and materials for spintronics.

The fulvalene compound of the present invention has the above-described configuration, has a low LUMO energy level, and has functionality such as an n-type organic semiconductor material, particularly an organic thin film solar cell material, an organic transistor material, and a light emitting device such as an organic EL element. It can be suitably used as an electronic element material. In addition, the method for producing a fulvalene compound of the present invention enables the synthesis of compounds having various fulvalene skeletons that have been difficult to synthesize so far, and is greatly used in the research and development of compounds more suitable as functional electronic device materials. This is a contributing manufacturing method.

It is the figure which showed the result of having measured the current-voltage characteristic under light irradiation of the solar cell produced in Example 8. FIG. It is the figure which showed the result of having measured the output characteristic of the organic transistor element produced in Example 12. FIG.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

In the following examples and comparative examples, ¹ H-NMR was measured as follows.
^<1 H-NMR>
The obtained fulvalene compound was measured as a deuterated chloroform solution using a high-resolution nuclear magnetic resonance apparatus (product name “Gemini 2000”; 300 MHz, manufactured by Varian, Inc.). The chemical shift was recorded as 1 / 1,000,000 (ppm; δ scale) on the low magnetic field side from tetramethylsilane, and the hydrogen nucleus (δ0.00) of tetramethylsilane was referred to.

[Fulvalene compound]
Example 1
In a 30 ml Schlenk tube, 2,6′-dibromobiphenyl (156 mg, 0.5 mmol), 2-ethynylbiphenyl (89.1 mg, 0.5 mmol), palladium catalyst (35.1 mg, 0.1 mmol), copper iodide (7 .6 mg, 0.05 mmol) and DBU (380.6 mg, 2.5 mmol) were added to replace with nitrogen, and 3 ml of DMF was added as a solvent. This was heated to 140 ° C. and stirred for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the solvent was distilled off. The product purified by silica gel chromatography (mobile phase: hexane) was further purified by recycle preparative GPC to obtain the desired product (47 mg, 0.14 mmol). This reaction is a reaction of the following formula (10).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDCl ₃ ): δ 7.24-7.29 (m, 8H), 7.36-7.40 (m, 4H), 7.66-7.69 (m, 4H)

Example 2
In a 30 ml Schlenk tube, 2,6′-diiodo-4,4′-dibromobiphenyl (282 mg, 0.5 mmol), 2-ethynylbiphenyl (98.0 mg, 0.55 mmol), palladium catalyst (35.1 mg, 0.1 mmol) ), Copper iodide (7.6 mg, 0.05 mmol) and DBU (380.6 mg, 2.5 mmol) were added, and the atmosphere was replaced with nitrogen. 3 ml of DMF was added as a solvent. This was heated to 140 ° C. and stirred for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the solvent was distilled off. The product purified by silica gel chromatography (mobile phase: hexane) was further purified by recycle preparative GPC to obtain the desired product (15 mg, 0.03 mmol). This reaction is a reaction of the following formula (11).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDCl3): δ 7.24-7.27 (m, 2H), 7.37 (t, 2H), 7.45-7.47 (m, 2H), 7.56 (d, 2H) 7.69 (d, 2H), 8.28 (d, 2H), 8.49 (d, 2H)

Example 3
In a 30 ml Schlenk tube, 2,6′-diiodobiphenyl (203 mg, 0.5 mmol), 3-ethynyl-2,2′-bithiophene (104.7 mg, 0.55 mmol), palladium catalyst (35.1 mg, 0.1 mmol) ), Copper iodide (7.6 mg, 0.05 mmol) and DBU (380.6 mg, 2.5 mmol) were added, and the atmosphere was replaced with nitrogen. 3 ml of DMF was added as a solvent. This was heated to 140 ° C. and stirred for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the solvent was distilled off. The product purified by silica gel chromatography (mobile phase: hexane) was further purified by recycle preparative GPC to obtain the desired product (12 mg, 0.04 mmol). This reaction is a reaction of the following formula (12).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDCl3): δ 7.08 (m, 2H), 7.24-7.29 (d, 2H), 7.34-7.38 (m, 2H), 7.57 (d, 2H) 7.68-7.70 (m, 2H), 8.28 (d, 2H)

