JP2015020958A - Compound having dicyclopentadienylidene-cyclohexadiene skeleton, polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having various structures having a new dicyclopentadienylidene-cyclohexadiene skeleton capable of being suitably used as a functional organic material such as an n-type organic semiconductor, and a production method enabling synthesis of the compound, and a polymer having the dicyclopentadienylidene-cyclohexadiene skeleton capable of being suitably used as the functional organic material such as the n-type organic semiconductor.SOLUTION: There are provided a compound having a dicyclopentadienylidene-cyclohexadiene skeleton and a method for producing the same, and a polymer obtained by polymerizing a monomer component containing the compound.

Description

The present invention relates to a compound having a dicyclopentadienylidenecyclohexadiene skeleton, a polymer, and a method for producing the same. More specifically, a compound having a dicyclopentadienylidenecyclohexadiene skeleton, a polymer, and a production thereof that can be suitably used as a functional electronic element material such as an organic semiconductor material used for an organic thin film solar cell or an organic transistor Regarding the method.

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. Active research and development are being 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 the LUMO energy level is actually lowered. Research examples and development examples of compounds having such a fluorenylidene structure have been reported (for example, see Non-Patent Documents 1 and 2).
By the way, Non-Patent Document 3 discloses a radical battery that does not physically move ions but moves electrons in a stable radical organic material. Non-Patent Document 4 discloses a biradical compound as Compound 1 in Scheme 1, and discloses its oxidation-reduction mode. There is a possibility that such a compound can be applied to a battery as disclosed in Non-Patent Document 3.
In addition, radical organic compounds are disclosed (see, for example, Non-Patent Documents 5 and 6).

Brian Halton, “Tetrahedron Letters”, 2006, 47, p. 1077-1079 J. et al. One outside of J. Castaner, “Journal of Organic Chemistry”, 1991, Vol. 56, p. 5445-5448 One person from Hiroyuki Nishiide, “The Electrochemical Society Winter 2005”, p. 32-36 Eight people outside Takashi Kubo, “Angevante Chemie International Edition”, 2004, No. 43, p. 6474-6479 Nine Takashi Kubo, “Organic Letters”, 2007, Vol. 9, No. 1, p. 81-84 Ten people outside Takashi Kubo, “Angevante Chemie International Edition”, 2005, No. 44, p. 6564-6568

As described above, organic compounds having a fluorenylidene structure have been reported. For example, increasing variations of organic compounds that are suitably used in applications such as electronic device materials such as organic semiconductor materials can be used in various applications. Since the range of selection in the case of using the organic compound for the purpose is expanded, there is a great technical significance. For this reason, the further development of the compound suitable for an electronic device material use is calculated | required. In addition, it is preferable that an organic semiconductor material that can form a semiconductor layer by coating is easier to manufacture the semiconductor. For this reason, development of the polymer which has the characteristic as an electronic device material is also calculated | required.
In addition, the method for producing a compound having a fluorenylidene structure disclosed in the above non-patent document is obtained by reacting under severe conditions such as very high temperature and high vacuum. There is a need for a method that can produce a compound having a fluorenylidene structure. Furthermore, the radical organic compound described in Non-Patent Document 4 is considered to be stable even when ions are taken in and out to form an ion, and can be stored. The battery disclosed in Non-Patent Document 3 By using a radical organic compound, noble metals need not be used, and charging and discharging are possible at high speed. For this reason, if the compound used for an electronic device material use is a compound which has radical property, the use which can use the said compound can further be expanded, and it is preferable.

This invention is made | formed in view of the said present condition, and synthesize | combines easily the organic compound and polymer which can be used suitably as functional organic materials, such as an n-type organic semiconductor, and this organic compound. It aims at providing the manufacturing method which enables.

This inventor examined the compound which can be used suitably as functional organic materials, such as an n-type organic semiconductor, and its simple manufacturing method. As a result, the present inventor has developed organic compounds having various structures having a dicyclopentadienylidenecyclohexadiene skeleton, and this compound has a low LUMO energy level, and is an organic semiconductor material, particularly an organic thin film solar cell material. The present inventors have found that it can be suitably used as an organic transistor material, an actuator material, or the like.
Furthermore, among compounds having a dicyclopentadienylidenecyclohexadiene skeleton, compounds in which an aromatic ring such as a benzene ring is condensed on the dicyclopentadienylidenecyclohexadiene skeleton must be present stably in a radical state. I found out that I can. Since this compound has a high dielectric constant, for example, excitons can be easily separated into a positive charge and a negative charge, so that it can be suitably applied to an organic thin film solar cell, and is more suitable as an electronic device material. In addition, when this compound is used as a battery (electrode) material, it is considered that charge and discharge can be performed by movement of electrons, which is faster than a lithium ion battery in which lithium ions move with charge and discharge. It is also expected as a material that enables the manufacture of batteries that can be charged and discharged.

The inventor obtains a compound having a dicyclopentadienylidenecyclohexadiene skeleton by a coupling reaction between a ring structure-containing compound having a conjugated diene structure in the basic skeleton and a compound having a conjugated diene structure in the basic skeleton. A new manufacturing method was developed. The conventional method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton requires very severe conditions such as high temperature and high vacuum described in Non-Patent Document 1 above. According to the method, it is possible to produce a compound having a cyclopentadienylidenecyclohexadiene skeleton under milder conditions and with a smaller number of steps. In addition, according to the method of the present invention, various cyclic structures of dicyclopenta can be obtained by changing the ring structure condensed to the basic skeleton of the starting compound and the substituents bonded to the ring structure or the basic skeleton to various ones. A compound having a dienylidenecyclohexadiene skeleton can be synthesized.

The inventor then produced a compound having a dicyclopentadienylidenecyclohexadiene skeleton having a reactive group by the production method of the present invention, and using the compound, dicyclopentadienylidene was produced. The inventors have also found that a polymer having a structural unit derived from a compound having a cyclohexadiene skeleton as a repeating unit can be produced, and have conceived that the above problems can be solved brilliantly, and have reached the present invention.

That is, the present invention is a compound having a cyclic structure having an unsaturated bond, wherein the compound is represented by the following formula (1);

(In the formula, the six dotted arcs may form a ring structure together with a part of the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, and the ring structure X ^{1 to} X ⁶ are the same or different and each represents a hydrogen atom or a monovalent substituent, and each of X ^{1 to} X ^{6 is} dicyclopentadienylidenecyclohexane. When the dotted arc between the 5-membered ring or 6-membered ring skeleton constituting the hexadiene skeleton forms a ring structure together with a part of the 5-membered ring or skeleton of the 6-membered ring, the ring A plurality of bonds may be bonded to the ring structure, and a dotted arc between the five-membered or six-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton When the ring structure is not formed, 5-membered ring or a part of the skeleton portion of the 6-membered ring, the dotted arc is bound to become part of carbon atoms of the ring structure when to form a ring structure .X ¹ and X ² And the dotted dotted arc between the 6-membered skeleton part constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the 6-membered skeleton part form a naphthalene ring, and X ³ to When four dotted arcs between X ⁶ and the five-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the five-membered skeleton form a benzene ring X ^{1 to} X ⁶ each represents a monovalent substituent, and ^{two of} X ¹ and X ² and the skeleton part of the 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton All dotted arcs are ring structures Not formed, X ³ to X ⁶ and dicyclopentadiene Eni part of the four arcs skeletal portion of both the 5-membered ring of the dotted line between the 5-membered skeleton portion of the ring constituting the dibenzylidene cyclohexadiene skeleton Together with a benzene ring, and when X ^{1 to} X ⁶ contain a chlorine atom, at least one of X ^{1 to} X ⁶ is a hydrogen atom or a monovalent substituent other than a chlorine atom. It is a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by: The above-mentioned “carbon atom that is a part of the skeleton part of the 5-membered ring or the 6-membered ring and that is a part of the ring structure when a dotted arc forms the ring structure” is a dotted line Refers to the carbon atoms located at both ends of the arc. The same applies to the following.

The present invention is also a polymer having a cyclic structure having an unsaturated bond, the polymer polymerizing a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton and a reactive group. The compound having a dicyclopentadienylidenecyclohexadiene skeleton and a reactive group obtained by the following formula (2);

(In the formula, the six dotted arcs may form a ring structure together with a part of the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, and the ring structure X ^{7 to} X ¹² are the same or different and each represents a hydrogen atom or a monovalent substituent, and at least one of X ^{7 to} X ¹² is a reactive group. For each of X ^{7 to} X ¹² , a dotted arc between the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton is the 5-membered ring or When a ring structure is formed together with a part of the skeleton of the 6-membered ring, it may be bonded to the ring structure, and a plurality of each may be bonded to the ring structure: dicyclopentadienylidenecyclohexadiene 5 members constituting the skeleton Alternatively, when a dotted arc between the skeleton part of the 6-membered ring does not form the ring structure, the arc of the dotted line is a part of the skeleton part of the 5-membered ring or the 6-membered ring. And a polymer that is bonded to a carbon atom that becomes a part of the ring structure when the structure is formed.

The present invention is also a solar cell material including a polymer obtained by polymerizing a compound having a dicyclopentadienylidenecyclohexadiene skeleton or a monomer component containing the compound having the skeleton and a reactive group. is there.
This invention is also a solar cell element produced using the solar cell material of this invention.

The present invention also provides a material for an organic transistor comprising a polymer obtained by polymerizing a compound having a dicyclopentadienylidenecyclohexadiene skeleton or a monomer component containing a compound having the skeleton and a reactive group. is there.
The present invention is also an organic transistor element produced using the organic transistor material of the present invention.

The present invention further relates to a method for producing a compound having a cyclic structure having an unsaturated bond, wherein the production method comprises the following formula (i):

(In the formula, two dotted arcs indicate that a ring structure may be formed together with a part of the skeleton of a 6-membered ring, and the ring structure may not be formed. X ¹ , X ² are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ¹ and X ² , a dotted arc between the 6-membered ring skeleton part is one of the 6-membered skeleton parts. In the case of forming a ring structure together with a portion, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. If no form is part of the backbone portion of the 6-membered ring, the dotted arc is bound to become part of carbon atoms of the ring structure when to form a ring structure .R ¹ to R ⁴ are the same or different, monovalent represents a substituent.) unsaturated bond-containing compound represented by the (I), the following (Ii);

(In the formula, a dotted arc represents that a ring structure may be formed together with carbon atoms bonded to each other by a double bond, and the ring structure may not be formed. X ³ , X ⁴ Are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ³ and X ⁴ , a dotted circular arc between carbon atoms bonded to each other by a double bond is In the case of forming a ring structure with bonded carbon atoms, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. In the case where the dotted arc does not form the ring structure, it is bonded to the carbon atoms bonded to each other by the double bond, and R ⁵ and R ⁶ are the same or different and different from R ^{1 to} R ^4. An unsaturated bond-containing compound represented by (II represents a monovalent substituent) When the following formula (iii);

(In the formula, a dotted arc represents that a ring structure may be formed together with carbon atoms bonded to each other by a double bond, or the ring structure may not be formed. X ⁵ , X ⁶ Are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ⁵ and X ⁶ , a dotted circular arc between carbon atoms bonded to each other by a double bond is In the case of forming a ring structure with bonded carbon atoms, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. In the case where the dotted arc does not form the ring structure, it is bonded to the carbon atoms bonded to each other by the double bond, R ⁷ and R ⁸ are the same or different and different from R ^{1 to} R ^4. An unsaturated bond-containing compound represented by (II represents a monovalent substituent) ) And comprises a step of reacting, the manufacturing method is also a process for the preparation of a compound having a di cyclopentadienylidene cyclohexadiene skeleton is intended to obtain a compound having a di cyclopentadienylidene cyclohexadiene skeleton.

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.

In the following, the compound having the dicyclopentadienylidenecyclohexadiene skeleton of the present invention, the polymer of the present invention, the use of the compound having the dicyclopentadienylidenecyclohexadiene skeleton of the present invention and the polymer, The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton and a polymer will be described in this order.

