WO2014115823A1

WO2014115823A1 - Fluorine-containing aromatic compound, production method therefor, and organic semiconductor material

Info

Publication number: WO2014115823A1
Application number: PCT/JP2014/051424
Authority: WO
Inventors: 山崎　孝; 重之山田; 今日子山本
Original assignee: 旭硝子株式会社
Priority date: 2013-01-28
Filing date: 2014-01-23
Publication date: 2014-07-31
Also published as: JP2016056098A

Abstract

The present invention pertains to a fluorine-containing aromatic compound indicated by formula (1) (in the formula, R^f1 and R^f2 are different groups; R^f1 is a C1-3 linear perfluoroalkyl group; R^f2 is a C2-12 linear perfluoroalkyl group; R can be the same or different and are groups selected from C1-12 monovalent hydrocarbon groups, monovalent aromatic hydrocarbon groups, monovalent heteroaromatic groups, halogen atoms, and hydrogen atoms; m is an integer of at least 0; n is an integer of at least 1; and m+n is 3-6.)

Description

Fluorine-containing aromatic compound, method for producing the same, and organic semiconductor material

The present invention relates to an organic semiconductor material, a novel fluorine-containing aromatic compound useful as the organic semiconductor material, and a method for producing the same. Furthermore, this invention relates to the organic-semiconductor thin film, organic-semiconductor element, and organic-semiconductor transistor containing a fluorine-containing aromatic compound.

In recent years, organic semiconductor elements using organic compounds as semiconductor materials are easier to process than semiconductor elements using conventional inorganic semiconductor materials such as silicon. Has been. Further, since organic compound semiconductor materials are structurally flexible, it is expected to realize devices such as flexible displays by using them in combination with a plastic substrate.

The organic semiconductor processing process includes a dry process by vapor deposition and a wet process using an organic solvent such as coating, printable, and inkjet. Conventional organic semiconductor materials have low solubility in organic solvents, and it has been difficult to apply wet processes, and thus dry processes have been widely used. On the other hand, the wet process is an easy and inexpensive manufacturing process with a low environmental load.

Generally, improvement of carrier mobility is required for organic semiconductor materials. In organic semiconductor materials, effective means have not yet been established as means for improving carrier mobility, but enhancement of intermolecular interaction and control of molecular arrangement are considered important. For example, a condensed polycyclic compound has been tried to be used as an organic semiconductor material because its conjugated system is expanded by a planar structure and has a strong intermolecular interaction due to a π-π stack (Non-patent Document 1).

Among the condensed polycyclic compounds, acene compounds are expected to have excellent functions as organic semiconductor materials. For example, Patent Document 1 discloses a technique for increasing solubility in an organic solvent by introducing a group such as an alkyl group into an acene skeleton in order to use an acene compound as an organic semiconductor material by a wet process. Yes. Patent Document 2 discloses a method for producing an acene compound having a perfluoroalkyl group by a coupling reaction using a heavy metal.

Japanese Unexamined Patent Publication No. 2007-13097 International Publication No. 2011/022678

However, Patent Documents 1 and 2 do not disclose any acene-based condensed polycyclic compounds having a skeleton as in the present invention.

The present invention provides an acene-type condensed polycyclic compound having a structure that can be applied to both a dry process and a wet process and has a high carrier mobility, a method for producing the same, and an organic semiconductor material containing the compound The purpose is to do.

The present inventors have newly found a fluorine-containing aromatic compound having a specific structure that is relatively soluble in a low-polar solvent, and completed the present invention.

That is, the present invention relates to the following <1> to <10>.
<1> A fluorine-containing aromatic compound represented by the following formula (1).

[In the above formula, R ^f1 and R ^f2 are groups different from each other, R ^f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R ^f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is a group.
R may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. It is a group. When a hydrogen atom bonded to a carbon atom is present in the R, at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be substituted with a group selected from a perfluoroalkyl group and a phenyl group.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6. ]
<2> The fluorine-containing aromatic compound according to <1>, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

[However, the symbols in the formula have the same meaning as described above. ]
<3> The fluorine-containing aromatic compound according to <1>, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-11).

[However, the symbols in the formula have the same meaning as described above. ]
<4> An organic semiconductor material comprising the fluorine-containing aromatic compound according to any one of the above items <1> to <3>.
<5> An organic semiconductor thin film composed of the organic semiconductor material according to <4>.
<6> An organic semiconductor thin film made of the organic semiconductor material according to <4> and having crystallinity.
<7> An organic semiconductor element in which the organic semiconductor thin film according to <5> or <6> is formed on a substrate.
<8> A transistor comprising a gate electrode, a dielectric layer, a source electrode, a drain electrode, and a semiconductor layer, wherein the semiconductor layer is composed of the organic semiconductor thin film according to <5> or <6>.
<9> A compound represented by the following formula (2) is reacted with a compound represented by the formula R ^f1 —Si (CH ₃ ) ₃ to obtain a compound represented by the following formula (3). A compound represented by the following formula (4) is obtained by reacting a compound represented by the formula (3) with a compound represented by the formula R ^f2 -X. Next, the compound represented by the formula (4) is obtained. A method for producing a fluorine-containing aromatic compound represented by the following formula (1), wherein a deprotection reaction and an aromatization reaction are performed on the compound.

[In the above formula, R ^f1 and R ^f2 are groups different from each other, R ^f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R ^f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is a group.
R may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. It is a group. When a hydrogen atom bonded to a carbon atom is present in the R, at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be substituted with a group selected from a perfluoroalkyl group and a phenyl group.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6.
X is an iodine atom or a bromine atom. ]
<10> A compound represented by the following formula (2A) is reacted with a compound represented by the formula R ^f1 —Si (CH ₃ ) ₃ to obtain a compound represented by the following formula (3A). The compound represented by the formula (3A) and the compound represented by the formula R ^f2 -X are reacted to obtain a compound represented by the following formula (4A). Next, the compound represented by the formula (4A) is represented. The compound represented by the following formula (1A) is obtained by performing a deprotection reaction and an aromatization reaction on the compound, and then R ^A is a halogen atom in the compound represented by the formula (1A). ^A method for producing a compound represented by the following formula (1B), wherein ^B is substituted.

[In the above formula, R ^f1 and R ^f2 are groups different from each other, R ^f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R ^f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is a group.
R ^A may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. One or more of R ^A represents a halogen atom. When a hydrogen atom bonded to a carbon atom is present in the ^RA , at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. The perfluoroalkyl group and a group selected from phenyl groups may be substituted.
R ^B is a group corresponding to R ^A, is R ^B corresponding to R ^A is a halogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, monovalent aromatic hydrocarbon group, a monovalent heteroaromatic And a group selected from a halogen atom. The If there is a hydrogen atom bonded to the carbon atom in R ^B, 1 or more alkyl groups of 1 to 6 carbon atoms hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, 1 to 6 carbon atoms The perfluoroalkyl group and a group selected from phenyl groups may be substituted.
R ^B corresponding to R ^A other than a halogen atom is the same group as R ^A.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6.
X is an iodine atom or a bromine atom. ]

The fluorine-containing aromatic compound of the present invention is a compound in which a fluorine-containing alkyl group is introduced into a carbon atom forming an aromatic skeleton, and is a compound having high solubility in an organic solvent. For this reason, in the manufacture of the organic semiconductor material, it is possible to manufacture using a wet process. Furthermore, since the fluorine-containing alkyl group is an electron-attracting group, the cohesive force becomes strong and the intermolecular interaction is strengthened based on the fluorophyric effect, so that it exhibits high carrier mobility as an organic semiconductor material.
That is, the organic semiconductor material using the fluorine-containing aromatic compound of the present invention can form a high-performance organic semiconductor thin film and can be applied to an organic semiconductor element.

FIG. 1 is a graph showing measurement results of output characteristics of the compound (e4). FIG. 2 is a diagram showing an Out-of-plane X-ray diffraction pattern of a vapor-deposited thin film of compound (e4).