Example 4
In a 50 ml Schlenk tube, 3,3′-dibromobithiophene (324 mg, 1.0 mmol), diboronic acid ester (451.7 mg, 1.1 mmol), palladium catalyst (57.8 mg, 0.05 mmol), potassium carbonate (829. 3 mg, 6.0 mmol), 20 ml of THF and 4 ml of water were added and the atmosphere was replaced with nitrogen. This was heated to 65 ° C. and stirred for 48 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by recycle preparative HPLC (mobile phase: chloroform) to obtain the desired product (177 mg, 0.5 mmol). This reaction is a reaction of the following formula (13).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDC13): δ 7.08 (m, 2H), 7.24-7.29 (d, 2H), 7.34-7.38 (m, 2H), 7.57 (d, 2H) 7.68-7.70 (m, 2H), 8.28 (d, 2H)

Example 5
In a 30 ml Schlenk tube, tetrabromide (246.9 mg, 0.2 mmol), diboronic acid ester (213.2 mg, 0.5 mmol), palladium catalyst (28.9 mg, 0.03 mmol), potassium carbonate (414.6 mg, 3. 0 mmol), 10 ml of THF and 2 ml of water were added, and the atmosphere was replaced with nitrogen. This was heated to 60 ° C. and stirred for 48 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 5/1) to obtain the desired product (209 mg, 0.43 mmol). This reaction is a reaction of the following formula (14).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDC13): δ 7.24-7.27 (m, 2H), 7.37 (t, 2H), 7.45-7.47 (m, 2H), 7.56 (d, 2H) 7.69 (d, 2H), 8.28 (d, 2H), 8.49 (d, 2H)

Example 6
In a 30 ml Schlenk tube, dibromide (67.2 mg, 0.2 mmol), diboronic acid ester (89.3 mg, 0.22 mmol), palladium catalyst (11.6 mg, 0.01 mmol), potassium carbonate (165.9 mg, 1.2 mmol) ), THF (4 ml) and water (1 ml) were added, and the atmosphere was replaced with nitrogen. This was heated to 60 ° C. and stirred for 48 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (mobile phase: hexane) to obtain the desired product (59.1 mg, 0.18 mmol). This reaction is a reaction of the following formula (15).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDC13): δ 7.24-7.29 (m, 8H), 7.36-7.40 (m, 4H), 7.66-7.69 (m, 4H)

Example 7
Dibromide (167.0 mg, 0.35 mmol), boronic acid (104.7 mg, 0.71 mmol), palladium catalyst (17.6 mg, 0.03 mmol), sodium hydroxide (82.8 mg, 2.1 mmol) in a 30 ml Schlenk tube ), THF (10 ml) and water (2 ml) were added, and the atmosphere was replaced with nitrogen. This was heated to 70 ° C. and stirred for 12 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (mobile phase: chloroform), and the solvent was distilled off. The obtained solid was collected by filtration, washed with methanol, and dried to obtain the desired product (150.0 mg, 0.28 mmol). This reaction is a reaction of the following formula (16).
The physical properties of the obtained fulvalene compound are as follows.
1H-NMR (CDC13): δ 7.03-7.14 (m, 4H), 7.24-7.29 (m, 4H), 7.33-7.40 (m, 6H), 7.49- 7.53 (m, 6H), 7.69 (d, 2H), 7.76 (d, 2H), 8.46 (d, 2H), 8.57 (s, 2H)