[Compound having dicyclopentadienylidenecyclohexadiene skeleton]
The compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention has the following formula (1);

(In the formula, the six dotted arcs may form a ring structure together with a part of the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, and the ring structure X ^{1 to} X ⁶ are the same or different and each represents a hydrogen atom or a monovalent substituent, and each of X ^{1 to} X ^{6 is} dicyclopentadienylidenecyclohexane. When the dotted arc between the 5-membered ring or 6-membered ring skeleton constituting the hexadiene skeleton forms a ring structure together with a part of the 5-membered ring or skeleton of the 6-membered ring, the ring A plurality of bonds may be bonded to the ring structure, and a dotted arc between the five-membered or six-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton When the ring structure is not formed, 5-membered ring or a part of the skeleton portion of the 6-membered ring, the dotted arc is bound to become part of carbon atoms of the ring structure when to form a ring structure .X ¹ and X ² And the dotted dotted arc between the 6-membered skeleton part constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the 6-membered skeleton part form a naphthalene ring, and X ³ to When four dotted arcs between X ⁶ and the five-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the five-membered skeleton form a benzene ring X ^{1 to} X ⁶ each represents a monovalent substituent, and ^{two of} X ¹ and X ² and the skeleton part of the 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton All dotted arcs are ring structures Not formed, X ³ to X ⁶ and dicyclopentadiene Eni part of the four arcs skeletal portion of both the 5-membered ring of the dotted line between the 5-membered skeleton portion of the ring constituting the dibenzylidene cyclohexadiene skeleton Together with a benzene ring, and when X ^{1 to} X ⁶ contain a chlorine atom, at least one of X ^{1 to} X ⁶ is a hydrogen atom or a monovalent substituent other than a chlorine atom. It has a structure represented by.

In the formula (1), X ^{1 to} X ⁶ are the same or different and each represents a hydrogen atom or a monovalent substituent, and each of X ^{1 to} X ⁶ constitutes a dicyclopentadienylidenecyclohexadiene skeleton. The dotted arc between the 5-membered ring or 6-membered skeleton (hereinafter also referred to as “the skeleton of the compound of the present invention”) represents the 5-membered ring or the 6-membered skeleton. When a ring structure is formed together with a part, it may be bonded to the ring structure and a plurality of each may be bonded to the ring structure.
This is because, in the above formula (1), for each of X ^{1 to} X ⁶ , when the arc portion of the dotted line connected by a line forms a ring structure, the arc of the dotted line among X ^{1 to} X ⁶ What is connected to means that it is bonded to an atom constituting the ring structure. For example, in the above formula (1), when the arc of the dotted line connected to X ⁵ by a line forms a benzene ring together with a part of the skeleton of the compound of the present invention, X ⁵ is a carbon atom constituting the benzene ring. Will be bound to.
In the above formula (1), when the dotted arc between the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton does not form the ring structure, X ¹ to X ⁶ is a part of the 5-membered ring or a part of the skeleton of the 6-membered ring, and is bonded to a carbon atom that becomes a part of the ring structure when a dotted arc forms the ring structure.
As described above, “a carbon atom that is a part of the skeleton portion of the 5-membered ring or the 6-membered ring and that is a part of the ring structure when a dotted arc forms the ring structure” Carbon atoms located at both ends of the dotted arc.
That is, when the arc portion of the dotted line does not form a ring structure, X ^{1 to} X ⁶ are carbon atoms of the skeleton portion of the compound of the present invention, and X ^{1 to} X ⁶ are each connected by a line It is directly bonded to carbon atoms located at both ends of the arc. For example, if X ⁵ in the above formula (1) binds directly to a carbon atom of the backbone moiety of the compound of the present invention, X ⁵ is a carbon atom of the backbone moiety of the compound of the present invention, in X ⁵ and lines They are directly bonded to the carbon atoms located at both ends of the dotted dotted arc.

At least one of the six dotted arcs in the above formula (1) forms a ring structure together with a part of the skeleton portion of the 5-membered ring or 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. Preferably it is. More preferably, a ring structure having aromaticity is formed together with a part of the skeleton portion of the 5-membered ring or 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. The arc of the dotted line forms a ring structure having aromaticity together with a part of the skeleton portion of the 5-membered ring or 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton, so that the dicyclopenta of the present invention is formed. A compound having a dienylidenecyclohexadiene skeleton can exist more stably in a radical state.

The compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention comprises X ³ , X ⁴ and the dicyclopentadienylidenecyclohexadiene skeleton among the six dotted arcs in the above formula (1). More preferably, at least one of the two dotted arcs between the member rings is a ring structure having aromaticity. Particularly preferably, the two dotted arcs are both ring structures having aromaticity.
When the two dotted arcs between X ³ and X ⁴ and the 5-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton are both aromatic ring structures, they are represented by the above formula (1). The compound having a dicyclopentadienylidenecyclohexadiene skeleton is represented by the following formula (3):

In the above, a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1) is partially a compound that can exist stably in a state where the carbon atom marked with * is a radical. Exists in a radical state. When the two dotted arcs between X ³ and X ⁴ and the five-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton are both aromatic structures, the above formula ( The compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by 1) is a compound having a structure in which three aromatic rings are bonded to a carbon atom marked with *, and the generated radical is steric. This is thought to be for the purpose of receiving a special protection. Such a structure is considered to be a factor that the carbon marked with * can exist as a radical in a particularly stable manner.

The same applies to the two dotted arcs between X ⁵ and X ⁶ and the 5-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. That is, the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention includes X ^{3 to} X ⁶ in the above formula (1) and a skeleton part of a 5-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. It is preferable that the four dotted arcs between each form an aromatic ring structure together with a part of the five-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton. Two dotted arcs between X ³ and X ⁴ and the 5-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton, and X ⁵ and X ⁶ constitute the dicyclopentadienylidene cyclohexadiene skeleton When the two dotted arcs between the five-membered rings are all ring structures having aromaticity, a compound in which two carbon radicals exist stably in the structure is obtained. That is, the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1) exists in a state as shown in the following formula (4).

Further, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention, X ¹ and X ² in the above formula (1) and the skeleton portion of the 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton At least one of the two dotted arcs in between preferably forms a ring structure together with a part of the six-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton. More preferably, both of the two dotted arcs between X ¹ , X ² and the 6-membered ring skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are dicyclopentadienylidenecyclohexadiene skeleton. Forming a ring structure together with a part of the skeleton part of the 6-membered ring constituting

The ring structure formed together with a part of the 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton is preferably a ring structure having aromaticity. When a ring structure having aromaticity is formed together with a part of the skeleton portion of the 6-membered ring, the conjugated system in the compound having a dicyclopentadienylidenecyclohexadiene skeleton becomes long, and the dicyclopentadi of the present invention It becomes possible for the compound having an arylidenecyclohexadiene skeleton to exist more stably in a radical state. Particularly preferably, both of the two dotted arcs between X ¹ and X ² in the formula (1) and the six-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are dicyclopenta It is to form a ring structure having aromaticity together with a part of the skeleton portion of the 6-membered ring constituting the dienylidenecyclohexadiene skeleton. In other words, the two dotted arcs between X ¹ and X ² in the above formula (1) and the six-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are respectively dicyclopentadieny. It is preferable to form a ring structure having aromaticity together with a part of the skeleton portion of the 6-membered ring constituting the redenecyclohexadiene skeleton.

In the above formula (1), X ^{1 to} X ⁶ are the same or different and each represents a hydrogen atom or a monovalent substituent.
In the case where the dotted arcs form the ring structure, a plurality of X ^{1 to} X ⁶ may be bonded to the part formed by the dotted arc part of the ring structure. That is, when X ¹ is a hydrogen atom, the ring structure having X ¹ has no substituent. Similarly, when X ^{2 to} X ⁶ are hydrogen atoms, the ring structure having each of X ^{2 to} X ⁶ does not have a substituent.
X ^{1 to} X ⁶ are a part of the carbon 5-membered ring or 6-membered ring skeleton that forms the dicyclopentadienylidenecyclohexadiene skeleton when the dotted arc does not form the ring structure. When a dotted arc forms the ring structure, it is bonded to a carbon atom that becomes a part of the ring structure. That is, when X ¹ is a hydrogen atom, the carbon atom having X ¹ does not have a substituent. Similarly, when X ^{2 to} X ⁶ are hydrogen atoms, the carbon atom having each of X ^{2 to} X ⁶ 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 addition, any one of X ^{1 to} X ⁶ is a monovalent substituent and a plurality of X ^{1 to} X ⁶ may be bonded to each other, but it is preferable that the same substituent is bonded to each other.

The compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1) is one in which any one of X ^{1 to} X ⁶ is a monovalent substituent and the remaining 5 are hydrogen atoms, Any two of X ^{1 to} X ⁶ are monovalent substituents, the remaining four are hydrogen atoms, all of X ^{1 to} X ⁶ are hydrogen atoms, and all of X ^{1 to} X ⁶ are 1 Each of the valent substituents is preferred. More preferably, any two of X ^{1 to} X ⁶ are monovalent substituents, the remaining four are hydrogen atoms, and all of X ^{1 to} X ⁶ are monovalent substituents. is there.

When X ^{1 to} X ⁶ are monovalent substituents, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl chloride group, methyl bromide group and methyl iodide group Haloalkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. 1 -4 linear or branched alkyl groups; C5-C7 cyclic alkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, Carbon such as isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group 1-8 linear or branched alkoxy groups; hydroxyl group; thiol group; epoxy group; nitro group; azo group; allyl group; cyano group; amino group; methylamino group, ethylamino group, dimethylamino group, Mono- or dialkylamino groups having 1 to 4 carbon atoms such as diethylamino 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, allyl group, butenyl group, styryl group and other alkenyl groups having 2 to 8 carbon atoms; ethynyl group, 1-propynyl group, propargyl group, phenylacetylinyl and other alkynyl groups having 2 to 8 carbon atoms; vinyloxy group, allyloxy Alkenyloxy groups such as alkynyloxy 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. In the present specification, a boryl group is represented by (RO) ₂ B— (Rs are the same or different and each represents a hydrogen atom or a hydrocarbon group, and two Rs may be bonded to each other). Say the group. The same applies to the following.

X ^{1 to} X ⁶ are preferably a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom among the above substituents; a methyl chloride group, a methyl bromide group and 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, 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. A reactive group of 1 to 4 carbon atoms Or 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 reaction A linear or branched alkoxy group having 1 to 8 carbon atoms substituted with a reactive group; an aryl group or an aryl group substituted with the reactive group; an oligoaryl group or an oligoaryl 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 substituted with the reactive group ; Alkynyl group substituted with an alkynyl group or the reactive group. 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 compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention, when X ^{1 to} X ⁶ are monovalent substituents, the bond position and the number of bonds of the monovalent substituent to the ring structure are as follows: There is no particular limitation. In this case, it is sufficient that at least one monovalent substituent is bonded to the ring structure, and there may be an atom to which the monovalent substituent is not bonded. Usually, a hydrogen atom is bonded to an unbonded atom.

Moreover, it is also one of the preferred embodiments of the present invention that at least one of X ^{1 to} X ⁶ in the formula (1) is a substituent having a reactive group. Thereby, the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention is suitable as a raw material for the polymer. When at least one of the X ^{1 to} X ⁶ is a substituent having a reactive group among those described above, such a substituent includes 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 (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 A substituted alkynyl group is 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 A substituted monovalent heterocyclic group, a monovalent oligoheterocyclic group substituted with the reactive group, an alkenyl group or an alkenyl group substituted with the reactive group, an alkynyl group or the reactive group A substituted 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 or an alkenyl group substituted with the reactive group, or an alkynyl group or substituted with the reactive group Alkynyl group.

In the case where at least one of X ^{1 to} X ⁶ 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 ⁶ alone. Or (ii) at least two of X ^{1 to} X ⁶ as a substituent having a reactive group, and a combination of at least two reactive groups reacting with one kind of dicyclo Either a compound having a pentadienylidenecyclohexadiene skeleton can be polycondensed alone, or (iii) contains two or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by formula (1) The compound having a dicyclopentadienylidenecyclohexadiene skeleton has a combination of reactive groups that can be copolymerized, or ( v) Reaction in which one or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (1) can be copolymerized with another compound having at least one reactive group By making it have the combination of a sex group, it can use suitably as a raw material of a polymer.
In the above (iii) and (iv), the copolymerization includes polycondensation. That is, (iii) includes two or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (1), and these compounds having a dicyclopentadienylidenecyclohexadiene skeleton are heavy. Those having a combination of reactive groups that can be condensed are included, and (iv) includes one or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (1) And those having a combination of reactive groups capable of polycondensation with other compounds having at least one reactive group.
Among these, the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention is independent or other than the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (1). Those having a substituent capable of polycondensation with one or more monomers are preferred.
A polymer obtained from such a compound having a dicyclopentadienylidenecyclohexadiene skeleton 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 the part of the 5-membered ring or 6-membered skeleton part forming the dicyclopentadienylidenecyclohexadiene skeleton may be a cyclic structure. For example, benzene ring, 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 ring, isoindole ring, quinoline ring, isoquinoline ring and phenanthridine ring, which are represented by the following formulas (6-1) to (6-22), respectively. The Further, formulas (7-1), (7-2), (7-4), (7-5), (7-7), (7-9), (7-13), (7-) 19) and a ring structure containing a 5-membered or 6-membered skeleton that forms a dicyclopentadienylidenecyclohexadiene skeleton, such as (7-20). Among these, aromatic groups are preferable as described above, and for example, a benzene ring, a naphthalene ring, a thiophene ring, and a pyridine ring are more preferable.

The compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention has a structure represented by the above formula (1), but X ¹ and X ² and dicyclopentadienylidenecyclohexadiene skeleton are Two dotted arcs between the constituting 6-membered ring skeleton and a part of the 6-membered skeleton form a naphthalene ring, respectively, and X ^{3 to} X ⁶ and dicyclopentadienylidenecyclohexadiene When four dotted arcs between the skeleton and the five-membered skeleton constituting the skeleton each form a benzene ring together with a part of the five-membered skeleton, X ^{1 to} X ⁶ are at least 1 One represents a monovalent substituent. That is, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1), the ring structure to which X ¹ and X ² are bonded is a naphthalene ring, and X ^{3 to} X ⁶ When all the ring structures to which are bonded are benzene rings, at least one of X ^{1 to} X ⁶ is not a hydrogen atom but a monovalent substituent.

In addition, the two dotted arcs between X ¹ and X ² and the 6-membered ring skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton do not form a ring structure, and X ^{3 to} X ⁶ All of the four dotted arcs between the 5-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the 5-membered skeleton form a benzene ring, and X ¹ to when containing the chlorine atom in the X ⁶ is X ¹ to X ⁶ is at least one hydrogen atom, or a monovalent substituent other than a chlorine atom. That is, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1), each of X ¹ and X ² is a 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. A dotted arc between the skeleton and the skeleton does not form a ring structure, but is a part of the skeleton of the six-membered ring, and a dotted arc forms the ring structure. When any of the ring structures to which X ^{3 to} X ⁶ are bonded is a benzene ring, at least one of X ^{1 to} X ⁶ is a hydrogen atom or a monovalent other than a chlorine atom Is a substituent. Incidentally, preferable examples of the monovalent substituent other than a chlorine atom, a preferred examples of the monovalent substituent when X ¹ to X ⁶ described above is a monovalent substituent, but excluding a chlorine atom is there.

Furthermore, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1), 1 to 5 of X ^{1 to} X ⁶ in the formula (1) are carbon-carbon double bonds or A monovalent substituent containing a triple bond is preferred. That is, at least one of X ^{1 to} X ⁶ in the formula (1) is a monovalent substituent containing a carbon-carbon double bond or triple bond, but all of X ^{1 to} X ⁶ are carbon-carbon. A monovalent substituent containing a double bond or triple bond between them, and a monovalent substituent containing a hydrogen atom or a carbon-carbon double bond or triple bond in X ^{1 to} X ⁶ A compound having a dicyclopentadienylidenecyclohexadiene skeleton containing at least one monovalent substituent that is not a substituent is preferable.
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-described X ^{1 to} X ⁶ 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 compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (1), at least one of X ^{1 to} X ^{6 is} a monovalent substituent containing a carbon-carbon double bond or triple bond In this case, the substituent that is not a monovalent substituent containing a carbon-carbon double bond or triple bond is a monovalent substitution when X ^{1 to} X ⁶ described above are monovalent substituents. Among those preferable as the group, those not containing a carbon-carbon double bond or triple bond are preferable.

In the above formula (1), the ring structure formed by the dotted arc and a part of the 5-membered ring or 6-membered skeleton part forming the dicyclopentadienylidenecyclohexadiene skeleton includes a benzene ring, A naphthalene ring, a thiophene ring, a pyridine ring, or a benzothiophene ring is preferred.

It is preferable that an even number among the six dotted arcs in the above formula (1) forms a thiophene ring together with a part of the 5-membered ring or 6-membered skeleton part constituting the dicyclopentadienylidenecyclohexadiene skeleton. . More preferably, two or four of the six dotted arcs form a thiophene ring together with a part of the skeleton. Among them, two dotted arcs between X ¹ and X ² in the above formula (1) and the 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are respectively dicyclopentadienylidene. A thiophene ring is formed together with a part of a skeleton portion of a 6-membered ring constituting the cyclohexadiene skeleton, or a 5-membered ring constituting the X ^{3 to} X ⁶ and the dicyclopentadienylidene cyclohexadiene skeleton in the above formula (1) It is preferable that the four dotted arcs between each of the skeleton portions form a thiophene ring together with a part of the 5-membered skeleton portion constituting the dicyclopentadienylidenecyclohexadiene skeleton.

In the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention, when six dotted arcs form a ring structure, the six ring structures are composed of two or three kinds of ring structures, and X ¹ and X ² It is one of the preferred embodiments of the present invention that the ring structures to which X ³ and X ⁴ and X ⁵ and X ⁶ are bonded are the same. 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 ring structure, and the ring structure to which X ³ is bonded and the ring structure to which X ⁴ is bonded are The ring structure to which X ⁵ is bonded and the ring structure to which X ⁶ is bonded are the same ring structure, and the ring structure to which X ¹ and X ² are bonded and X ^{3 to} X ⁶ are A compound having a dicyclopentadienylidenecyclohexadiene skeleton having a ring structure different from the ring structure to be bonded is one of the preferred embodiments of the present invention. At this time, the ring structure to which X ³ and X ⁴ are bonded and the ring structure to which X ⁵ and X ⁶ are bonded may be the same or different.
In the above formula (1), among the six ring structures to which X ^{1 to} X ⁶ are bonded, it is also preferable that five are the same ring structure and only one is a ring structure different from the other five.
In addition, all of the ring structures to which X ^{1 to} X ⁶ are bonded are the same ring structure, and ^{one set} of X ¹ and X ² , X ³ and X ⁴ , or X ⁵ and X ⁶ is the same The other four are preferably hydrogen atoms or the same monovalent substituent, and are different from the one set of substituents.
Further, all of the ring structures to which X ^{1 to} X ⁶ are bonded are the same ring structure, and any one of X ^{1 to} X ⁶ is a monovalent substituent, and the other five are hydrogen atoms. Or any one of X ^{1 to} X ⁶ is the same or different and is a monovalent substituent, and the remaining one is preferably a hydrogen atom.

As described above, the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention is a structural site constituted by the ring structure in which X ¹ and X ¹ are bonded in the above formula (1), X ² and X ^A structural part constituted by a ring structure to which ² is bonded, a structural part constituted by a ring structure to which X ³ and X ³ are bonded, a structural part constituted by a ring structure to which X ⁴ and X ⁴ are bonded, At least one of the six structural parts of the structural part constituted by the ring structure to which X ⁵ and X ⁵ are bonded and the structural part constituted by the ring structure to which X ⁶ and X ⁶ are bonded is the other It is preferably different from at least one of the five structural sites.

It is also preferred that all of the ring structures to which X ^{1 to} X ⁶ are bonded are the same ring structure, and all of X ^{1 to} X ⁶ are hydrogen atoms.

Preferred examples of the compound having a dicyclopentadienylidenecyclohexadiene skeleton according to the present invention include compounds having structures such as the following formulas (7-1) to (7-37).

Since the compound and polymer having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention have a low LUMO energy level, they can be suitably used as a functional organic material such as an n-type semiconductor. However, the LUMO energy level of a compound used for such a use is preferably, for example, 3.0 eV to 5.2 eV. In such a range, when used as a functional organic material such as an n-type semiconductor, 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. Particularly preferably, it is 3.6 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 squares and ultrasonically cleaned in acetone and isopropyl alcohol for 10 minutes, respectively, and then subjected to UV ozone treatment for 20 minutes.
Thereafter, in the case of a compound (monomer), this substrate was fixed to a substrate holder of a vacuum deposition apparatus (manufactured by ULVAC, Inc.) connected to a glove box in an argon atmosphere. A sample to be measured is put in a quartz crucible, and the pressure is reduced to about 1 × 10 ⁻³ Pa.
In the case of a polymer, a sample solution adjusted to a concentration of 0.5 to 2% by weight is dropped on this substrate and spin-coated at a speed of 1000 to 3000 revolutions per minute to obtain a measurement sample.
About the produced measurement sample, an ionization potential is measured using an ultraviolet photoelectron spectrometer (made by Kobelco Research Institute, Inc.), and the measured value is set as the energy level of the highest occupied orbit (HOMO) of the sample.
At the same time, an 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).
B. G. = 1240 / λ (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.

(LUMO energy level) = (HOMO energy level) − (BG) (2)

[Polymer]
The polymer of the present invention is obtained by polymerizing a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton and a dicyclopentadienylidenecyclohexadiene skeleton having a reactive group. The compound having a pentadienylidenecyclohexadiene skeleton and a reactive group is represented by the following formula (2):

(In the formula, the six dotted arcs may form a ring structure together with a part of the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, and the ring structure X ^{7 to} X ¹² are the same or different and each represents a hydrogen atom or a monovalent substituent, and at least one of X ^{7 to} X ¹² is a reactive group. For each of X ^{7 to} X ¹² , a dotted arc between the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton is the 5-membered ring or When a ring structure is formed together with a part of the skeleton of the 6-membered ring, it may be bonded to the ring structure, and a plurality of each may be bonded to the ring structure: dicyclopentadienylidenecyclohexadiene 5 members constituting the skeleton Alternatively, when a dotted arc between the skeleton part of the 6-membered ring does not form the ring structure, the arc of the dotted line is a part of the skeleton part of the 5-membered ring or the 6-membered ring. When the structure is formed, it is bonded to a carbon atom that becomes a part of the ring structure. In the polymer of the present invention, a part of the repeating unit derived from a compound having a dicyclopentadienylidenecyclohexadiene skeleton is present as a radical such as a biradical having no dicyclopentadienylidenecyclohexadiene skeleton. In this way, a part may be a radical.

The compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is a carbon having a dicyclopentadienylidenecyclohexadiene structure as a basic skeleton and forming a dicyclopentadienylidenecyclohexadiene skeleton. In this compound, six ring structures may be formed together with a part of the skeleton of the 5-membered ring or 6-membered ring, and the ring structure may not be formed.

In the above formula (2), X ^{7 to} X ¹² are the same or different and each represents a hydrogen atom or a monovalent substituent.
In the case where the dotted arcs form the ring structure, a plurality of X ^{7 to} X ¹² may be bonded to the part formed by the dotted arc part of the ring structure. That is, when X ⁷ is a hydrogen atom, the ring structure having X ⁷ has no substituent. Similarly, when X ^{8 to} X ¹² are hydrogen atoms, the ring structure having each of X ^{8 to} X ¹² does not have a substituent.
Further, when the dotted arc does not form the above ring structure, it is a part of the carbon 5-membered or 6-membered skeleton that forms the dicyclopentadienylidenecyclohexadiene skeleton, and the dotted arc is When the ring structure is formed, it is bonded to a carbon atom that becomes a part of the ring structure. That is, when X ⁷ is a hydrogen atom, the carbon atom having X ⁷ has no substituent. Similarly, when X ^{8 to} X ¹² are hydrogen atoms, the carbon atom having each of X ^{8 to} X ¹² does not have a substituent.

When X ^{7 to} X ¹² are monovalent substituents, the substituents are the same as the substituents when X ^{1 to} X ⁶ in Formula (1) are monovalent substituents. This also applies to the point that the substituent may be substituted with a reactive group.
In ^the case X 7 ^{to X 12} is a monovalent substituent, the number of binding position and coupling of ^X 7 ^{to X 12} for the ring structure is not particularly ^limited, the number of X 7 ^{to X 12} are each 1 It is preferably ~ 5. More preferably, it is 1-4. In this case, the ring structure may have an atom to which a monovalent substituent is not bonded, and a hydrogen atom is usually bonded to an atom to which the monovalent substituent is not bonded.

In the present invention, at least one of X ^{7 to} X ¹² in the above formula (2) is a substituent having a reactive group. Examples of the substituent having a reactive group include the same groups as those in the case where X ^{1 to} X ⁶ in the above formula (1) are substituents having a reactive group.

The compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is a monovalent substituent in which any one of X ^{7 to} X ¹² has a reactive group, X ⁷ as any two of to X ¹² is a monovalent substituent having a reactive group, respectively although all X ⁷ to X ¹² is a monovalent substituent having a reactive group is preferred. Among them, among X ^{7 to} X ¹² , X ⁷ and X ⁸ are monovalent substituents having a reactive group, and X ⁷ and X ¹⁰ are monovalent substituents having a reactive group , X ⁷ and X ¹² are monovalent substituents having a reactive group, X ⁸ and X ⁹ are monovalent substituents having a reactive group, X ⁸ and X ¹¹ are reactive groups Are monovalent substituents having X, X ⁹ and X ¹⁰ are monovalent substituents having a reactive group, X ⁹ and X ¹² are monovalent substituents having a reactive group , X ¹⁰ and X ¹¹ are monovalent substituents having a reactive group, X ¹¹ and X ¹² are monovalent substituents having a reactive group, and all of X ^{7 to} X ¹² are reacted. Any one of monovalent substituents having a functional group is more preferred. Here, among the X ⁷ to X ^12, it is other than a monovalent substituent having a reactive group, typically a substituent other than a substituent having a hydrogen atom or a reactive group.

Among the monovalent substituents of X ^{7 to} X ¹² , examples of the substituent other than the substituent having a reactive group include a linear or branched alkyl group having 1 to 4 carbon atoms; An aryl group; an oligoaryl group; a monovalent heterocyclic group; a monovalent oligoheterocyclic group; an alkylthio group; an aryloxy group; an arylthio group; an arylalkyl group; An arylalkylthio group is preferred. More preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, an aryl group, an oligoaryl group, represented by the above formula (5). A monovalent heterocyclic group and a monovalent oligoheterocyclic group.

The monomer component used as the raw material of the polymer of the present invention in which at least one of X ^{7 to} X ¹² is a substituent having a reactive group is any of the following.
(I) a main chain of the polymer containing one kind of compound having a dicyclopentadienylidenecyclohexadiene skeleton which is a substituent having a reactive group capable of polymerizing one of X ^{7 to} X ¹² alone Containing no other compounds that form
(Ii) two of X ^{7 to} X ¹² are substituents having a reactive group, and the two reactive groups can react with each other, and one kind of dicyclopentadienylidene Including one compound with dicyclopentadienylidenecyclohexadiene skeleton, which is a combination of reactive groups capable of polycondensation by itself with a compound having cyclohexadiene skeleton, and other compounds that form the main chain of the polymer Nothing.
(Iii) One containing two or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2) and having a combination of reactive groups such that these compounds can be copolymerized.
(Iv) one or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2) and another compound having at least one reactive group, which are copolymerized Having a combination of reactive groups.
In the above (iii) and (iv), the copolymerization includes polycondensation. That is, (iii) includes a combination of reactive groups that include two or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2), and these compounds can polycondense. (Iv) includes one or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2), and other compounds having at least one reactive group. Those having a combination of reactive groups capable of polycondensation with a compound are included.
Among these, the monomer component which is a raw material of the polymer of the present invention includes one or more compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2), and these are A compound having a combination of reactive groups capable of polycondensation or a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2) and at least one reactive group And other compounds having a combination of reactive groups such that they can be polycondensed.

In the above formula (2), the ring structure formed by the dotted arc and a part of the 5-membered ring or 6-membered skeleton part forming the dicyclopentadienylidenecyclohexadiene skeleton is represented by the above formula (1). ), A ring structure similar to that formed by a dotted arc and a part of a 5-membered ring or 6-membered skeleton portion forming a dicyclopentadienylidenecyclohexadiene skeleton can be used. Among these, a benzene ring, a naphthalene ring, a thiophene ring, and a pyridine ring are preferable.

In the above formula (2), the ring structure formed by the dotted arc and a part of the 5-membered ring or 6-membered skeleton part forming the dicyclopentadienylidenecyclohexadiene skeleton is a benzene ring or naphthalene. It is preferably any of a ring, a thiophene ring and a pyridine ring.

It is preferable that an even number among the six dotted arcs in the above formula (2) forms a thiophene ring together with a part of the 5-membered ring or 6-membered skeleton part constituting the dicyclopentadienylidenecyclohexadiene skeleton. . More preferably, two or four of the six dotted arcs form a thiophene ring together with a part of the skeleton. In particular, two dotted arcs between X ⁷ and X ⁸ in the above formula (2) and the 6-membered ring skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are respectively dicyclopentadienylidene. A thiophene ring is formed together with a part of the skeleton portion of the 6-membered ring constituting the cyclohexadiene skeleton, or a 5-membered ring constituting the X ^{9 to} X ¹² in the above formula (2) and the dicyclopentadienylidene cyclohexadiene skeleton It is preferable that the four dotted arcs between each of the skeleton portions form a thiophene ring together with a part of the 5-membered skeleton portion constituting the dicyclopentadienylidenecyclohexadiene skeleton.

In the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2), six ring structures are composed of two or three kinds of ring structures, and X ⁷ and X ⁸ , X ⁹ and X ¹⁰ It is one of the preferred embodiments of the present invention that the ring structures to which X ¹¹ and X ¹² are bonded are the same ring structure. That is, in the above formula (2), the ring structure to which X ⁷ is bonded and the ring structure to which X ⁸ are bonded are the same ring structure, and the ring structure to which X ⁹ is bonded and the ring structure to which X ¹⁰ is bonded are The ring structure to which X ¹¹ is bonded and the ring structure to which X ¹² is bonded are the same ring structure, and the ring structure to which X ⁷ and X ⁸ are bonded and X ^{9 to} X ¹² are A compound having a dicyclopentadienylidenecyclohexadiene skeleton having a ring structure different from the ring structure to be bonded is one of the preferred embodiments of the present invention. At this time, the ring structure to which X ⁹ and X ¹⁰ are bonded and the ring structure to which X ¹¹ and X ¹² are bonded may be the same or different.
In the above formula (2), among the 6 ring structures to which X ^{7 to} X ¹² are bonded, 5 are the same ring structure, and only one is a different cyclostructure than the other 5 dicyclopentadieni. A polymer having a compound having a redenecyclohexadiene skeleton as a monomer component is also one preferred embodiment of the present invention.
Further, all of the ring structures to which X ^{7 to} X ¹² are bonded are the same ring structure, and any one set of X ⁷ and X ⁸ , X ⁹ and X ¹⁰ , or X ¹¹ and X ¹² is the same And the other four are both hydrogen atoms or the same monovalent substituent and are a substituent different from the one set of substituents. A polymer containing a compound having an arylidenecyclohexadiene skeleton as a monomer component is also one preferred embodiment of the present invention.
Furthermore, all of the ring structures to which X ^{7 to} X ¹² are bonded are the same ring structure, and any one of X ^{7 to} X ¹² is a monovalent substituent, and the other five are hydrogen atoms. Or a compound having a dicyclopentadienylidenecyclohexadiene skeleton in which any five of X ^{7 to} X ¹² are the same or different and are monovalent substituents and the remaining one is a hydrogen atom A polymer containing a monomer component is also one preferred embodiment of the present invention.

Thus, in the above formula (2), the polymer of the present invention is constituted by a structural part constituted by a ring structure to which X ⁷ and X ⁷ are bonded, and a ring structure to which X ⁸ and X ⁸ are bonded. A structural part constituted by a ring structure in which X ⁹ and X ⁹ are bonded, a structural part constituted by a ring structure in which X ¹⁰ and X ¹⁰ are bonded, and a ring structure in which X ¹¹ and X ¹¹ are bonded And at least one of the other five structural sites is one of the six structural sites of the structural site configured by X ¹² and the ring structure to which X ¹² is bonded. Are different and are preferably obtained from a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton.

The compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is formed between X ⁷ and X ⁸ and a 6-membered ring skeleton constituting the dicyclopentadienylidene cyclohexadiene skeleton. The two dotted arcs together form a naphthalene ring together with a part of the 6-membered skeleton, and X ^{9 to} X ¹² and a 5-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, When the four dotted arcs between each form a benzene ring together with a part of the skeleton of the 5-membered ring, at least one of X ^{7 to} X ¹² preferably represents a monovalent substituent. . That is, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2), the ring structure to which X ⁷ and X ⁸ are bonded is a naphthalene ring, and X ^{9 to} X ¹² When all the ring structures to which are bonded are benzene rings, it is preferable that at least one of X ^{7 to} X ¹² is not a hydrogen atom but a monovalent substituent.

In addition, the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is obtained by combining X ⁷ and X ⁸ with a 6-membered ring skeleton constituting the dicyclopentadienylidene cyclohexadiene skeleton. None of the two dotted arcs between them form a ring structure, and four dotted arcs between X ^{9 to} X ¹² and the five-membered ring skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton Each form a benzene ring together with a part of the skeleton of the 5-membered ring, and when X ^{7 to} X ¹² contain a chlorine atom, at least one of X ^{7 to} X ¹² is a hydrogen atom. Or it is preferable to represent monovalent substituents other than a chlorine atom. That is, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2), each of X ⁷ and X ⁸ is a 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. A dotted arc between the skeleton and the skeleton does not form a ring structure, but is a part of the skeleton of the six-membered ring, and a dotted arc forms the ring structure. When any of the ring structures to which X ^{9 to} X ¹² are bonded is a benzene ring, at least one of X ^{7 to} X ¹² is a hydrogen atom or a monovalent other than a chlorine atom It is preferable that it is a substituent. Incidentally, preferable examples of the monovalent substituent other than a chlorine atom, a preferred examples of the monovalent substituent when X ⁷ to X ¹² described above is a monovalent substituent, but excluding a chlorine atom is there.

Furthermore, in the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2), 1 to 5 of X ^{7 to} X ¹² in the formula (2) are carbon-carbon double bonds or A monovalent substituent containing a triple bond is preferred. That is, at least one of X ^{7 to} X ¹² in Formula (2) is a monovalent substituent containing a carbon-carbon double bond or triple bond, but all of X ^{7 to} X ¹² are carbon-carbon. A monovalent substituent containing a double bond or triple bond between them, and a monovalent substituent containing a hydrogen atom or a carbon-carbon double bond or triple bond in X ^{7 to} X ¹² A compound having a dicyclopentadienylidenecyclohexadiene skeleton containing at least one monovalent substituent that is not a substituent is preferable.
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 X ^{7 to} X ¹² described above 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 compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2), at least one of X ^{7 to} X ^{12 is} a monovalent substituent containing a carbon-carbon double bond or triple bond In this case, the substituent that is not a monovalent substituent containing a carbon-carbon double bond or triple bond is a monovalent substitution when X ^{1 to} X ⁶ described above are monovalent substituents. Among those preferable as the group, those not containing a carbon-carbon double bond or triple bond are preferable.

The compound having the dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) includes a dotted arc and a 5-membered or 6-membered skeleton part forming the dicyclopentadienylidenecyclohexadiene skeleton. The ring structure formed by a part of is preferably a benzene ring, a naphthalene ring, a thiophene ring, a pyridine ring, or a benzothiophene ring.

Among the compounds having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) in the present invention, those having a halogen atom or an alkenyl group as a substituent having a reactive group, For example, the above formulas (7-1), (7-3), (7-6), (7-8), (7-11), (7-15), (7-18), (7-20) ) To (7-23), (7-25), (7-26) and (7-31) are more preferred. Of these, those having a long-chain alkyl group, an alkoxy group, etc. are preferred so that the polymer has solubility. For example, compounds having structures such as the above formulas (7-18), (7-20) to (7-23), (7-25), (7-26), and (7-31) are more preferable. Can be mentioned.

The polymer of the present invention has a repeating unit formed by polycondensation of at least two groups of X ^{7 to} X ¹² in the formula (2) or polymerization of at least one group. . That is, the following formula (8);

(In the formula, the dotted circular arc is the same as that in the formula (2). X ⁷ ′ to X ¹² ′ are the same groups as those in the formula (2) X ^{7 to} X ¹² , divalent groups, A polymer having a repeating unit structure represented by a valent group or a direct bond). The above formula (8) means that any one or more of X ⁷ ′ to X ¹² ′ form a bond as a part of the main chain of the polymer. When at least two groups among X ^{7 to} X ^{12 in} the above formula (2) are polycondensed to form a polymer, at least two groups among X ⁷ ′ to X ¹² ′ in the above formula (8) Is a divalent group or a direct bond. When at least one group of X ^{7 to} X ¹² in the formula (2) is polymerized alone to form a polymer, at least one of X ⁷ ′ to X ¹² ′ in the formula (8) The group is a trivalent group or a direct bond.
The polymer having a repeating unit represented by the above formula (8) may be composed of one kind of the structure represented by the above formula (8), or two kinds represented by the above formula (8). The above structure may be included. Moreover, you may have repeating units other than the repeating unit represented by the said Formula (8). When two or more types of structures represented by the above formula (8) are included, the two or more types of structures may be random polymers, block polymers, graft polymers, or the like. Further, the polymer main chain may be branched and the terminal chain may be 3 or more or a dendrimer.