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
In the present specification, the compound represented by the formula (X) is also referred to as “compound (X)”.
In this specification, weight% and mass% are treated as synonymous.

<Fluorine-containing aromatic compound>
The fluorine-containing aromatic compound according to the present invention is represented by the following formula (1).

In the above formula, R ^f1 and R ^f2 are groups different from each other, R ^f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R ^f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is.
R may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. It is a group. When a hydrogen atom bonded to a carbon atom is present in the R, at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be substituted with a group selected from a perfluoroalkyl group and a phenyl group.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited. When there are a plurality of each of the ring structures A and B, they may be connected in a block shape or may be bonded at random.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6.

The fluorine-containing aromatic compound according to the present invention has different linear perfluoroalkyl groups R ^f1 and R ^f2 in the minor axis direction of the compound, that is, the direction perpendicular to the condensation direction of the aromatic ring. The perfluoroalkyl group refers to a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. In the condensed polycyclic compound, intermolecular interaction due to π-π stacking increases as the number of condensed rings increases, and an increase in carrier mobility is expected. On the other hand, strong intermolecular interactions also lead to a decrease in solubility in organic solvents.
The compound of the present invention drastically improved the solubility in an organic solvent by introducing one or more pairs of R ^f1 and R ^f2 which are such linear perfluoroalkyl groups into the molecule. Also, R ^f1 and R ^f2 are in a para-position, which means that when a fluorine-containing aromatic compound is used as an organic semiconductor material, the orientation with respect to the substrate is improved and the crystallinity of the thin film To preferred. Further, the perfluoroalkyl group is preferably linear, from the viewpoint of improving the intermolecular interaction due to the interaction of fluorine atoms.

If the perfluoroalkyl group has too many carbon atoms, it tends to weaken the intermolecular interaction between the condensed rings due to steric hindrance. In order to improve the solubility of the acene compound in the organic solvent without impairing the strong intermolecular interaction due to π-π stacking, the carbon number of the perfluoroalkyl group is R ^f1 of 1 to 3, and R ^f2 is 2-12. Further, from the viewpoint of the balance between the intermolecular interaction and the improvement in solubility, the carbon number of R ^f1 is preferably 1 to 3, and R ^f2 is preferably 2 to 10.

A plurality of R in the formula may be the same or different from each other, and are a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, And a group selected from a hydrogen atom.
The monovalent hydrocarbon group having 1 to 12 carbon atoms is preferably an alkyl group, an alkoxy group, an alkenyl group, or an alkynyl group from the viewpoint of improving solubility.
The monovalent aromatic hydrocarbon group is preferably a phenyl group, an aryl group, a 2-thienyl group, or a 3-thienyl group from the viewpoint of improving solubility.
As the halogen atom, a bromine atom and an iodine atom are preferable from the viewpoint that they can be converted into other substituents and can impart a function according to the purpose to the fluorinated aromatic compound.
If at least one of R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, or a monovalent heteroaromatic group, the solubility in an organic solvent can be further improved. it can.
When at least one of R is a halogen atom, the halogen atom can be further converted into a substituent having a desired function, and a function according to the purpose can be imparted to the fluorinated aromatic compound. Examples of the substituent to be converted include the aforementioned monovalent hydrocarbon group having 1 to 12 carbon atoms, monovalent aromatic hydrocarbon group, monovalent heteroaromatic group and the like.
Further, when a hydrogen atom bonded to a carbon atom is present in R, at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, It may be substituted with a group selected from 6 perfluoroalkyl groups and a phenyl group. Thus, the structure of R can be variously selected according to the purpose.

A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the number of repetitions of the benzene ring structure A, and is an integer of 0 or more, preferably 1 to 2.
n is the repeating number of the benzene ring structure B, and is an integer of 1 or more, preferably 1 or 2.
m + n is an integer of 3 to 6, preferably 3 to 5.

The fluorine-containing aromatic compound according to the present invention is preferably a compound represented by the following formula (1-1). However, the symbols in the formula have the same meaning as described above.

Furthermore, the fluorine-containing aromatic compound according to the present invention is preferably a compound represented by the following formula (1-10) to the following formula (1-12). However, the symbols in the formula have the same meaning as described above. Formula (1-10) is a compound wherein m is 2 and n is 1, Formula (1-11) is a compound where m is 4 and n is 1, Formula (1-12) is a compound where m is 3 This corresponds to a compound in which n is 2.

Specific examples of the fluorine-containing aromatic compound according to the present invention include the following compounds in which R is a hydrogen atom.

The fluorine-containing aromatic compound in the present invention is useful as an organic semiconductor material because it has a high carrier mobility. In addition, because it has good solubility in organic solvents, it can be formed in large quantities with high-performance organic semiconductor thin films using a wet process that is simple and does not damage the substrate. An organic semiconductor element and an organic semiconductor device can be obtained.

<Method for producing fluorine-containing aromatic compound>
The fluorine-containing aromatic compound of the present invention can be produced by the route shown below. That is, a compound represented by the following formula (2) is reacted with a compound represented by the formula R ^f1 —Si (CH ₃ ) ₃ to obtain a compound represented by the following formula (3). A compound represented by the following formula (4) is obtained by reacting a compound represented by the formula (3) with a compound represented by the formula R ^f2 —X, and then represented by the formula (4). It can manufacture by performing the deprotection reaction in a compound, obtaining the compound represented by the following Formula (5), and performing the aromatization reaction of the compound represented by this Formula (5).

The meanings and preferred embodiments of the symbols in the above formula are the same as the above-mentioned meanings and preferred embodiments. X is an iodine atom or a bromine atom, and an iodine atom is preferable in terms of a good yield.

According to the above production method, each of the keto groups in the para-position can be converted step by step into a perfluoroalkyl group, so that perfluoroalkyl groups R ^f1 and R ^f2 having different structures can be introduced into the acene compound. .

When one or more of R in the compound (1) is a halogen atom, the halogen atom may be converted into another substituent. That is, a compound represented by the following formula (2A) is reacted with a compound represented by the formula R ^f1 —Si (CH ₃ ) ₃ to obtain a compound represented by the following formula (3A). A compound represented by the following formula (4A) is obtained by reacting a compound represented by the formula (3A) with a compound represented by the formula R ^f2 —X, and then represented by the formula (4A). A deprotection reaction is performed on the compound to obtain a compound represented by the following formula (5A), an aromatization reaction is performed on the compound represented by the formula (5A), and a halogen atom is essential. Next, by substituting R ^B for R ^A which is a halogen atom in the compound represented by the formula (1A), a compound represented by the formula (1B) is obtained. A fluorine-containing aromatic compound can be produced.

The meanings and preferred embodiments of the symbols in the above formula are the same as described above.
A plurality of R ^A may be the same or different and each is a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom And one or more of R ^A represents a halogen atom. When a hydrogen atom bonded to a carbon atom is present in the ^RA , at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A perfluoroalkyl group and a group selected from phenyl groups.
For R ^B is R ^B corresponding to R ^A is a halogen atom, selected monovalent hydrocarbon group having 1 to 12 carbon atoms, monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, and a halogen atom Group. The If there is a hydrogen atom bonded to the carbon atom in R ^B, 1 or more alkyl groups of 1 to 6 carbon atoms hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, 1 to 6 carbon atoms A perfluoroalkyl group and a group selected from phenyl groups. R ^B corresponding to R ^A other than a halogen atom is the same group as R ^A.

A known quinone compound can be used as the starting compound (2) and compound (2A) (hereinafter, the two compounds are collectively referred to as “compound (2)”). For example, 9,10-anthraquinone, 2-bromo-9,10-anthraquinone, 2-iodo-9,10-anthraquinone, 2,6-dibromo-9,10-anthraquinone, 2,6-diiodo-9,10- And anthraquinone, 6,13-pentacenequinone, 5,7,12,14-tetrahydropentacene-5,7,12,14-tetraone, and the like.
As the compound (2), the following compounds are preferable.