[Solar cell]
Example 8
Organic thin-film solar cells were produced by the following steps [1] to [5].
[1] A commercially available transparent glass substrate with ITO having a patterned sheet resistance of 14 Ωm was prepared.
[2] This transparent glass substrate with ITO was subjected to ultrasonic cleaning for 10 minutes in the order of acetone and isopropanol. Thereafter, boiling washing with isopropanol was performed. As the next cleaning step, oxygen plasma treatment was performed under conditions of current 10 mA and 5 minutes. Specifically, using VPS020 manufactured by Sanyu Denshi, the treatment was performed after purging with oxygen 2-3 times.
[3] A film of PEDOT (polyethylenedioxythiophene), which is a polythiophene derivative, and PSS (polystyrene sulfonic acid) was formed as a hole transport material on the plasma-treated transparent electrode by spin coating. The conditions were a slope of 1 second 800 revolutions 180 seconds and a film thickness of 500 angstroms. This was formed into a film by baking at 200 ° C. for 10 minutes to form a hole transport layer.
[4] Next, the fulvalene compound obtained in Example 4 and P3HT (poly (3-hexylthiophene)) were mixed at a weight ratio of 3: 2 to prepare a 2.0 mass% dichlorobenzene solution. It was applied onto the hole transport layer by spin coating (1500 rpm / 180 seconds) and then dried. The drying condition of the liquid material was room temperature in the atmosphere. Thereby, a light emitting layer was obtained.
[5] Aluminum (Al) was vapor-deposited on the light-emitting layer with an average thickness of 150 nm using a vacuum vapor deposition apparatus to produce a cathode.
When the current-voltage characteristics under light irradiation were measured for the thus obtained device, a current-voltage curve as shown in FIG. 1 was obtained, and it was found that a photovoltaic force was obtained.
The open-circuit voltage was 0.51307 V, the short-circuit photocurrent was 0.27479 mA / cm ² , the fill factor was 43.82%, and the power generation efficiency was 0.0618%. Therefore, the device may exhibit solar cell performance. I understood.

[Organic transistor]
In producing the organic transistor, a fulvalene compound was newly synthesized according to Examples 9 to 11 below.
Example 9
The fulvalene compound synthesized in Example 3 (811 mg, 2.4 mmol), chloroform (12 ml) and acetic acid (3.5 ml) were added to a 50 ml Schlenk tube, and the atmosphere was replaced with nitrogen. This was stirred at room temperature for 3 minutes. N-bromosuccinimide (890 mg, 5.0 mmol) was added here, and it stirred at 60 degreeC overnight. The mixture was returned to room temperature, water was added, and the mixture was extracted with chloroform. The organic layer was dried over sodium sulfate s and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (solvent: chloroform / hexane = 1/10) to obtain the desired dibromofulvalene compound (997 mg, 2.0 mmol). This reaction is a reaction of the following formula (17).
The physical property values of the obtained dibromofulvalene compound are as follows.
¹ H-NMR (CDC1 ₃ ): δ 7.27-7.31 (m, 2H), 7.36-7.39 (m, 2H), 7.55 (s, 2H), 7.67 (d, 2H), 8.14 (d, 2H)

Example 10
The dibromofulvalene compound (548 mg, 1.1 mmol), phenylboronic acid (275 mg, 2.3 mmol) synthesized in Example 9 in a 30 ml Schlenk tube, palladium catalyst (56 mg, 0.11 mmol), sodium hydroxide (264 mg, 6 .6 mmol), 10 ml of THF and 10 ml of water were added, and the atmosphere was replaced with nitrogen. This was heated to 70 ° C. and stirred for 20 hours. After completion of the reaction, water was added and extracted three times with chloroform. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain the desired product (463 mg, 0.94 mmol). This reaction is a reaction of the following formula (18).
The physical properties of the obtained fulvalene compound are as follows.
¹ H-NMR (CDC1 ₃ ): δ 7.29-7.33 (m, 4H), 7.37-7.41 (m, 6H), 7.57-7.59 (m, 4H), 7. 71-7.73 (m, 2H), 7.82 (s, 2H), 8.34 (d, 2H)

Example 11
In a 100 ml Schlenk tube, dibromobiphenyl compound (864 mg, 2.0 mmol), diboronic acid ester (882 mg, 2.1 mmol), palladium catalyst (116 mg, 0.1 mmol), potassium carbonate (1658 mg, 12.0 mmol), THF 20 ml, water 4 ml Was added and replaced with nitrogen. This was heated to 70 ° C. and stirred for 48 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by column silica gel chromatography (solvent: toluene / chloroform = 1/1) to obtain the desired product (628 mg, 1.4 mmol). This reaction is a reaction of the following formula (19).
The physical properties of the obtained fulvalene compound are as follows.
¹ H-NMR (CDC1 ₃ ): δ 7.80 (s, 6H), 4.03 (s, 6H), 7.01 (s, 2H), 7.22-7.24 (m, 2H), 7 .30-7.33 (m, 2H), 7.74 (d, 2H), 7.89 (s, 2H), 8.43 (d, 2H)