Among the specific examples of the structure of the repeating unit represented by the above formula (8), the structure obtained by polycondensation is, for example, that two groups out of X ⁷ ′ to X ¹² ′ are divalent groups or directly It is a bond. Among these, X ⁷ ′, X ⁹ ′, or X ¹¹ ′ is a divalent group or a direct bond, and X ⁸ ′, X ¹⁰ ′, or X ¹² ′ is a divalent group, or A direct bond is preferred. More preferably, it is a repeating structure represented by the following formulas (9-1) to (9-3). That is, it has a structure represented by the formula (2), and X ⁷ and X ⁸ , X ⁹ and X ¹⁰ , or X ¹¹ and X ¹² in the formula (2) are substituents having a reactive group. A polymer obtained from a compound having a dicyclopentadienylidenecyclohexadiene skeleton is also one aspect of the present invention. In addition, when X ⁷ in the formula (2) is a substituent having a reactive group and there are two or more, a single amount of the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is used. In the polymer represented by the formula (8) obtained by polymerization as a body component, if any one of two or more X ⁷ ′ is a divalent group, a trivalent group, or a direct bond Good. Any of X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , and X ¹² in Formula (2) is a substituent having a reactive group, and the same applies to the case where there are two or more.

The combination of the reactive groups capable of polycondensation is not particularly limited as long as it can be polymerized. For example, carboxyl group and hydroxy group, carboxyl group and thiol group, carboxyl group and amino group, carboxylate ester and amino group. Group, carboxyl group and epoxy group, hydroxy group and epoxy group, thiol group and epoxy group, amino group and epoxy group, isocyanate group and hydroxy group, isocyanate group and thiol group, isocyanate group and amino group, hydroxy group and halogen atom, Thiol group and halogen atom, stannyl group and halogen atom, aldehyde group and phosphonium methyl group, vinyl group and halogen atom, aldehyde group and phosphonate methyl group, haloalkyl group and haloalkyl group, sulfonium methyl group and sulfonium methyl group, aldehyde group Acetonitrile group, an aldehyde group and an aldehyde group, a halogen atom and a boryl group, a halogen atom and a magnesium halide, and a halogen atom and a halogen atom.
Among these, combinations of halogen atoms and boryl groups, combinations of halogen atoms and halogen atoms, and combinations of stannyl groups and halogen atoms are preferable.

In the polymer represented by the above formula (8), two dotted arcs between X ⁷ ′ and X ⁸ ′ and the skeleton portion of the 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton Four dotted lines between X ⁹ ′ to X ¹² ′ and the five-membered ring skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, each forming a naphthalene ring together with a part of the six-membered skeleton In the case where each arc forms a benzene ring together with a part of the skeleton of the 5-membered ring, X ⁷ ′ to X ¹² ′ are at least one divalent group, trivalent group, or direct bond Is preferably represented. That is, in the polymer represented by the above formula (8), the ring structures to which X ⁷ and X ⁸ are bonded are both naphthalene rings, and the ring structures to which X ^{9 to} X ¹² are bonded are all. When it is a benzene ring, it is preferable that at least one of X ^{7 to} X ¹² represents a divalent group, a trivalent group, or a direct bond instead of a hydrogen atom.

In the polymer represented by the above formula (8), the two dotted arcs between X ⁷ ′ and X ⁸ ′ and the 6-membered ring skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton Are not formed, and four dotted arcs between X ⁹ ′ to X ¹² ′ and the five-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are all the five-membered ring. along with a portion of the skeletal portion ^to form a benzene ^ring, X 7'~X ¹² 'if it contains chlorine atom in ^the, X ^{7'~X 12'} is at least one hydrogen atom, a chlorine atom It preferably represents a monovalent substituent other than the above, a divalent group, a trivalent group, or a direct bond. That is, in the polymer represented by the above formula (8), each of X ⁷ ′ and X ⁸ ′ is a dotted line between the skeleton portion of the 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. When the arc does not form a ring structure and is a part of the skeleton portion of the 6-membered ring, and the dotted arc forms the ring structure, it binds to a carbon atom that becomes a part of the ring structure; When all the ring structures to which X ⁹ ′ to X ¹² ′ are bonded are benzene rings, at least one of X ⁷ ′ to X ¹² ′ is a hydrogen atom or a monovalent substituent other than a chlorine atom, It preferably represents a divalent group, a trivalent group, or a direct bond. Incidentally, preferable examples of the monovalent substituent other than a chlorine atom, a preferred examples of the monovalent substituent when X ⁷ to X ¹² described above is a monovalent substituent, but excluding a chlorine atom is there.

When at least two of X ^{7 to} X ^{12 in} the above formula (2) are polycondensed to form a polymer, at least two groups of X ⁷ ′ to X ¹² ′ in the above formula (8) are divalent. Or a direct bond, the divalent group represents a residue that is not eliminated by a polycondensation reaction between substituents having a reactive group. When a substituent having a reactive group that forms a combination of reactive groups capable of polycondensation undergoes a polycondensation reaction, the residue may or may not remain in the polymer. In this case, at least one of X ⁷ ′ to X ¹² ′ represents a residue that is not eliminated by a polycondensation reaction between substituents having a reactive group, and in the latter case, X ⁷ ′ to X ^{7 At} least one of ¹² 'will represent a direct bond.
Furthermore, when the repeating unit represented by formula (8) is two or more continues, between two repeating units, for ^example, -X 7 ^'-X 8'- as in, ^{X 7'} and X ^In this case, any one of the two may be a direct bond.

Specific examples of the case where a substituent having a reactive group that forms a combination of reactive groups capable of polycondensation causes a polycondensation reaction to leave a residue in the polymer include a substituent having a carboxyl group and a hydroxy group. The combination with the substituent which has group is mentioned. For example, when a —CH ₂ COOH group and a —CH ₂ CH ₂ OH group undergo a polycondensation reaction, the residue remaining in the polymer becomes a —CH ₂ (CO) —O—CH ₂ CH ₂ — group. Further, for example, when a substituent having a reactive group is composed only of a reactive group, such as a reaction between a —COOH group and an —OH group, the residue remaining in the polymer is — (CO) —O. -The basis.
In addition, specific examples of the case where the combination of reactive groups capable of polycondensation causes a polycondensation reaction and no residue remains in the polymer include a boryl group and a halogen atom, a halogen atom and a halogen atom, and a stannyl group and a halogen. A combination of an atom, a halogen atom and a magnesium halide can be used.

Among specific examples of the structure of the repeating unit represented by the above formula (8), as a structure obtained by polymerizing at least one of X ^{7 to} X ^{12 in} the above formula (2) alone, for example, X ¹² is The structure obtained by polymerization is a structure represented by the following formula (10). Thus, when X ¹² in formula (2) is a substituent having a reactive group that can be polymerized alone in the structure, X ¹² ′ is a trivalent group or a repeating unit having a structure in which it is a direct bond. It becomes. Similarly, when X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ in the formula (2) are substituents having a reactive group capable of being polymerized alone in the structure, X ⁷ ′, X ⁸ ′, X ⁹ ′, X ¹⁰ ′, and X ¹¹ ′ are repeating units of a structure in which a trivalent group or a direct bond is formed.

The polymer having a repeating unit represented by the above formula (10) may be composed of one type of the structure represented by the above formula (10), or two types represented by the above formula (10). The above structure may be included. Moreover, you may have a repeating unit other than the repeating unit represented by the said Formula (10). When two or more types of structures represented by the above formula (10) are included, the two or more types of structures may be random polymers, block polymers, graft polymers, or the like. Further, when the polymer main chain is branched and there are three or more terminal portions, a dendrimer may be used.

Examples of the reactive group that can be polymerized alone include 3,5-dibromophenyl group, alkenyl group, alkynyl group, and epoxy group. When the compound having the dicyclopentadienylidenecyclohexadiene skeleton of the above formula (2) has at least one of these groups, the compound of the above formula (2) can be polymerized alone. Among these, an alkenyl group, an epoxy group, and a 3,5-dibromophenyl group are preferable.

Of X ^{7 to} X ^{12 in} the above formula (2), the polycondensation group may be a substituent having in its structure a reactive group capable of polycondensation. Similarly, in the case of homopolymerization, any substituent may be used as long as it has a reactive group that can be polymerized alone. Examples of such a substituent include a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, and an aryl group. And a group in which a hydrogen atom of any group such as a heterocyclic group is substituted with a reactive group capable of polycondensation or a reactive group capable of being polymerized alone. Among these, a styryl group and a 3,5-dibromophenyl group are preferable.

As long as the polymer of the present invention can be obtained from a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2), the monomer component may contain other units. A mer may be included.
That is, a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the formula (2) and the following formula (11);

^{X 13 -A-X 14 (11} )

(In the formula, A represents a divalent group. X ¹³ and X ¹⁴ are the same or different and each represents a hydrogen atom or a monovalent substituent, and at least one group of X ¹³ and X ¹⁴ represents a reaction) Polymers formed by polymerizing with other monomers represented by the formula (1) are also included in the polymer of the present invention.

In the compound represented by the above formula (11), as X ¹³ and X ¹⁴ , the same monovalent substituents as those in X ^{7 to} X ¹² can be used.

A in the above formula (11) is not particularly limited as long as it is a divalent group, but examples of the corresponding compound names include benzene, naphthalene, anthracene, phenanthrene, chrysene, rubrene, pyrene, perylene, Indene, azulene, adamantane, fluorene, fluorenone, dibenzofuran, carbazole, dibenzothiophene, furan, pyrrole, pyrroline, pyrrolidine, thiophene, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran , Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, trithiane, norbornene, benzofuran, indo , Benzothiophene, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzoxadiazole, purine, quinoline, isoquinoline, coumarin, sinoline, quinoxaline, acridine, phenanthroline, phenothiazine, flavone, triphenylamine, acetylacetone, dibenzoylmethane , Metal coordination compounds such as picolinic acid, silole, porphyrin, iridium, or derivatives having a substituent, polymers or oligomers containing the structures of these derivatives, and the like.

As said A, in addition to what was mentioned above, the structure of following formula (12-1)-(12-4) is mentioned, for example.

(In the formula, Ar1, Ar2, and Ar3 are the same or different and each represents an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. Z1 represents —C≡C—, — N (Q3)-,-(SiQ4Q5) _b- , or a direct bond, Z2 represents -CQ1 = CQ2-, -C≡C-, -N (Q3)-,-(SiQ4Q5) _b- , or Q1 and Q2 are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group (heterocyclic group), a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Represents an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, or a cyano group, and Q3, Q4, and Q5 are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic ring. A group represents an arylalkyl group, a represents an integer of 0 to 1, and b represents an integer of 1 to 12.)

The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and the number of carbon atoms constituting the ring is usually 6 or more and 60 or less. The carbon number is preferably 20 or less. The aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene.
Examples of the arylene group include a phenylene group represented by the following formula (13-1), a naphthalenediyl group represented by the following formulas (13-2) to (13-3), and the following formula (13-4). To an anthracenediyl group represented by (13-7), a biphenyl-diyl group represented by the following formula (13-8), a fluorene-diyl group represented by the following formula (13-9), a formula (13 -10), a terphenyl-diyl group represented by the following formulas (13-11) to (13-12), and a stilbene-diyl group represented by the following formulas (13-13) to (13-14). Distylben-diyl groups, condensed ring compound groups represented by the following formulas (13-15) to (13-20), groups represented by the following formulas (13-21) to (13-23), and the like. It is done. Among these, a phenylene group, a biphenyl-diyl group, a fluorene-diyl group, and a stilbene-diyl group are preferable.
In the formulas (13-1) to (13-23), Rs are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, Arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, imido group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group Group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl Group or shear It represents a group. In the formula (13-1), a line attached so as to cross the ring structure like a line indicated by xy means that the ring structure is directly bonded to an atom in the bonded portion. That is, in the formula (13-1), it means that it is directly bonded to any of the carbon atoms that constitute the ring indicated by the line xy, and the bonding position in the ring structure is not limited. Like the line indicated by z- in formula (13-10), the line attached to the apex of the ring structure means that the ring structure is directly bonded to the atom in the bonded moiety at that position. . Moreover, the line with R attached so as to intersect the ring structure means that R may be bonded to the ring structure one or plural, and the bond The position is not limited.
In the formulas (13-1) to (13-10) and (13-15) to (13-20), the carbon atom may be replaced with a nitrogen atom, an oxygen atom or a sulfur atom, and a hydrogen atom May be substituted with a fluorine atom.

The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and the number of carbon atoms constituting the ring is usually 3 or more and 60 or less. As the heterocyclic compound, among organic compounds having a cyclic structure, the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic in the ring Is also included.