The compound represented by the formula R ^f1 —Si (CH ₃ ) ₃ (hereinafter also referred to as “R ^f1 TMS”) to be reacted with the quinone compound (2) is a commercially available compound or a known production method. It can obtain by manufacturing with.
In the production method of the present invention, R ^f1 TMS is added in an amount of 1.0 to 2.0 mol and cesium fluoride is added in an amount of 0.1 to 1 mol with respect to 1 mol of the compound (2). It is preferable to react at 1-30 ° C. for 1-5 hours to obtain compound (3). According to this condition, compound (3) in which only one of the keto groups is converted is obtained. As the organic solvent, tetrahydrofuran, diethyl ether and the like are preferable.

The compound represented by the formula R ^f2 —X to be reacted with the compound (3) can also be obtained from a commercially available compound or by producing it by a known production method.
In the production method of the present invention, 1.0 to 3.0 mol of R ^f2 -X and 1.0 to 3.0 mol of MeLi-LiBr are added to 1 mol of the compound (3), and the mixture is added in an organic solvent. The compound (4) is preferably obtained by reacting at a temperature of −80 ° C. or lower for 1 to 5 hours. According to this condition, the other of the keto group is also converted to obtain compound (4). As the organic solvent, tetrahydrofuran, diethyl ether and the like are preferable.

Next, the compound (5) is obtained by deprotecting the trimethylsilyl group (TMS group) of the compound (4). The reaction is preferably performed by a deprotection reaction by acid treatment using concentrated hydrochloric acid. The reaction is particularly preferably carried out by reacting with 1 to 20 mol of concentrated hydrochloric acid per 1 mol of compound (4) in an organic solvent under reflux for 3 to 24 hours. As the organic solvent, a water-soluble organic solvent is preferable, and ethanol and tetrahydrofuran are particularly preferable.
This deprotection of the TMS group can also be carried out using a fluoride source such as tetrabutylammonium fluoride. In this case, it is preferable to use a method in which 1 to 5 mol of tetrabutylammonium fluoride is added to 1 g of the compound (4) and reacted in an organic solvent at a temperature of about 0 ° C. for 0.5 to 5 hours.

Subsequently, the compound (5) is aromatized via elimination of the hydroxyl group to obtain the compound (1). The reaction conditions for the reaction are not limited, but in order to avoid contamination of the metal in the final product as much as possible, a reaction using a heavy metal (for example, tin chloride) used in a general aromatization reaction is not adopted. preferable. Examples of the reaction without using a heavy metal include a reaction by heat treatment at 220 ° C. or higher in a vacuum and a reaction using triphenylphosphine / carbon tetrabromide.
In the latter reaction, 3 to 10 mol of carbon tetrabromide and 2 to 10 mol of triphenylphosphine are added to 1 g of compound (5), and the mixture is refluxed at 10 to 40 ° C. in an organic solvent. It is preferable to employ a method of reacting for 3 to 24 hours. The organic solvent is preferably a chlorinated solvent, and examples thereof include dichloromethane, chloroform, and carbon tetrachloride. Dichloromethane is particularly preferred.
The obtained compound (1) becomes the fluorine-containing aromatic compound (1) of the present invention and can be used for the intended use.

Furthermore, when one or more of R in the compound (1) is a halogen atom (that is, in the case of the compound (1A) in which R is R ^A ), the halogen atom R ^A in the compound (1A) is substituted with R ^B , Can be derived into compound (1B). As the substitution reaction, a known reaction for producing a C—C bond from a C—X bond can be employed. For example, a Suzuki coupling reaction or a Sonogashira coupling reaction is preferable.

<Organic semiconductor materials>
The fluorine-containing aromatic compound of the present invention can be used as various functional materials, and is particularly a compound that can be usefully used as an organic semiconductor material.
The organic semiconductor material is a material that contains the fluorine-containing aromatic compound of the present invention and can be used for an organic semiconductor. The organic semiconductor material may be a material composed only of a fluorine-containing aromatic compound, or may be a material including a fluorine-containing aromatic compound and another material. Other materials include other organic semiconductor materials, various dopants, and the like. As the dopant, for example, when used as a light emitting layer of an organic EL device, coumarin, quinacridone, rubrene, stilbene derivatives, fluorescent dyes, and the like can be used.

In the fluorine-containing aromatic compound of the present invention, adjacent molecules aggregate due to the affinity between perfluoroalkyl groups (this effect is referred to as a fluorophyric effect), and contribute to more efficient charge transfer. Therefore, by using the fluorine-containing aromatic compound of the present invention, it is possible to produce an organic semiconductor thin film having high carrier mobility and an electronic device such as a transistor using the organic semiconductor thin film.

In contrast to the fluorine-containing aromatic compound of the present invention, anthracene and pentacene that do not have a perfluoroalkyl group behave as a p-type semiconductor when gold is used for the electrode. However, since the perfluoroalkyl group which is an electron withdrawing substituent is introduced into the fluorine-containing aromatic compound of the present invention, the conductivity can be changed depending on the substituent. Therefore, the fluorine-containing compound of the present invention can change the electron transition energy by a perfluoroalkyl group present in a part of the skeleton, can control the conductivity type, and can be a preferable material as an organic semiconductor material.

<Organic semiconductor thin film>
The organic semiconductor material according to the present invention can form a film on an organic semiconductor on a substrate using a dry process or a wet process according to a normal manufacturing method. Examples of the film include a thin film, a thick film, and a film having crystallinity.

When a thin film is formed by a dry process, a known method such as a vacuum deposition method, an MBE (Molecular Beam Epitaxy) method, a sputtering method, a laser deposition method, or a vapor transport growth method can be used.
Since these thin films and the like function as charge transporting members for various functional elements such as photoelectric conversion elements, thin film transistor elements, and light emitting elements, various electronic devices having the thin films can be manufactured.

In the case of forming a thin film using a vacuum deposition method, an MBE method, or a vapor transport growth method as a dry process, a vapor obtained by heating and sublimating an organic semiconductor material is used in a high vacuum, a vacuum, a low vacuum, or a normal vacuum. It is transported to the substrate surface by pressure. The thin film can be formed according to known methods and conditions. Specifically, the substrate temperature is preferably 20 to 200 ° C., and the thin film growth rate is preferably 0.001 to 1000 nm / sec. By setting it as this condition, a film having crystallinity and a thin surface smoothness can be formed.
When the substrate temperature is low, the thin film tends to be amorphous, and when the substrate temperature is high, the surface smoothness of the thin film tends to decrease. Further, if the growth rate of the thin film is slow, the crystallinity tends to decrease, and if it is too fast, the surface smoothness of the thin film tends to decrease.

When forming a thin film by a wet process, an organic semiconductor thin film can be formed by covering a substrate with a solution obtained by dissolving an organic semiconductor material containing a fluorine-containing aromatic compound in an organic solvent.
The fluorine-containing aromatic compound of the present invention is a compound having an advantage that the solubility in an organic solvent is improved as compared with a conventional organic semiconductor material and a wet process can be applied. The reason is that the organic semiconductor material according to the present invention exhibits lipophilicity due to the presence of the perfluoroalkyl group in the fluorine-containing compound, and thus becomes soluble in various organic solvents. Therefore, the organic semiconductor material according to the present invention can be applied with a wet process, and can be processed without damaging the semiconductor material.

Examples of the film forming method (method for coating the substrate) in the wet process include coating, spraying, and contact. Specific examples include known methods such as spin coating, casting, dip coating, ink jet, doctor blade, screen printing, and dispensing. Moreover, when taking the form of a flat crystal or a thick film state, a casting method or the like can be adopted. It is preferable to select a combination suitable for the device to be produced for the film forming method and the organic solvent.