Example 12
An organic transistor element was produced by the following steps [1] to [5].
[1] A commercially available Si substrate on which a SiO ₂ film was formed as a gate insulating film was prepared.
[2] The Si substrate with SiO ₂ was subjected to ultrasonic cleaning for 10 minutes in the order of acetone and isopropanol. Thereafter, boiling washing with isopropanol was performed. As the next cleaning step, oxygen plasma treatment was performed under conditions of current 10 mA and 5 minutes. Specifically, using VPS020 manufactured by Sanyu Denshi, the treatment was performed after purging with oxygen 2-3 times.
[3] A self-assembled monolayer was formed on the plasma-treated substrate by exposing it to the vapor of trichlorodecylsilane.
[4] The fulvalene compound obtained in Example 11 was deposited on the monomolecular layer with an average thickness of 100 nm using a vacuum deposition apparatus.
[5] A vapor deposition mask was set on the organic film, and aluminum metal was vapor-deposited as a source electrode and a drain electrode using a vacuum vapor deposition apparatus.
The results of measuring the output characteristics of the organic transistor element thus obtained are shown in FIG.
From FIG. 2, a current was obtained around 40 V applied as the gate voltage, and n-type transistor characteristics were confirmed.
In FIG. 2, V _DS represents the voltage between the source and drain electrodes, V _GS represents the voltage between the gate and drain electrodes, and I _DS represents the current value between the source and drain electrodes.

Claims (11)

A compound having a skeleton derived from fulvalene, wherein the compound has the following formula (1);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Alternatively, differently, a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure may be represented, and a plurality of each may be bonded to a ring structure forming a dotted arc portion. When all the ring structures are benzene rings, X ^{1 to} X ⁴ are not bonded to each other, and all of X ^{1 to} X ⁴ are not the same structure, and X ^{1 to} X ⁴ When a halogen atom is contained, at least one of X ^{1 to} X ⁴ is a monovalent substituent other than a halogen atom, and all four ring structures represented by dotted arcs are benzene rings. , ^X 1, ^{X 3} is the same monovalent substituents a ^{and,, X} 2, X ⁴ If a hydrogen atom or X ^1, X ³ is different from the same monovalent substituent B, or, a four ring structure are all benzene ring represented by the dotted arcs, X ^1, X ⁴ is When the same monovalent substituent A and X ² and X ³ are a hydrogen atom or the same monovalent substituent B different from X ¹ and X ⁴ , the monovalent substituent A is bromine X is a substituent other than an atom, a methoxy group, a carboxyl group, a —CO ₂ CH ₃ group, a —CH ₂ OH group, a —CONHR group (R represents a hydrocarbon group containing a phenyl group in the structure). ¹ and X ² are both bonded to a naphthalene ring, and X ³ and X ⁴ are all bonded to a benzene ring, at least one of X ³ and X ⁴ is It is a monovalent substituent other than a methoxy group, and there is no ring structure to which X ¹ and X ² are bonded. This is also a pyridine ring, and when the ring structure to which X ³ and X ⁴ are bonded is a benzene ring or both are pyridine rings, at least one of X ^{1 to} X ⁴ is monovalent. The four ring structures represented by dotted arcs are all thiophene rings, and the sulfur atom of the thiophene ring to which X ¹ is bonded and the sulfur atom of the thiophene ring to which X ² is bonded Has a structure in which X is bonded through two carbon atoms, and the sulfur atom of the thiophene ring to which X ³ is bonded and the sulfur atom of the thiophene ring to which X ⁴ is bonded are bonded through two carbon atoms. In this case, at least one of X ^{1 to} X ⁴ is formed from a hydrogen atom, a bromine atom, a 2-thiophene group, a 5-bromo-2-thiophene group, one or two thiophene rings and an alkyl group. Monovalent substituents other than groups It is. The fulvalene compound characterized by the above-mentioned. In the formula (1), a structural part constituted by a ring structure to which X ¹ and X ¹ are bonded, a structural part constituted by a ring structure to which X ² and X ² are bonded, and X ³ and X ³ are bonded. And at least one of the three other structural sites is at least one of the four structural sites of the structural site configured by the ring structure to which X ⁴ and X ⁴ are bonded. The fulvalene compound according to claim 1, wherein the fulvalene compound is different from one. The fulvalene compound according to claim 1, wherein at least one of X ^{1 to} X ⁴ in the formula (1) is a substituent having a reactive group. The fulvalene compound according to any one of claims 1 to 3, wherein one to three of the four ring structures represented by a dotted arc in the formula (1) is a thiophene ring. In the fulvalene compound, 1 to 3 of X ^{1 to} X ⁴ in the formula (1) are monovalent substituents containing a carbon-carbon double bond or a triple bond. The fulvalene compound in any one of -4. The fulvalene compound according to any one of claims 1 to 5, wherein the fulvalene compound is used for forming a light emitting device. It forms using the fulvalene compound in any one of Claims 1-6, The light-emitting device characterized by the above-mentioned. A solar cell material comprising a compound having a fulvalene-derived skeleton, wherein the compound is represented by the following formula (1 ′);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Alternatively, differently, a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure may be represented, and a plurality of each may be bonded to a ring structure forming a dotted arc portion. When all of the ring structures are benzene rings, X ^{1 to} X ⁴ are not all the same structure, and when all of the ring structures to which X ^{1 to} X ⁴ are bonded are naphthalene rings, X ¹ to X ⁴ At least one of X ⁴ is a monovalent substituent, the ring structure to which X ¹ and X ² are bonded is a naphthalene ring, and the ring structure to which X ³ and X ⁴ are bonded is If also a benzene ^ring, at least one of X 3, ^{X 4,} main Alkoxy is a monovalent substituent other than group .X ¹ to X ⁴ one of the four ring structures are attached, but one backbone moiety and the backbone portion of the 5-membered ring to form a fulvalene skeleton In the case where each of the four rings is a benzene ring or a naphthalene ring, at least one of X ^{1 to} X ⁴ is 1 other than a methoxy group or a 2-ethylheptoxy group. Or a fulvalene compound represented by the formula: X ^{1 to} X ⁴ are all hydrogen atoms. An organic transistor material comprising a compound having a fulvalene-derived skeleton, wherein the compound is represented by the following formula (1 ″);