Examples of the divalent heterocyclic group include a pyridine-diyl group represented by the following formula (14-1), a diazaphenylene group represented by the following formulas (14-2) to (14-3), A quinoline diyl group represented by the following formulas (14-4) to (14-6), a quinoxaline diyl group represented by the following formulas (14-7) to (14-9), and the following formulas (14-10) to ( 14-12) includes acridinediyl group, bipyridyldiyl group represented by the following formula (14-13), phenanthroline diyl group represented by the following formula (14-14), etc. A divalent heterocyclic group; a group having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a heteroatom represented by the following formulas (14-15) to (14-17); Heteroatom represented by (14-20) A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc .; 5 containing silicon, nitrogen, sulfur, selenium, etc. as heteroatoms represented by the following formulas (14-21) to (14-26) A 5-membered ring heterocyclic group represented by the following formulas (14-27) to (14-29), which is a 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom. A dimer or oligomer group bonded to each other; a 5-membered ring heterocyclic ring represented by the following formulas (14-30) to (14-35) containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom A group bonded to the phenyl group at the α-position of the hetero atom by a group; represented by the following formulas (14-36) to (14-38); A group in which a phenyl group, a furyl group, or a thienyl group is substituted on a ring-fused heterocyclic group; etc. And the like.
In formulas (14-1) to (14-38), R is the same as R in the arylene group. Y represents O, S, SO, SO ₂ , Se, or Te. For the line attached to intersect the ring structure, the line attached to the apex of the ring structure, and the line with R attached to intersect the ring structure, the formulas (13-1) to (13-23) It is the same.
In the formulas (14-1) to (14-38), the carbon atom may be replaced with a nitrogen atom, an oxygen atom or a sulfur atom, and the hydrogen atom may be replaced with a fluorine atom.

The divalent group having the metal complex structure is a remaining divalent group obtained by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand. The organic ligand usually has 4 or more and 60 or less carbon atoms, such as 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and Examples thereof include 2-phenyl-benzoxazole and derivatives thereof, porphyrin and derivatives thereof, and the like.

Examples of the central metal of the metal complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium. Examples of the metal complex having the organic ligand include low-molecular fluorescent materials, phosphorescence Examples of the material include known metal complexes and triplet luminescent complexes.

Specific examples of the divalent group having the metal complex structure include groups represented by the following formulas (15-1) to (15-7).
In the formulas (15-1) to (15-7), R is the same as R in the arylene group. About the line attached | subjected to the vertex of the ring structure, direct bond | bonding is meant like Formula (13-1)-(13-23).
In the formulas (15-1) to (15-7), the carbon atom may be replaced with a nitrogen atom, an oxygen atom or a sulfur atom, and the hydrogen atom may be replaced with a fluorine atom.

Moreover, as a structure of A, a structure like following formula (12-5) is also mentioned.

(In the formula, Ar 4, Ar 5, Ar 6 and Ar 7 are the same or different and represent an arylene group or a divalent heterocyclic group. Ar 8, Ar 9 and Ar 10 are the same or different and represent an aryl group or a monovalent heterocyclic ring. And m and n are the same or different and represent 0 or 1, and 0 ≦ m + n ≦ 1.

Specific examples of the structure represented by the above formula (12-5) include structures represented by the following formulas (16-1) to (16-8).

In the formulas (16-1) to (16-8), R is the same as R in the arylene group. About the line attached | subjected to the vertex of the ring structure, direct bond | bonding is meant like Formula (13-1)-(13-23). In the above formulas (16-1) to (16-8), one structural formula has a plurality of Rs, but they may be the same group or different groups. . In order to increase the solubility in a solvent, it is preferable to have one or more other than hydrogen atoms, and it is preferable that the symmetry of the shape of the structure including the substituent is small. Further, in the above formulas (16-1) to (16-8), when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents. . Moreover, in the substituent in which R contains an alkyl chain, they may be linear, branched or cyclic, or a combination thereof. Examples of the non-linear group include, for example, isoamyl group, 2-ethylhexyl group 3,7-dimethyloctyl group, cyclohexyl group, 4-C1 to C12 alkylcyclohexyl group (4-alkylcyclohexyl group having 1 to 12 carbon atoms in the alkyl group portion) and the like. In order to improve the solubility of the polymer of the present invention in a solvent, it is preferable that one or more cyclic or branched alkyl chains are contained.
A plurality of R may be connected to form a ring. Further, when R is a group containing an alkyl chain, the alkyl chain may be interrupted by a group containing a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

Among the structures described above, the structure of A is preferably formula (12-5), formula (13-9), formula (14-16), or formula (14-28).

The monomer component used as the raw material of the polymer of the present invention is a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) and another compound represented by the above formula (11) In the above formula (11), the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is contained in an amount of 5 to 95 mol% based on 100 mol% of the whole monomer component. It is preferable to contain 95-5 mol% of the other compounds represented. More preferably, the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is 10 to 90 mol%, and the other compound represented by the above formula (11) is 90 to 10 mol%. More preferably, the compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) is contained in an amount of 20 to 80 mol%, and the other compound represented by the above formula (11). 80 to 20 mol% is included.

The polymer of the present invention is obtained from a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) and another compound represented by the above formula (11). A repeating unit formed by polymerizing at least one group of X ^{7 to} X ¹² in formula (2) and at least one group of X ¹³ and X ^{14 in} formula (11) It is what has. That is, the following formula (17);

(In the formula, the dotted arc is the same as in formula (2). X ⁷ ′ to X ¹² ′ are the same as in formula (8). A is the same or different and represents a divalent group. X ¹³ ′ and X ¹⁴ ′ each represents a repeating unit represented by the same group as X ¹³ and X ^{14 in} formula (11), a divalent group, a trivalent group, or a direct bond. The polymer having the following structure is also included in the polymer of the present invention.

In the formula (17), any one or two of X ⁷ ′ to X ¹² ′ and X ¹³ ′ and / or X ¹⁴ ′ form a bond as a part of the main chain of the polymer. Means.
In the polymer having a repeating unit represented by the above formula (17), the repeating unit derived from the above formula (2) and the repeating unit derived from the above formula (11) may be a random polymer or a block polymer. There may also be a graft polymer. Further, when the polymer main chain is branched and there are three or more terminal portions, a dendrimer may be used. A structural unit formed by a reaction between a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) and a compound represented by the above formula (11) is a repeating unit. It may be.
In addition, the polymer having a repeating unit represented by the above formula (17) may include one repeating unit derived from the above formula (2) and one repeating unit derived from the above formula (11). Two or more types may be included. When two or more types of repeating units are included, the two or more types of structures may be a random polymer, a block polymer, or a graft polymer. Further, when the polymer main chain is branched and there are three or more terminal portions, a dendrimer may be used.

As the polymer represented by the above formula (17), (i) any two of X ^{7 to} X ^{12 in} the above formula (2), and X ¹³ and X ¹⁴ in the above formula (11), When used for forming a bond for forming the main chain of the polymer, (ii) any one of X ^{7 to} X ^{12 in} the above formula (2) and X ¹³ in the above formula (11) or Any one group of X ¹⁴ may form a bond as part of the main chain of the polymer. As specific examples of the structure of the repeating unit in these cases, for example, there are structures such as the following formulas (18) and (19).

(I) Any two of X ^{7 to} X ^{12 in} the above formula (2) and X ¹³ and X ¹⁴ in the above formula (11) form a bond for forming the main chain of the polymer. When used, the repeating unit derived from the above formula (2), the repeating unit derived from the above formula (11) may be randomly added, or may be a block added, or the above formula (2) Any of the groups X ^{7 to} X ^{12 in} the above and X ¹³ and / or X ^{14 in the} above formula (11) may be polycondensed, but among these, in the above formula (2) It is preferable that any group of X < ⁷ > -X < ¹² > of the above and X < ¹³ > and / or X < ¹⁴ > in the said Formula (11) are polycondensed. As an example of such a polymer, a product obtained by polycondensation of X ¹¹ and X ¹² in the above formula (2) with X ¹³ and X ¹⁴ in the above formula (11) is represented by the following formula (20). The polymer having the structure as a repeating unit.

As the combination of the reactive groups when any group of X ^{7 to} X ^{12 in} the above formula (2) and X ¹³ and / or X ^{14 in the} above formula (11) are polycondensed, those described above The same thing is mentioned. The preferable combination of reactive groups is also the same as described above. That is, when any group of X ^{7 to} X ¹² in the formula (2) and X ¹³ and / or X ^{14 in the} formula (11) undergo polycondensation, X ¹³ in the formula (11) And X ¹⁴ is preferably any of the above-described substituents having a reactive group capable of polycondensation in the structure. Among them, the polycondensation reaction between the compound having the dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2) and the compound represented by the above formula (11) is a preferable reactive group described above. Substituents that result in a combination reaction are preferred.
In addition, when any of X ¹³ and X ^{14 in} the above formula (11) is a substituent having a reactive group capable of being polymerized alone in the structure, the substituent can be polymerized alone as described above. It is preferably any of substituents having a reactive group in the structure.

The groups bonded to both ends of the polymer of the present invention are not particularly limited, and may be the same or different. Examples of the group bonded to both ends include a hydrogen atom, a halogen atom, an aryl group optionally having a substituent, an oligoaryl group, a monovalent heterocyclic group, and a monovalent oligoheterocyclic group. Alkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, amino group, azo group, carboxyl group, acyl group, Examples include an alkoxycarbonyl group, a formyl group, a nitro group, a cyano group, a silyl group, a stannyl group, a boryl group, a phosphino group, a silyloxy group, an arylsulfonyloxy group, and an alkylsulfonyloxy group.

The polymer of the present invention preferably has a weight average molecular weight of 10 ³ to 10 ⁸ . When the weight average molecular weight is in such a range, a thin film can be satisfactorily formed. More preferably, it is 10 < ³ > -10 < ⁷ >, More preferably, it is 10 < ⁴ > -10 < ⁶ >.
The weight average molecular weight can be measured by gel permeation chromatography (GPC apparatus, developing solvent: chloroform) in terms of polystyrene under the following apparatus and measurement conditions.
High-speed GPC apparatus: Measured using HLC-8220 GPC (manufactured by Tosoh Corporation).
Developing solvent Chloroform column TSK-gel GMHXL x 2 Eluent flow rate 1 ml / min
Column temperature 40 ° C

[Use of compounds and polymers having dicyclopentadienylidenecyclohexadiene skeleton]
The present invention is also a solar cell material including a polymer obtained by polymerizing a compound having a dicyclopentadienylidenecyclohexadiene skeleton or a monomer component containing the compound having the skeleton and a reactive group. .
The compound having a dicyclopentadienylidenecyclohexadiene skeleton in the solar cell material of the present invention is preferably a compound having the dicyclopentadienylidenecyclohexadiene skeleton of the present invention represented by the above formula (1) or a preferred one thereof. The form is preferred. The polymer in the solar cell material of the present invention is obtained by polymerizing a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2). It is preferable that it is a polymer, the polymer of this invention which has a structure of the repeating unit represented by said Formula (8), and those preferable forms.
This invention is also a solar cell element produced using the solar cell material of this invention.

The present invention also provides a material for an organic transistor comprising a polymer obtained by polymerizing a compound having a dicyclopentadienylidenecyclohexadiene skeleton or a monomer component containing a compound having the skeleton and a reactive group. is there.
The compound having a dicyclopentadienylidenecyclohexadiene skeleton in the organic transistor material of the present invention is preferably a compound having the dicyclopentadienylidenecyclohexadiene skeleton of the present invention represented by the above formula (1) or a preferred one thereof. The form is preferred. The polymer in the organic transistor material of the present invention is obtained by polymerizing a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton represented by the above formula (2). It is preferable that it is a polymer, the polymer of this invention which has a structure of the repeating unit represented by said Formula (8), and those preferable forms.
The present invention is also an organic transistor element produced using the organic transistor material of the present invention.
The compound having the dicyclopentadienylidenecyclohexadiene skeleton of the present invention and the polymer of the present invention can be suitably applied to devices such as actuators and organic batteries in addition to the above-described solar cell elements and organic transistor elements. it can.