In the wet process, crystal growth can be controlled by applying at least one selected from a temperature gradient, an electric field, and a magnetic field to the interface between the solution of the fluorine-containing aromatic compound and the substrate. By adopting this method, a highly crystalline organic semiconductor thin film can be produced, and excellent semiconductor characteristics based on the performance of the highly crystalline thin film can be obtained. In addition, a high crystalline organic semiconductor thin film can be manufactured by controlling the vapor pressure in solvent drying by making the environmental atmosphere a solvent atmosphere during wet process film formation.

Examples of organic solvents that can dissolve fluorine-containing aromatic compounds in the wet process include aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; aromatics such as benzene, toluene, and xylene. Examples of non-halogen solvents such as group hydrocarbons; ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane; alcohols such as methanol, ethanol and 2-propanol; or mixtures thereof It is done.

Examples of the halogen-containing solvent include chlorinated hydrocarbons, fluorinated hydrocarbons, chlorinated fluorinated hydrocarbons, and fluorine-containing ether compounds. Specifically, methylene chloride, chloroform, 2,3,3-trichloroheptafluorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1- Dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, carbon tetrachloride, 1,2-dichloroethane, dichloropentafluoropropane NC ₆ F ₁₃ -C ₂ H ₅ , nC ₄ F ₉ OCH ₃ , nC ₄ F ₉ OC ₂ H _{5 and the} like.
A solvent may use only 1 type or may use 2 or more types together. When using 2 or more types together, it is preferable to use a non-halogen type solvent and a halogen-containing solvent together, and the solvent which mixed these in arbitrary ratios is preferable.

When the fluorine-containing aromatic compound in the present invention is dissolved in an organic solvent and a wet process is performed, the amount of the organic semiconductor material dissolved in the organic solvent is preferably 0.01% by weight or more from the viewpoint of work efficiency, About 0.2% by weight is more preferable. Further, the amount of the organic semiconductor material in the organic solvent is preferably 0.01 to 10% by weight, and particularly preferably 0.2 to 10% by weight.
In addition, since the fluorine-containing aromatic compound of the present invention is excellent in solubility in an organic solvent, the fluorine-containing aromatic compound obtained by the above production method can be highly purified by a simple purification method such as column chromatography or recrystallization. May be.

The substrate surface can be coated by a wet process in the air or in an inert gas atmosphere. In particular, when the solution of the semiconductor material is easily oxidized, it is preferably in an inert gas atmosphere, and nitrogen, argon, or the like can be used.
After coating the substrate surface, the organic semiconductor thin film is formed by volatilizing the solvent. If the residual amount of the solvent in the thin film is large, the stability of the thin film and the semiconductor properties may be deteriorated. Therefore, it is preferable to remove the remaining solvent by performing heat treatment or reduced pressure treatment again after the thin film is formed. .

The shape of the substrate that can be used in the wet process is not particularly limited, and a sheet-like substrate or a plate-like substrate is usually preferable. The material used for the substrate is not particularly limited, and examples thereof include ceramics, metal substrates, semiconductors, resins, paper, and nonwoven fabrics.

Examples of when the substrate is a ceramic substrate include substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, and silicon carbide. Examples of the metal substrate include gold, copper, and silver substrates. Examples of the semiconductor substrate include silicon (crystalline silicon, amorphous silicon), germanium, gallium arsenide, gallium phosphide, gallium nitride, and the like. Polyester, polyethylene, polypropylene, polyvinyl, polyvinyl alcohol, ethylene vinyl alcohol copolymer, cyclic polyolefin, polyimide, polyamide, polystyrene, polycarbonate, polyether sulfone, polysulfone, polymethyl methacrylate, polyethylene terephthalate, triacetyl Examples of the substrate include cellulose and norbornene.

The organic semiconductor thin film using the fluorine-containing aromatic compound can be a crystalline thin film. A crystalline thin film is preferable from the viewpoint that high carrier mobility can be expected due to high crystallinity and thereby excellent organic semiconductor device characteristics are exhibited.
The crystalline state of the thin film can be known by oblique incidence X-ray diffraction measurement of the thin film, transmission electron diffraction, or a method of measuring diffraction by making X-rays incident on the edge of the thin film. In particular, oblique incidence X-ray diffraction, which is a crystal analysis technique in the thin film field, is used. In X-ray diffraction, there are an Out-of-plane XRD method and an In-plane XRD method depending on the direction of the lattice plane to be measured. The Out-of-plane XRD method is a method for observing a lattice plane parallel to the substrate. The In-plane XRD method is a method for observing a lattice plane perpendicular to the substrate. That the thin film is crystalline means that a diffraction peak derived from the organic semiconductor material forming the thin film is observed. Specifically, diffraction based on crystal lattice of organic semiconductor material, diffraction derived from molecular length, or characteristic diffraction peak appearing when molecules have alignment parallel or perpendicular to the substrate are observed. Means that. In the case of a non-crystalline film, this diffraction is not observed, which means that the thin film in which the diffraction peak appears is a crystalline thin film.

The thickness of the organic semiconductor thin film layer used in the organic semiconductor element is usually preferably 10 to 1,000 nm.

<Organic semiconductor element, organic semiconductor transistor>
The fluorine-containing aromatic compound in the present invention has a high carrier mobility. Therefore, an organic semiconductor material containing a fluorine-containing aromatic compound can form an organic semiconductor thin film without impairing the high carrier mobility of the fluorine-containing compound.
An organic semiconductor element including a semiconductor layer formed by laminating layers of organic semiconductor thin films is very useful for various semiconductor devices.

Examples of semiconductor devices include organic semiconductor transistors, organic semiconductor lasers, organic photoelectric conversion devices, and organic molecular memories. Among these, an organic semiconductor transistor is preferable as the semiconductor device, and a field effect transistor (FET) is more preferable.

An organic semiconductor transistor is usually composed of a substrate, a gate electrode, an insulator layer (dielectric layer), a source electrode, a drain electrode, and a semiconductor layer. In addition, a back gate or a bulk may be included.
There are no particular restrictions on the order in which the components in the organic semiconductor transistor are arranged. Further, among the above components, a plurality of gate electrodes, source electrodes, drain electrodes, and semiconductor layers may be provided. When there are a plurality of semiconductor layers, they may be provided in the same plane or stacked.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

(Evaluation methods)
In the examples, the structures of the synthesized compounds were identified by the following analysis methods and analysis conditions.

Nuclear magnetic resonance analysis was performed using a Fourier transform high resolution nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL.
¹ H NMR (300 MHz) Solvent: chloroform-d (CDCl ₃ ), methanol-d ₄ (CD ₃ OD) or acetone-d ₆ (acetone-d ₆ ). Internal standard: Tetramethylsilane (TMS).
¹³ C NMR (75 MHz) Solvent: chloroform-d (CDCl ₃ ), methanol-d ₄ (CD ₃ OD) or acetone-d ₆ (acetone-d ₆ ). Internal standard: Chloroform-d (CDCl ₃ ).
¹⁹ F NMR (283 MHz) Solvent: chloroform-d (CDCl ₃ ), methanol-d ₄ (CD ₃ OD) or acetone-d ₆ (acetone-d ₆ ). Internal standard: hexafluorobenzene (C ₆ F ₆ ) was set to −163 ppm (CFCl ₃ was set to 0 ppm).

For infrared absorption spectroscopy, Fourier transform infrared spectrophotometer (FT-IR), FT / IR-4100 manufactured by JASCO Corporation was used. For elemental analysis, a fully automatic elemental analyzer 2400 series II manufactured by PerkinElmer was used. For the melting point measurement, a melting point measuring device MP-21 manufactured by Yamato Kagaku was used.