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure, and a plurality of them may be bonded to the ring structure forming the dotted arc portion). A material for an organic transistor, characterized in that: Formula (1 '') below;

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or differently, a hydrogen atom or a monovalent substituent which is a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part). A method of manufacturing comprising:
The production method comprises the following formula (2):

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ¹ and X ² are the same or different and represent a hydrogen atom or A monovalent substituent serving as a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part, and Y represents a hydrogen atom or a monovalent substituent. An unsaturated bond-containing compound (I) represented by the following formula (3);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ³ and X ⁴ are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ¹ and R ² may be bonded to the ring structure forming the dotted arc portion. A process for reacting the unsaturated bond-containing compound (II) represented by the formula (II). Formula (1 '') below;

(In the formula, four dotted arcs are the same or different and represent that a ring structure is formed together with a part of a skeleton portion of a 5-membered ring forming a fulvalene skeleton. X ^{1 to} X ⁴ are the same. Or differently, a hydrogen atom or a monovalent substituent which is a substituent of the ring structure may be bonded to a ring structure forming a dotted arc part). A method of manufacturing comprising:
The production method comprises the following formula (3 ′);

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ³ and X ⁴ are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ¹ ′ and R ² ′ may be the same or different and may be bonded to a ring structure forming a dotted arc portion. An unsaturated bond-containing compound (II ′) represented by the following formula (4):

(In the formula, a dotted arc represents that a ring structure is formed together with two carbon atoms constituting a double bond between carbon atoms. X ¹ and X ² are the same or different and represent a hydrogen atom or Represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of R ³ and R ⁴ may be bonded to the ring structure forming the dotted arc portion. A process for reacting with the unsaturated bond-containing compound (III) represented by the formula (1): a method for producing a fulvalene compound.

Images