[Method for producing compound having dicyclopentadienylidenecyclohexadiene skeleton]
Next, a method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention will be described.
In addition, the compound which has the dicyclopentadienylidene cyclohexadiene skeleton represented by the said Formula (2) used as the raw material of the polymer of this invention also uses the following formula (i)-(iii) using the same manufacturing method. of X ¹ to X ^6, it is possible at least one of manufacturing by using an unsaturated bond-containing compound such as a substituted group having a reactive group as a starting material.
The present invention is a method for producing a compound having a cyclic structure having an unsaturated bond, wherein the production method comprises the following formula (i);

(In the formula, two dotted arcs indicate that a ring structure may be formed together with a part of the skeleton of a 6-membered ring, and the ring structure may not be formed. X ¹ , X ² are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ¹ and X ² , a dotted arc between the 6-membered ring skeleton part is one of the 6-membered skeleton parts. In the case of forming a ring structure together with a portion, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. If no form is part of the backbone portion of the 6-membered ring, the dotted arc is bound to become part of carbon atoms of the ring structure when to form a ring structure .R ¹ to R ⁴ are the same or different, monovalent represents a substituent.) unsaturated bond-containing compound represented by the (I), the following (Ii);

(In the formula, a dotted arc represents that a ring structure may be formed together with carbon atoms bonded to each other by a double bond, and the ring structure may not be formed. X ³ , X ⁴ Are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ³ and X ⁴ , a dotted circular arc between carbon atoms bonded to each other by a double bond is In the case of forming a ring structure with bonded carbon atoms, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. In the case where the dotted arc does not form the ring structure, it is bonded to the carbon atoms bonded to each other by the double bond, and R ⁵ and R ⁶ are the same or different and different from R ^{1 to} R ^4. An unsaturated bond-containing compound represented by (II represents a monovalent substituent) When the following formula (iii);

(In the formula, a dotted arc represents that a ring structure may be formed together with carbon atoms bonded to each other by a double bond, or the ring structure may not be formed. X ⁵ , X ⁶ Are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ⁵ and X ⁶ , a dotted circular arc between carbon atoms bonded to each other by a double bond is In the case of forming a ring structure with bonded carbon atoms, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. In the case where the dotted arc does not form the ring structure, it is bonded to the carbon atoms bonded to each other by the double bond, R ⁷ and R ⁸ are the same or different and different from R ^{1 to} R ^4. An unsaturated bond-containing compound represented by (II represents a monovalent substituent) ) Includes the step of reacting the above manufacturing method is a manufacturing method of a compound having a di cyclopentadienylidene cyclohexadiene skeleton is intended to obtain a compound having a di cyclopentadienylidene cyclohexadiene skeleton. In addition, the compound having a dicyclopentadienylidenecyclohexadiene skeleton obtained by the production method of the present invention may partially contain a radical such as a biradical having no dicyclopentadienylidenecyclohexadiene skeleton. Yes, some of them may be radicals.

The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton according to the present invention includes a ring structure in which X ^{1 to} X ⁶ are bonded by appropriately selecting the unsaturated bond-containing compounds (I) to (III). It is possible to produce a compound having a dicyclopentadienylidenecyclohexadiene skeleton in which is varied.
Moreover, the polymer of this invention which uses the compound as a raw material can also manufacture what has a structure of a various repeating unit.
The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention includes a step of reacting the unsaturated bond-containing compounds (I) to (III). In this reaction step, the unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III) may each be used alone or in combination of two or more. May be. In addition, the unsaturated bond-containing compound (II) and the unsaturated bond-containing compound (III) may be the same compound.
The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention includes the unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III As long as it includes the step of reacting with (), other steps may be included. Furthermore, as long as the said unsaturated bond containing compound (I)-(III) is used as a reaction raw material, the said reaction process may be performed by one process, and may be performed by several processes. Good.

The dotted arc in the above formula (i), the above formula (ii), and the above formula (iii) may form a ring structure together with two carbon atoms constituting a double bond between carbon atoms. This means that the structure may not be formed. That is, each of the compounds represented by the above formula (i), formula (ii), and formula (iii) may have one or two ring structures in the structure, and has the ring structure. In the above formula (i), formula (ii), and formula (iii), when the structure has one or two ring structures, the double bond portion between carbon atoms is the ring structure. It is included as part of.
In the formula (i), X ¹ and X ² are the same or different and represent a hydrogen atom or a monovalent substituent. In the formula (ii), X ³ and X ⁴ are the same or different and represent a hydrogen atom. Alternatively, it represents a monovalent substituent, and in the above formula (iii), X ⁵ and X ⁶ are the same or different and each represents a hydrogen atom or a monovalent substituent.
Specific examples and preferred structures of the structures of X ^{1 to} X ⁶ , specific examples and preferred structures of structures represented by dotted arcs, and the position at which the monovalent substituent is bonded are represented by X ¹ in the above formula (1). specific examples and preferred structure of the structure of to X ^6, specific examples and preferred structure of the structure represented by the dashed arc, and is the same as the position in which the monovalent substituent is attached.

Said R < ¹ > -R < ⁸ > is the same or different and represents a monovalent substituent. R ^{5 to} R ⁸ may be different from any of R ^{1 to} R ⁴ , respectively. The monovalent substituent may be any substituent that allows Pd (0) species to undergo oxidative addition. Further, the ^R 1 to R ⁸ may, for example, is preferably a group that departs during polymerization. For example, a halogen atom, a triflate group, a tosylate group, or a boryl group is preferable. Among these, a bromine atom, an iodine atom, and a boryl group are preferable. R ^{1 to} R ⁴ are preferably the same substituent. Moreover, it is preferable that R < ⁵ > -R < ⁸ > is the same substituent.
In the present specification, the triflate group refers to a [(trifluoromethyl) sulfonyl] oxy group. The tosylate group refers to a [p-toluenesulfonyl] oxy group. The boryl group is as described above.

In the step of reacting the unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III), with respect to 1 mole of the unsaturated bond-containing compound (I). The reaction is preferably carried out using 0.5 to 1.5 mol of the unsaturated bond-containing compound (II) and 0.5 to 1.5 mol of the unsaturated bond-containing compound (III). By using in such a ratio, a compound having a dicyclopentadienylidenecyclohexadiene skeleton can be produced in a high yield. More preferably, the unsaturated bond-containing compound (II) is 0.7 to 1.3 mol, and the unsaturated bond-containing compound (III) is 0.7 to 1 mol of the unsaturated bond-containing compound (I). It is to use -1.3 mol.
When the group of R ^{1 to} R ⁴ has a boryl group and the group of R ^{5 to} R ⁸ has a bromine atom or an iodine atom, the unsaturated bond-containing compound (II) and the unsaturated bond-containing It is more preferable to use 0.9 to 1.2 mol of the unsaturated bond-containing compound (I) with respect to 2 mol of the total amount of the compound (III). Further, when the group of R ^{1 to} R ⁴ has a bromine atom or an iodine atom and the group of R ^{5 to} R ⁸ has a boryl group, with respect to 1 mol of the unsaturated bond-containing compound (I), More preferably, 0.9 to 1.2 mol of the unsaturated bond-containing compound (II) and 0.9 to 1.2 mol of the unsaturated bond-containing compound (III) are used.

The step of reacting the unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III) 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), it is preferable to use one or more palladium complexes such as palladium acetate (Pd _{(OAc) 2).} More preferably, Pd (PPh ₃ ) ₄ or Pd (P ^t Bu ₃ ) ₂ is used.
Moreover, it is preferable to use it as a usage-amount of a catalyst so that it may become 0.001-0.2 mol with respect to 1 mol of said unsaturated bond containing compound (I). More preferably, it is used so that it may become 0.01-0.15 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 (for example, 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 unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III) is particularly as long as the reaction proceeds. Although it does not restrict | limit, It is preferable to use 1 type, or 2 or more types of ether type | system | group polar solvents, such as tetrahydrofuran, diethyl ether, and a dioxane. More preferred is tetrahydrofuran.
Furthermore, you may use what mixed 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 unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III) 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 unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III) is preferably 20 ° C. or higher. More preferably, it is 40 ° C. or higher. Moreover, it is preferable that this reaction temperature is 100 degrees C or less. More preferably, it is 80 degrees C or less. Thus, the method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention can be suitably carried out under relatively mild conditions.
The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure. The reaction time is preferably 1 hour or longer. More preferably, it is 10 hours or more, and particularly preferably 12 hours or more from the industrial and practical aspects. The reaction time is preferably 48 hours or less. More preferably, it is 36 hours or less, and particularly preferably 30 hours or less from the viewpoint of industrial and practical use.

In the method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention, the unsaturated bond-containing compound (I), the unsaturated bond-containing compound (II), and the unsaturated bond-containing compound (III) After the step of reacting, a step of purifying the obtained compound having a dicyclopentadienylidenecyclohexadiene skeleton 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 method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention is a method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention represented by the above formula (1). It can be suitably used as a method. That is, the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention represented by the above formula (1) is produced using the method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention. This is one of the preferred embodiments of the method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention.

[Method for producing polymer]
The present invention provides a reaction step in the method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention, and a single amount of the compound having a dicyclopentadienylidenecyclohexadiene skeleton obtained by the reaction step. It is also a method for producing a polymer including a step of obtaining a polymer by reacting as a body component. In addition, the polymer obtained by the method for producing a polymer of the present invention has a part of repeating units derived from a compound having a dicyclopentadienylidenecyclohexadiene skeleton that does not have a dicyclopentadienylidenecyclohexadiene skeleton. It may exist in radicals such as biradicals, and some of them may be radicals.
Examples of the solvent used in producing the polymer from the monomer component containing the compound represented by the above formula (2) include one or more of toluene, xylene, tetrahydrofuran, dioxane, chloroform, dichloromethane and the like. It is done. Among these, toluene, chloroform, and tetrahydrofuran are preferable. More preferred are toluene and tetrahydrofuran.

The reaction temperature for producing the polymer from the monomer component containing the compound represented by the above formula (2) is preferably -100 ° C to 300 ° C. More preferably, it is -50 degreeC-200 degreeC, More preferably, it is 0 degreeC-150 degreeC.
The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure. Moreover, it is preferable that reaction time is 1 to 72 hours. More preferably, it is 10 to 48 hours, More preferably, it is 10 to 24 hours.

When the polymer of the present invention is produced from a monomer component containing the compound represented by the above formula (2), a catalyst or a polymerization initiator can be used.
When the reaction for polymerizing the monomer component containing the compound represented by the formula (2) is a polycondensation reaction, the catalyst may be an inorganic acid such as hydrochloric acid, an organic acid, an inorganic base, an organic base, or An organometallic compound or the like can be used, and can be appropriately selected and used according to the type of reactive group that undergoes polycondensation reaction.
The amount of the catalyst or polymerization initiator used is preferably 0.0001 to 1000 mol with respect to 1 mol of the compound represented by the above formula (2). More preferably, it is 0.001-100 mol.

Moreover, when polymerizing the monomer component containing the compound represented by the above formula (2), a chain transfer agent may be used.
The chain transfer agent can be appropriately selected from hydroxystyrene, thiol mercaptan, and the like.
As for the usage-amount of a chain transfer agent, 0.0001-1000 mol is preferable with respect to 1 mol of compounds represented by the said Formula (2). More preferably, it is 0.001-100 mol.

As described above, the compound having a specific structure represented by the above formula and the polymer can be suitably used as a functional organic material such as an n-type semiconductor. It is suitable as a material for batteries and organic transistors. Moreover, it can apply suitably also to devices, such as an actuator and an organic battery.
In addition, when the compound or polymer having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention has a radical property, when used as a battery electrode material, charge and discharge can be performed by movement of electrons. It is considered as a material that enables the manufacture of a battery that can be charged and discharged at a higher speed than a lithium ion battery in which lithium ions move with charge and discharge.
Furthermore, compounds and polymers having a dicyclopentadienylidenecyclohexadiene skeleton having a specific structure represented by the above formula include other materials for telecommunications equipment, materials for electrochromics, materials for thermochromics, electric fields Suitable for various applications such as materials for effect transistors, materials for integrated circuits, materials for gas sensors, materials for electrochemical cells, materials for organic laser diodes, materials for spin valves, materials for light receiving elements, materials for spintronics, etc. Can be used.

The compound and polymer having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention have the above-described configuration, have a low LUMO energy level, and are an n-type organic semiconductor material, particularly an organic thin-film solar cell material, organic It can be suitably used as a functional electronic element material such as a transistor material. The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton according to the present invention enables the synthesis of various compounds having a dicyclopentadienylidenecyclohexadiene skeleton, and is a functional electronic device material. This is a production method that greatly contributes to the research and development of more suitable compounds.

FIG. 2 is a diagram showing the results of ESR measurement of a compound having a dicyclopentadienylidenecyclohexadiene skeleton prepared in Example 1. 4 is a diagram showing the results of ESR measurement of a compound having a dicyclopentadienylidenecyclohexadiene skeleton prepared in Example 2. FIG. It is the figure which showed the result of having measured the current-voltage characteristic with respect to the organic-semiconductor element produced in Example 3. FIG. It is the figure which showed the result of having measured the impedance using the organic-semiconductor element produced in Example 3. 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 organic 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.