<Example 1>
(1) Synthesis of Compound (a1) (9- (Trifluoromethyl) -9- (trimethylsilyl) anthrcen-10-one) CsF (0.304 g, 2.0 mmol) was added to a 300 mL three-necked flask and dried by heating. Replacement was performed. THF (150 mL) and anthracene-9,10-dione (4.164 g, 20.0 mmol) were added, and TMSCF ₃ (3.55 mL, 24.0 mmol) dissolved in THF (25 mL) was slowly added dropwise using a dropping funnel. did. After stirring at room temperature for 3 hours, the reaction was quenched with saturated aqueous NH ₄ Cl and extracted with ethyl acetate. The organic layer was dried over anhydrous Na ₂ SO ₄ and the solvent was removed. The product was isolated and purified by column chromatography (developing solvent hexane: CH ₂ Cl ₂ = 2: 1) to obtain the target compound (a1) as a white solid (6.311 g, 18.0 mmol, yield 90%). .

(result of analysis)
M.M. P. 84-86 ° C.
¹ H NMR (CDCl ₃ ) δ −0.09 (s, 9H), 7.63 (td, 2H, J = 7.6, 0.9 Hz), 7.74 (td, 2H, J = 7.2) 1.8 Hz), 8.15 (dt, 2H, J = 6.3, 1.5 Hz), 8.34 (dd, 2H, J = 7.8, 1.2 Hz).
¹⁹ F NMR (CDCl ₃ ) δ −81.66 (s).
¹³ C NMR (CDCl ₃ ) δ 1.7, 74.6 (q, J = 29.8 Hz), 123.8 (q, J = 286.6 Hz), 127.5, 129.0 (d, J = 1.8 Hz), 129.9, 131.4, 133.0, 139.0, 182.7.
IR (KBr) ν 3006, 2971, 2905, 1668, 1599, 1457, 1253, 1082, 956, 818, 712, 679 cm ⁻¹ .
_{HRMS (APCI) Calcd for (M} + H) C 18 H 17 F 12 O 2 Si: 350.1028, Found 349.1008.

(2) Synthesis of Compound (a2) (9- (Nonafluorbutyl) -10- (trifluoromethyl) -10- (trimethylsilyl) anthracen-9-ol) Compound (a1) (0.350 g (0.350 g) 1.0 mmol)), diethyl ether (10 mL), CF ₃ (CF ₂ ) ₂ CF ₂ I (0.36 mL (2.1 mmol)) were added, and the mixture was cooled to −80 ° C. A 1.5 M MeLi-LiBr ether solution (1.33 mL (2.0 mmol)) was slowly added dropwise using a dropping funnel, followed by stirring at 80 ° C. for 2 hours. 1N HCl aqueous solution was added to stop the reaction, extraction was performed with ethyl acetate, and the organic layer was dried over anhydrous Na ₂ SO ₄ . After concentration under reduced pressure, isolation and purification were performed by column chromatography (developing solvent hexane: CH ₂ Cl ₂ = 2: 1) to obtain the target compound (a2) as a white solid (0.449 g, 0. 79 mmol, yield 79%).

(result of analysis)
M.M. P. 99-101 ° C.
¹ H NMR (CDCl ₃ ) δ 0.03 (s, 9H), 2.98 (s, 1H), 7.50-7.60 (m, 4H), 7.91-7.98 (m, 2H) ), 8.00-8.09 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −81.55 (s, 3F), −82.21 (t, J = 9.0 Hz, 3F), −116.49 (m, 2F), −120.15 (m , 2F), -127.28 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 1.8, 74.2 (tt, J = 19.8, 1.8 Hz), 76.0 (q, J = 27.3 Hz), 124.1 (q, J = 289.0 Hz), 128.6 (tt, J = 5.6, 1.8 Hz), 129.0, 129.5, 129.6, 132.8, 133.4.
IR (KBr) ν 3589, 3563, 2963, 1449, 1357, 1235, 1170, 940, 878, 763 cm ⁻¹ .
HRMS (FAB) Calcd for (M−H) C ₂₂ H ₁₇ F ₁₂ O ₂ Si: 569.0806, Found 569.0824.

(3) Synthesis of Compound (a3) (9- (Nonafluorbutyl) -10- (trifluoromethyl) anthracene-9,10-diol) To a 30 mL two-necked eggplant type flask equipped with a Dimroth condenser, compound (a2) .506 g (0.89 mmol)), THF (5 mL) and concentrated hydrochloric acid (0.5 mL) were added, and the mixture was refluxed for 3 hours. After extraction with ethyl acetate, the organic layer was dried over anhydrous Na ₂ SO ₄ and then concentrated under reduced pressure. Isolation and purification were performed by column chromatography (developing solvent hexane: CH ₂ Cl ₂ = 2: 1) to obtain the target compound (a3) as a white solid (0.351 g, 0.71 mmol, yield 79%). .

(result of analysis)
M.M. P. 118-120 ° C.
¹ H NMR (CDCl ₃ ) δ 2.88 (s, 1H), 3.15 (d, J = 1.2 Hz, 1H), 7.55-7.63 (m, 4H), 8.00-8 .08 (m, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.19 (s, 3F), −82.19 (t, J = 9.0 Hz, 3F), −119.32 (m, 2F), −121.64 (m , 2F), -127.47 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 73.3 (q, J = 27.9 Hz), 73.7 (tt, J = 18.6, 2.5 Hz), 124.0 (q, J = 287.8 Hz) , 128.3 (q, J = 3.1 Hz), 128.4 (t, J = 5.6 Hz), 129.8, 129.9, 132.6, 132.8.
IR (KBr) ν 3610, 3481, 3083, 1450, 1363, 1202, 1185, 1135, 1026, 804, 767 cm ⁻¹ .
HRMS (FAB) Calcd for (M−H) C ₁₉ H ₉ F ₁₂ O ₂ : 497.0411, Found 497.0401.

(4) Synthesis of Compound (a4) (9- (Nonafluorbutyl) -10- (Trifluoromethyl) anthracene) Compound (a3) (0.232 g (0.47 mmol)), Four Carbon bromide (0.468 g (1.4 mmol)) was added and dissolved in 5 mL of CH ₂ Cl ₂ . Triphenylphosphine (0.551 g (2.1 mmol)) was added and stirred at room temperature for 15 hours, and then the reaction was stopped by adding a saturated aqueous NH ₄ Cl solution. After extraction with CH ₂ Cl ₂ , the organic layer was dried over anhydrous Na ₂ SO ₄ and then concentrated under reduced pressure. Isolation and purification were performed from column chromatography (developing solvent hexane) to obtain the target compound (a4) as a yellow solid (0.205 g, 0.44 mmol, yield 93%).

(result of analysis)
M.M. P. 89-91 ° C.
¹ H NMR (CDCl ₃ ) δ 7.57-7.65 (m, 4H), 8.35-8.45 (m, 2H), 8.50-8.55 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −49.62 (s, 3F), −81.87 (t, J = 9.0 Hz, 3F), −93.04 (t, J = 16.1 Hz, 2F), −119.39 (q, J = 11.6 Hz, 2F), −126.86 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 124.8 (q, J = 6.3 Hz), 125.4 (tt, J = 9.9, 4.3 Hz), 125.6 (q, J = 277.9 Hz) , 126.4, 126.9 (q, J = 1.2 Hz), 127.2 (t, J = 2.3 Hz), 129.4, 131.0 (t, J = 2.5 Hz).
IR (KBr) ν 3155, 3100, 3052, 1350, 1290, 1238, 1134, 1032, 932, 829, 765 cm ⁻¹ .
HRMS (FAB) Calcd for (M +) C ₁₉ H ₈ F ₁₂ : 464.0434, Found 464.0402.

<Example 2>
(1) Synthesis of Compound (b2) (9- (Tridecafluorohexyl) -10- (trifluoromethyl) -10- (trimethylsilyl) anthracen-9-ol) In the synthesis of Compound (a2), CF ₃ (CF ₂ ) ₂ CF ₂ The target compound (b2) was obtained as a white solid in the same manner except that I was changed to CF ₃ (CF ₂ ) ₄ CF ₂ I (0.456 g, 0.68 mmol, yield 68%).