Example 1
In the following formula (21), “Chemical Formula” represents a chemical formula. “Exact Mass” represents exact mass. “Molecular Weight” represents molecular weight.

In a 100 ml Schlenk tube, dibromobithiophene (1296 mg, 4.0 mmol), boronate ester (1381 mg, 2.0 mmol), palladium catalyst (231 mg, 0.2 mmol), potassium carbonate (231 mg, 6.0 mmol), THF 40 ml, water 8 ml Was added and replaced with nitrogen. This was heated to 70 ° C. and stirred for 24 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 chromatography (mobile phase: ethyl acetate / hexane) to obtain the desired product.

The physical property values are as follows.
¹ H-NMR (CDCl ₃ ): δ 6.90-6.92 (m, 4H), 7.26-7.27 (m, 4H), 7.39-7.42 (m, 4H), 7. 98-8.00 (m, 4H)

Example 2
In the following formula (22), “Chemical Formula”, “Exact Mass”, and “Molecular Weight” are the same as described above.

In a 100 ml Schlenk tube, dibromobiphenyl (1248 mg, 4.0 mmol), boronic ester (1451 mg, 2.1 mmol), palladium catalyst (231 mg, 0.2 mmol), potassium carbonate (231 mg, 6.0 mmol), THF 40 ml, water 8 ml. In addition, nitrogen substitution was performed. This was heated to 70 ° C. and stirred for 24 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 chromatography (mobile phase: ethyl acetate / hexane) to obtain the desired product.

The physical property values are as follows.
¹ H-NMR (CDCl ₃ ): δ 7.05-7.09 (m, 4H), 7.26-7.31 (m, 8H), 7.66-7.68 (m, 4H), 7. 96-7.99 (m, 4H), 8.04-8.06 (m, 4H)

FIG. 1 is a diagram showing the results of ESR measurement of a compound having a dicyclopentadienylidenecyclohexadiene skeleton prepared in Example 1. FIG. 2 is a graph showing the results of ESR measurement of a compound having a dicyclopentadienylidenecyclohexadiene skeleton prepared in Example 2. As shown in the above formulas (23) and (24) by ESR measurement (used to detect radicals), a part of biradical state having no dicyclopentadienylidenecyclohexadiene skeleton is present. Was confirmed. It was clarified that a part of the compound having a dicyclopentadienylidenecyclohexadiene skeleton prepared in Examples 1 and 2 is a radical. As described above, the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention may be partially a radical.

Example 3
An organic semiconductor element was obtained by the following procedures [1] to [4].
[1] A commercially available transparent glass substrate with indium tin oxide (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 using acetone and isopropanol in this order. 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 a VPS020 manufactured by Sanyu Denshi, purging with oxygen two or three times and then performing oxygen plasma treatment.
[3] The following compound obtained in Example 1 was vapor-deposited with an average thickness of 100 nm on the plasma-treated transparent electrode using a vacuum vapor deposition apparatus.
[4] Aluminum (Al) was vapor-deposited with an average thickness of 100 nm on the organic layer obtained by vapor-depositing the above compound, using a vacuum vapor deposition apparatus to produce an electrode.

When the current-voltage characteristics of the obtained element were measured, the graph shown in FIG. 3 was obtained.
In FIG. 3, each graph shows a current value (Current) with respect to a voltage value (Voltage). In the obtained element, two measurement points (measurement point 1 and measurement point 2) are provided in one element. In FIG. 3, “1-3” and “1-4” are the measurement points 1 respectively. The third and fourth data are represented, and “2-1” to “2-4” represent the first to fourth data of the measurement location 2, respectively. “Ohm” represents ohmic. In the low voltage region, the current-voltage characteristic is a straight line, that is, an ohmic contact.
When calculating the electron mobility by the space charge limited current (SCLC) method from the space charge limited region seen in this graph,
It was estimated to be 6.20 × 10 ⁻⁷ cm ² / Vs.
From this result, it was speculated that characteristics as an n-type organic semiconductor can be expected.
Further, when the impedance was measured using the same element, the data shown in FIG. 4 was obtained.
In FIG. 4, the graph indicated by “C” indicates the capacitance with respect to the frequency (Frequency), and the graph indicated by “R” indicates the resistance value (Resistance) with respect to the frequency (Frequency). The film thickness of the organic layer was 104 nm, and the relative dielectric constant of the compound was estimated to be 4.78 from this and the graph obtained (FIG. 4). This value is extremely high as an organic semiconductor.

From the above examples, it was clarified that the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention has a radical property and the radical is stable. Moreover, it turned out that the compound which has dicyclopentadienylidene cyclohexadiene frame | skeleton of this invention has a high dielectric constant, and can be used suitably as n-type organic-semiconductor material etc. Furthermore, it has been found that the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention has a low LUMO level.

In the above examples, the six dotted arcs in the formula (1) have aromaticity together with a part of the skeleton portion of the 5-membered ring or 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. Although the compound having a ring structure is shown, the compound having the dicyclopentadienylidenecyclohexadiene skeleton of the present invention has a radical property even if the ring structure is not formed. A dielectric constant and a low LUMO level can be achieved, and it can be suitably used as a functional electronic element material such as an n-type organic semiconductor material, particularly an organic thin film solar cell material, an organic transistor material, or the like. Such a mechanism is all the same when the compound having a dicyclopentadienylidenecyclohexadiene skeleton of the present invention is used. Therefore, from the results of the above-described embodiments, the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in the present specification, and advantageous effects can be exhibited. Note that at least one of the six dotted arcs in the formula (1) has aromaticity together with a part of the skeleton portion of the 5-membered ring or 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton. Any material that forms a ring structure can be made radical and stable with a radical.

Claims (11)

A compound having a cyclic structure with an unsaturated bond,
The compound has the following formula (1);

(In the formula, the six dotted arcs may form a ring structure together with a part of the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, and the ring structure X ^{1 to} X ⁶ are the same or different and each represents a hydrogen atom or a monovalent substituent, and each of X ^{1 to} X ^{6 is} dicyclopentadienylidenecyclohexane. When the dotted arc between the 5-membered ring or 6-membered ring skeleton constituting the hexadiene skeleton forms a ring structure together with a part of the 5-membered ring or skeleton of the 6-membered ring, the ring A plurality of bonds may be bonded to the ring structure, and a dotted arc between the five-membered or six-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton When the ring structure is not formed, 5-membered ring or a part of the skeleton portion of the 6-membered ring, the dotted arc is bound to become part of carbon atoms of the ring structure when to form a ring structure .X ¹ and X ² And the dotted dotted arc between the 6-membered skeleton part constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the 6-membered skeleton part form a naphthalene ring, and X ³ to When four dotted arcs between X ⁶ and the five-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton together with a part of the five-membered skeleton form a benzene ring X ^{1 to} X ⁶ each represents a monovalent substituent, and ^{two of} X ¹ and X ² and the skeleton part of the 6-membered ring constituting the dicyclopentadienylidenecyclohexadiene skeleton All dotted arcs are ring structures Not formed, X ³ to X ⁶ and dicyclopentadiene Eni part of the four arcs skeletal portion of both the 5-membered ring of the dotted line between the 5-membered skeleton portion of the ring constituting the dibenzylidene cyclohexadiene skeleton Together with a benzene ring, and when X ^{1 to} X ⁶ contain a chlorine atom, at least one of X ^{1 to} X ⁶ is a hydrogen atom or a monovalent substituent other than a chlorine atom. And a compound having a dicyclopentadienylidenecyclohexadiene skeleton characterized by being represented by: Four dotted arcs between X ^{3 to} X ⁶ in the formula (1) and the five-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are respectively dicyclopentadienylidenecyclohexadiene. 2. The compound having a dicyclopentadienylidenecyclohexadiene skeleton according to claim 1, wherein a ring structure having aromaticity is formed together with a part of a skeleton portion of a 5-membered ring constituting the skeleton. Two dotted arcs between X ¹ and X ² in the formula (1) and the 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton are respectively dicyclopentadienylidenecyclohexadiene. The compound having a dicyclopentadienylidenecyclohexadiene skeleton according to claim 1 or 2, wherein a ring structure having aromaticity is formed together with a part of a skeleton portion of a six-membered ring constituting the skeleton. The dicyclopentadienylidenecyclohexadiene skeleton according to any one of claims 1 to 3, wherein at least one of X ^{1 to} X ⁶ in the formula (1) is a substituent having a reactive group. A compound having A polymer having a cyclic structure with an unsaturated bond,
The polymer is obtained by polymerizing a monomer component containing a compound having a dicyclopentadienylidenecyclohexadiene skeleton and a reactive group,
The compound having a dicyclopentadienylidenecyclohexadiene skeleton and a reactive group is represented by the following formula (2):

(In the formula, the six dotted arcs may form a ring structure together with a part of the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton, and the ring structure X ^{7 to} X ¹² are the same or different and each represents a hydrogen atom or a monovalent substituent, and at least one of X ^{7 to} X ¹² is a reactive group. For each of X ^{7 to} X ¹² , a dotted arc between the 5-membered ring or 6-membered skeleton constituting the dicyclopentadienylidenecyclohexadiene skeleton is the 5-membered ring or When a ring structure is formed together with a part of the skeleton of the 6-membered ring, it may be bonded to the ring structure, and a plurality of each may be bonded to the ring structure: dicyclopentadienylidenecyclohexadiene 5 members constituting the skeleton Alternatively, when a dotted arc between the skeleton part of the 6-membered ring does not form the ring structure, the arc of the dotted line is a part of the skeleton part of the 5-membered ring or the 6-membered ring. A polymer that is bonded to a carbon atom that forms part of the ring structure when forming a structure. A solar cell material comprising: a compound obtained by polymerizing a compound having a dicyclopentadienylidenecyclohexadiene skeleton or a monomer component containing a compound having the skeleton and a reactive group. A solar cell element produced using the solar cell material according to claim 6. An organic transistor material comprising: a compound obtained by polymerizing a compound having a dicyclopentadienylidenecyclohexadiene skeleton or a monomer component containing a compound having the skeleton and a reactive group. An organic transistor element produced using the organic transistor material according to claim 8. A method for producing a compound having a cyclic structure having an unsaturated bond, comprising:
The production method comprises the following formula (i):

(In the formula, two dotted arcs indicate that a ring structure may be formed together with a part of the skeleton of a 6-membered ring, and the ring structure may not be formed. X ¹ , X ² are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ¹ and X ² , a dotted arc between the 6-membered ring skeleton part is one of the 6-membered skeleton parts. In the case of forming a ring structure together with a portion, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. If no form is part of the backbone portion of the 6-membered ring, the dotted arc is bound to become part of carbon atoms of the ring structure when to form a ring structure .R ¹ to R ⁴ are the same or different, monovalent represents a substituent.) unsaturated bond-containing compound represented by the (I), the following (Ii);

(In the formula, a dotted arc represents that a ring structure may be formed together with carbon atoms bonded to each other by a double bond, and the ring structure may not be formed. X ³ , X ⁴ Are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ³ and X ⁴ , a dotted circular arc between carbon atoms bonded to each other by a double bond is In the case of forming a ring structure with bonded carbon atoms, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. In the case where the dotted arc does not form the ring structure, it is bonded to the carbon atoms bonded to each other by the double bond, and R ⁵ and R ⁶ are the same or different and different from R ^{1 to} R ^4. An unsaturated bond-containing compound represented by (II represents a monovalent substituent) When the following formula (iii);

(In the formula, a dotted arc represents that a ring structure may be formed together with carbon atoms bonded to each other by a double bond, or the ring structure may not be formed. X ⁵ , X ⁶ Are the same or different and each represents a hydrogen atom or a monovalent substituent, and for each of X ⁵ and X ⁶ , a dotted circular arc between carbon atoms bonded to each other by a double bond is In the case of forming a ring structure with bonded carbon atoms, the ring structure may be bonded to each other, and a plurality of each may be bonded to the ring structure. In the case where the dotted arc does not form the ring structure, it is bonded to the carbon atoms bonded to each other by the double bond, R ⁷ and R ⁸ are the same or different and different from R ^{1 to} R ^4. An unsaturated bond-containing compound represented by (II represents a monovalent substituent) ) And it comprises a step of reacting,
The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton is characterized in that a compound having a dicyclopentadienylidenecyclohexadiene skeleton is obtained. The method for producing a compound having a dicyclopentadienylidenecyclohexadiene skeleton according to claim 10, wherein R ^{1 to} R ⁸ are a halogen atom, a triflate group, a tosylate group, or a boryl group.

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