(result of analysis)
M.M. P. 58-60 ° C.
¹ H NMR (CDCl ₃ ) δ 0.04 (s, 9H), 3.01 (s, 1H), 7.50-7.60 (m, 4H), 7.91-8.00 (m, 2H) ), 8.03-8.09 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −81.62 (s, 3F), −82.17 (t, J = 9.0 Hz, 3F), −116.45 (m, 2F), −119.28 (m , 2F), -123.11 (brs, 2F), -124.20 (brs, 2F), -127.449 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 2.3, 74.6 (tt, J = 19.8, 1.9 Hz), 76.4 (q, J = 27.9 Hz), 124.5 (q, J = 289.0 Hz), 129.0 (tt, J = 5.6, 1.2 Hz), 129.4, 129.9, 130.0, 133.2, 133.8.
IR (KBr) ν 3585, 3445, 2966, 1237, 1198, 1151, 1032, 937, 848, 761 cm ⁻¹ .
_{HRMS (APCI) Calcd for (M} +) C 24 H 17 F 16 O 2 Si: 670.0821, Found 669.0778.

(2) Synthesis of Compound (b3) (9- (Tridecafluorohexyl) -10- (trifluoromethyl) anthracen-9,10-diol) In the synthesis of Compound (a3), Compound (a2) was changed to Compound (b2) Similarly, the target compound (b3) was obtained as a white solid (0.409 g, 0.68 mmol, yield 77%).

(result of analysis)
M.M. P. 91-93 ° C.
¹ H NMR (CDCl ₃ ) δ 2.88 (d, J = 3.0 Hz, 1H), 3.16 (dd, J = 3.9, 1.2 Hz, 1H), 7.58-7.63 ( m, 4H), 8.01-8.07 (m, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.17 (s, 3F), −82.17 (t, J = 9.0 Hz, 3F), −119.15 (m, 2F), −120.06 (m , 2F), −123.28 (brs, 2F), −124.15 (brs, 2F), −127.56 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 73.2 (q, J = 27.9 Hz), 73.7 (tt, J = 19.2, 1.8 Hz), 124.0 (q, J = 287.2 Hz) , 128.3 (q, J = 2.5 Hz), 128.4 (t, J = 5.6 Hz), 129.6, 129.8, 132.7, 132.9.
IR (KBr) ν 3489, 3228, 1453, 1360, 1244, 1182, 1025, 924, 768 cm ⁻¹ .
HRMS (FAB) Calcd for (M−H) C ₂₁ H ₉ F ₁₆ O ₂ : 597.0347, Found 597.0385.

(3) Synthesis of Compound (b4) (9- (Tridecafluorohexyl) -10- (trifluoromethyl) anthracene) In the synthesis of Compound (a4), except that Compound (a3) was changed to Compound (b3), Compound (b4) was obtained as a yellow solid (0.169 g, 0.30 mmol, yield 64%).

(result of analysis)
M.M. P. 101-103 ° C.
¹ H NMR (CDCl ₃ ) δ 7.57-7.65 (m, 4H), 8.36-8.46 (m, 2H), 8.46-8.56 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −49.64 (s, 3F), −81.94 (t, J = 9.0 Hz, 3F), −92.92 (t, J = 15.8 Hz, 2F), -118.52 (m, 2F), -122.76 (m, 2F), -123.74 (m, 2F), -127.22 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 124.7 (q, J = 5.6 Hz), 125.4 (tt, J = 9.3, 4.4 Hz), 125.5 (q, J = 277.3 Hz) 125.8, 126.4, 126.8, 127.2, 129.4, 131.0.
IR (KBr) ν 3165, 3048, 2927, 1364, 1243, 1223, 1146, 1115, 1063, 937, 774 cm ⁻¹ .
HRMS (FAB) Calcd for (M +) C ₂₁ H ₈ F ₁₆ : 564.0370, Found 564.0394.

<Example 3>
(1) Synthesis of Compound (c2) (9- (Heptadecafluorooctyl) -10- (trifluoromethyl) -10- (trimethylsilyl) anthracen-9-ol) In the synthesis of Compound (a2), CF ₃ (CF ₂ ) ₂ CF ₂ The target compound (c2) was obtained as a white solid in the same manner except that I was changed to CF ₃ (CF ₂ ) ₆ CF ₂ I (0.539 g, 0.70 mmol, yield 70%).

(result of analysis)
M.M. P. 84-86 ° C.
¹ H NMR (CDCl ₃ ) δ 0.03 (s, 9H), 2.98 (s, 1H), 7.50-7.59 (m, 4H), 7.91-7.97 (m, 2H) ), 8.03-8.09 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −81.59 (s, 3F), −82.07 (t, J = 9.0 Hz, 3F), −116.40 (m, 2F), −119.18 (brs) , 2F), −122.90 (brs, 2F), −123.22 (brs, 4F), −124.08 (brs, 2F), −127.44 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 1.8, 74.3 (tt, J = 19.9, 2.4 Hz), 76.0 (q, J = 27.9 Hz), 124.2 (q, J = 289.0 Hz), 128.6 (t, J = 5.6 Hz), 128.9, 129.5, 129.6, 132.8, 133.5.
IR (KBr) ν 3586, 3078, 2971, 1371, 1235, 1180, 1155, 1035, 908, 877, 763 cm ⁻¹ .
HRMS (APCI) Calcd for (M +) C ₂₆ H ₁₈ F ₂₀ O ₂ Si: 770.0757, Found 769.0758.

(2) Synthesis of Compound (c3) (9- (Heptadecafluorooctyl) -10- (trifluoromethyl) anthracene-9,10-diol) In the synthesis of Compound (a3), Compound (a2) was changed to Compound (c2) Similarly, the target compound (c3) was obtained as a white solid (0.416 g, 0.60 mmol, yield 67%).

(result of analysis)
M.M. P. 117-119 ° C.
¹ H NMR (CDCl ₃ ) δ 2.87 (s, 1H), 3.15 (d, J = 1.2 Hz, 1H), 7.54-7.63 (m, 4H), 8.00-8 .08 (m, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.17 (s, 3F), −82.09 (t, J = 9.0 Hz, 3F), −119.12 (m, 2F), −120.58 (m , 2F), -123.10 (m, 4F), -123.34 (m, 2F), -124.13 (brs, 2F), -127.47 (m, 2F).
IR (KBr) ν 3596, 3440, 3086, 1450, 1368, 1211, 1151, 1019, 919, 766 cm ⁻¹ .
_{HRMS (APCI) Calcd for (M} -H) C 23 H 9 F 20 O 2: 697.0283, Found 697.0316.

(3) Synthesis of Compound (c4) (9- (Heptadecafluorooctyl) -10- (trifluoromethyl) anthracene) In the synthesis of Compound (a4), except that Compound (a3) was changed to Compound (c3), Compound (c4) was obtained as a yellow solid (0.197 g, 0.29 mmol, yield 63%).

(result of analysis)
M.M. P. 114-116 ° C.
¹ H NMR (CDCl ₃ ) δ 7.55-7.65 (m, 4H), 8.32-8.45 (m, 2H), 8.46-8.57 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −49.65 (s, 3F), −81.97 (t, J = 9.0 Hz, 3F), −92.91 (t, J = 16.1 Hz, 2F), -118.46 (m, 2F), -122.52 to -123.04 (m, 6F), -123.88 (brs, 2F), -127.33 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 124.7 (q, J = 8.0 Hz), 125.4 (tt, J = 9.4, 5.0 Hz), 125.5 (q, J = 277.9 Hz) , 125.8, 126.3, 126.8, 127.2, 129.3, 131.0.
IR (KBr) ν 3156, 3098, 3051, 1446, 1368, 1241, 1148, 990, 766 cm ⁻¹ .
_{HRMS (FAB) Calcd for (M} +) C 23 H 8 F 20: 664.0307, Found 664.0336.

<Example 4>
(1) Synthesis of Compound (d2) (9- (Henicosafluordecyl) -10- (trifluoromethyl) -10- (trimethylsilyl) anthracen-9-ol) In the synthesis of Compound (a2), CF ₃ (CF ₂ ) ₂ CF ₂ The target compound (d2) was similarly obtained as a white solid (0.461 g, 0.53 mmol, yield 53%) except that I was changed to CF ₃ (CF ₂ ) ₈ CF ₂ I.

(result of analysis)
M.M. P. 107-109 ° C.
¹ H NMR (CDCl ₃ ) δ 0.04 (s, 9H), 3.01 (s, 1H), 7.50-7.59 (m, 4H), 7.92-7.97 (m, 2H) ), 8.03-8.09 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −81.60 (s, 3F), −82.05 (t, J = 9.3 Hz, 3F), −116.41 (brs, 2F), −119.20 (brs) , 2F), -123.13 (brs, 10F), -124.04 (brs, 2F), -127.42 (brs, 2F).
¹³ C NMR (CDCl ₃ ) δ 2.1, 74.6 (tt, J = 19.8, 1.9 Hz), 76.4 (q, J = 27.9 Hz), 124.5 (q, J = 289.0 Hz), 129.0 (t, J = 5.6 Hz), 129.4, 129.9, 130.0, 133.2, 133.8.
IR (KBr) (nu) 3585,3076,2973,1339,1224,1173,1160,1037,940,879,763cm < ^-1 >.
_{HRMS (FAB) Calcd for (M} +) C 28 H 18 F 24 O 2 Si: 870.0693, Found 870.0744.

(2) Synthesis of Compound (d3) (9- (Henicosafluordecyl) -10- (trifluoromethyl) anthracene-9,10-diol) Similarly, the target compound (d3) was obtained as a white solid (0.562 g, 0.71 mmol, yield 80%).

(result of analysis)
M.M. P. 132-134 ° C.
¹ H NMR (CDCl ₃ ) δ 2.86 (s, 1H), 3.14 (d, J = 0.6 Hz, 1H), 7.55-7.64 (m, 4H), 8.01-8 .08 (m, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.17 (s, 3F), −82.05 (t, J = 9.3 Hz, 3F), −119.11 (brs, 2F), −120.57 (brs) , 2F), -123.14 (brs, 10F), -124.06 (brs, 2F), -127.45 (brs, 2F).
¹³ C NMR (CDCl ₃ ) δ 73.2 (q, J = 27.9 Hz), 73.7 (tt, J = 14.3, 1.8 Hz), 124.0 (q, J = 287.2 Hz) , 128.3 (q, J = 3.1 Hz), 128.4 (t, J = 5.6 Hz), 129.7, 129.8, 132.6, 132.8.
IR (KBr) ν 3585, 3077, 2910, 1450, 1338, 1222, 1175, 1037, 939, 879, 763 cm ⁻¹ .
_{HRMS (APCI) Calcd for (M} -H) C 25 H 9 F 24 O 2: 797.0219, Found 797.0199.

(3) Synthesis of Compound (d4) (9- (Henicosafluordecyl) -10- (Trifluoromethyl) anthracene) The same as the synthesis of Compound (a4) except that Compound (a3) was changed to Compound (d3). Compound (d4) was obtained as a yellow solid (0.313 g, 0.41 mmol, yield 87%).

(result of analysis)
M.M. P. 115-117 ° C.
¹ H NMR (CDCl ₃ ) δ 7.57-7.65 (m, 4H), 8.35-8.45 (m, 2H), 8.48-8.55 (m, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −49.65 (s, 3F), −81.98 (t, J = 9.0 Hz, 3F), −92.91 (t, J = 15.8 Hz, 2F), -118.46 (m, 2F), -122.25 to -123.22 (m, 10F), -123.94 (m, 2F), -127.34 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 124.7 (q, J = 5.6 Hz), 125.4 (tt, J = 10.0, 4.4 Hz), 125.5 (q, J = 276.7 Hz) , 125.8, 126.4, 126.8, 127.2, 129.3, 130.9.
IR (KBr) ν 3098, 3075, 3048, 1340, 1215, 1153, 1115, 917, 841, 776 cm ⁻¹ .
_{HRMS (FAB) Calcd for (M} +) C 25 H 8 F 24: 764.0243, Found 764.0210.

<Example 5>
(1) Synthesis of Compound (e1) (6- (Trifluoromethyl) -6- (trimethylsilyl) pentacen-13-one) In the synthesis of Compound (a1), anthracene-9,10-dione was converted to pentacene-6,13-dione. The target compound (e1) was similarly obtained as a white solid (5.31 g, 11.8 mmol, yield 59%), except that

(result of analysis)
M.M. P. 220-221 ° C.
¹ H NMR (CDCl ₃ ) δ −0.04 (s, 9H), 7.68 (m, 4H), 8.02 (d, 2H, J = 7.2 Hz), 8.13 (d, J = 2H, J = 7.8 Hz), 8.53 (s, 2H), 8.97 (s, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −81.42 (s, 3F).
¹³ C NMR (CDCl ₃ ) δ 1.9, 75.2 (q, J = 29.8 Hz), 124.2 (q, J = 286.6 Hz), 127.9, 128.3, 129.1, 129.2, 129.5 (q, J = 1.9 Hz), 129.6, 129.8, 133.0, 134.4, 135.0.
IR (KBr) ν 3066, 2961, 1669, 1624, 1454, 1344, 1193, 991, 844, 748, 476 cm ⁻¹ .
_{HRMS (FAB) Calcd for (M} +) C 26 H 21 F 3 O 2 Si: 450.1263, Found 450.1276.

(2) Synthesis of Compound (e2) (6- (Nonafluorbutyl) -13- (trifluoromethyl) -13- (trimethylsilyl) pentacen-6-ol) In the synthesis of Compound (a2), Compound (a1) was converted to Compound (e1) The target compound (e2) was similarly obtained as a white solid (0.407 g, 0.60 mmol, yield 60%), except that

(result of analysis)
M.M. P. 180-181 ° C.
¹ H NMR (CDCl ₃ ) δ 0.15 (s, 9H), 3.32 (s, 1H), 7.59-7.67 (m, 4H), 7.98-8.03 (m, 4H) ), 8.49 (s, 2H), 8.65 (s, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −82.10 (s, 3F), −82.21 (t, J = 9.3 Hz, 3F), −116.66 (m, 2F), −119.91 (m , 2F), -127.22 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 2.1, 75.6 (tt, J = 20.4, 1.8 Hz), 76.8 (q, J = 27.3 Hz), 124.4 (q, J = 288.3 Hz), 127.6, 127.8, 128.2, 128.5, 129.3 (t, J = 5.0 Hz), 130.0 (q, J = 2.5 Hz), 130.4 132.7, 133.1.
IR (KBr) ν 3586, 3563, 3078, 2962, 2902, 1235, 1170, 878, 852, 763, 703 cm ⁻¹ .
_{HRMS (FAB) Calcd for (M} +) C 30 H 22 F 12 O 2 Si: 670.1197, Found 670.1174.

(3) Synthesis of Compound (e3) (6- (Nonafluorbutyl) -13- (trifluoromethyl) pentacene-6,13-diol) In the synthesis of Compound (a3), Compound (a2) was changed to Compound (e2) Similarly, the target compound (e3) was obtained as a white solid (0.532 g, 0.76 mmol, yield 85%).

(result of analysis)
M.M. P. 228-229 ° C.
¹ H NMR (CDCl ₃ ) δ 3.19 (s, 1H), 3.43 (s, 1H), 7.63-7.66 (m, 4H), 8.00-8.04 (m, 4H) ), 8.63 (s, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.84 (s, 3F), −82.20 (t, J = 9.0 Hz, 3F), −119.63 (m, 2F), −121.12 (m , 2F), -127.39 (m, 2F).
¹³ C NMR (CDCl ₃ ) δ 74.1 (q, J = 27.9 Hz), 73.7 (tt, J = 18.6, 2.5 Hz), 124.3 (q, J = 287.2 Hz) , 127.8, 127.9, 128.3, 128.5, 129.0 (q, J = 2.9 Hz), 129.2 (t, J = 4.7 Hz), 129.6, 133.1 , 133.2.
IR (KBr) ν 3598, 3452, 3059, 1219, 1185, 754, 479 cm ⁻¹ .
HRMS (FAB) Calcd for (MH) C ₂₇ H ₁₃ F ₁₂ O ₂ : 597.0724, Found 597.0752.

(4) Synthesis of Compound (e4) (6- (Nonafluorbutyl) -13- (trifluoromethyl) pentacene) The same as the synthesis of Compound (a4) except that Compound (a3) was changed to Compound (e3). Compound (e4) was obtained as dark blue crystals (0.078 g, 0.14 mmol, yield 30%).

(result of analysis)
M.M. P. 200 ° C. (decomposition).
¹ H NMR (CDCl ₃ ) δ 7.26-7.47 (m, 4H), 7.91-7.97 (m, 4H), 9.02 (s, 2H), 9.13 (s, 2H ).
¹⁹ F NMR (CDCl ₃ ) δ −49.43 (s, 3F), −81.73 (t, J = 9.0 Hz, 3F), −92.98 (t, J = 14.0 Hz, 2F), -118.17 (q, J = 9.3 Hz, 2F), -126.80 (m, 2F).
IR (KBr) [nu] 3155,1353,1229,1132,1106,876,743,729 cm < ^-1 >.
_{HRMS (FAB) Calcd for (M} +) C 27 H 12 F 12: 564.0747, Found 564.0736.

<Example 6>
(1) Synthesis of Compound (f2) (6- (Tridecafluorohexyl) -13- (trifluoromethyl) -13- (trimethylsilyl) pentacen-6-ol) In the synthesis of Compound (e2), CF ₃ (CF ₂ ) ₂ CF ₂ The target compound (f2) was obtained as a white solid in the same manner except that I was changed to CF ₃ (CF ₂ ) ₄ CF ₂ I (0.475 g, 0.61 mmol, yield 61%).

(result of analysis)
M.M. P. 175-177 ° C.
¹ H NMR (CDCl ₃ ) δ 0.15 (s, 9H), 3.32 (s, 1H), 7.59-7.67 (m, 4H), 7.98-8.03 (m, 4H) ), 8.49 (s, 2H), 8.65 (s, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −82.12 (s, 3F), −82.21 (t, J = 9.0 Hz, 3F), −116.58 (brs, 2F), −118.93 (brs) , 2F), −123.02 (brs, 2F), −124.16 (brs, 2F), −127.52 (brs, 2F).
¹³ C NMR (CDCl ₃ ) δ 2.1, 75.1 (tt, J = 20.1, 1.8 Hz), 76.7 (q, J = 27.9 Hz), 124.3 (q, J = 289.0 Hz), 127.6, 127.8, 128.1, 128.5, 129.3 (t, J = 5.0 Hz), 129.9 (q, J = 2.5 Hz), 130.3 132.7, 133.1.
IR (KBr) ν 3528, 3062, 2960, 2902, 1243, 1170, 1149, 905, 848, 641, 520 cm ⁻¹ .
HRMS (FAB) Calcd for (M−H) C ₃₂ H ₂₁ F ₁₆ O ₂ Si: 769.1055, Found 769.10.10.

(2) Synthesis of Compound (f3) (6- (Tridecafluorohexyl) -13- (trifluoromethyl) pentacene-6,13-diol) In the synthesis of Compound (e3), Compound (e2) was changed to Compound (f2) Similarly, the target compound (f3) was obtained as a white solid (0.572 g, 0.82 mmol, yield 92%).

(result of analysis)
M.M. P. 230-231 ° C.
¹ H NMR (CDCl ₃ ) δ 3.20 (s, 1H), 3.44 (s, 1H), 7.62-7.65 (m, 4H), 8.00-8.03 (m, 4H) ), 8.62 (d, J = 2.4 Hz, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.82 (s, 3F), −82.24 (t, J = 9.0 Hz, 3F), −119.48 (brs, 2F), −120.17 (brs) , 2F), -123.25 (brs, 2F), -124.16 (brs, 2F), -127.63 (m, 2F).
IR (KBr) ν 3551, 3478, 3065, 1197, 1166, 753, 647, 480 cm ⁻¹ .
_{HRMS (FAB) Calcd for (M} -H) C 29 H 13 F 16 O 2: 697.0660, Found 697.0684.

(3) Synthesis of Compound (f4) (6- (Tridecafluorohexyl) -13- (trifluoromethyl) pentacene) In the synthesis of Compound (e4), except that Compound (e3) was changed to Compound (f3), Compound (f4) was obtained as dark blue crystals (0.068 g, 0.10 mmol, yield 22%).

(result of analysis)
M.M. P. 195 ° C (decomposition).
¹ H NMR (CDCl ₃ ) δ 7.42-7.49 (m, 4H), 7.93-7.97 (m, 4H), 9.03 (s, 2H), 9.13 (s, 2H ).
¹⁹ F NMR (CDCl ₃ ) δ −49.42 (s, 3F), −81.90 (t, J = 9.0 Hz, 3F), −92.82 (brs, 2F), −117.94 (m , 2F), −122.65 (brs, 2F), −123.60 (m, 2F), −127.15 (m, 2F).
IR (KBr) ν 3060, 1233, 1145, 1105, 740, 713, 679 cm ⁻¹ .
HRMS (FAB) Calcd for (M +) C ₂₉ H ₁₂ F ₁₆ : 664.0684, Found 664.0701.

<Example 7>
(1) Synthesis of compound (g2):
In the synthesis of Compound _(e2), as similar except for changing CF ₃ and _(CF _{₂₎ 2} CF ₂ I in _{_{_{CF 3 (CF 2) 6 CF}}} 2 I, to give the desired compound (g2) as a white solid ( 0.548 g, 0.63 mmol, yield 63%).

(result of analysis)
M.M. P. 181-183 ° C.
¹ H NMR (CDCl ₃ ) δ 0.15 (s, 9H), 3.32 (s, 1H), 7.59-7.67 (m, 4H), 7.98-8.03 (m, 4H) ), 8.49 (s, 2H), 8.65 (s, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −82.12 (m, 6F), −116.56 (brs, 2F), −118.88 (brs, 2F), −122.82 (brs, 2F), −123 .25 (brs, 4F), -124.14 (brs, 2F), -127.49 (brs, 2F).
¹³ C NMR (CDCl ₃ ) δ 2.1, 75.2 (tt, J = 20.4, 2.5 Hz), 77.0 (q, J = 30.4 Hz), 124.3 (q, J = 288.3 Hz), 127.6, 127.8, 128.2, 128.5, 129.3 (t, J = 4.9 Hz), 130.0 (q, J = 2.5 Hz), 130.4 132.7, 133.1.
IR (KBr) ν 3582, 3064, 2955, 2898, 1237, 1173, 881, 747, 558, 524 cm ⁻¹ .
_{HRMS (APCI) Calcd for (M} -H) C 34 H 21 F 20 O 2 Si: 869.0991, Found 869.1067.

(2) Synthesis of Compound (g3) (6- (Heptadecafluorooctyl) -13- (trifluoromethyl) pentacene-6,13-diol) In the synthesis of Compound (e3), Compound (e2) was changed to Compound (g2) Similarly, the target compound (g3) was obtained as a white solid (0.535 g, 0.67 mmol, yield 75%).

(result of analysis)
M.M. P. 233-234 ° C.
¹ H NMR (CDCl ₃ ) δ 3.18 (s, 1H), 3.42 (s, 1H), 7.63-7.65 (m, 4H), 8.00-8.03 (m, 4H) ), 8.62 (s, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.67 (s, 3F), −81.96 (t, J = 9.0 Hz, 3F), −119.29 (brs, 2F), −119.95 (brs) , 2F), −122.93 (brs, 4F), −123.27 (brs, 2F), −124.00 (brs, 2F), −127.34 (brs, 2F).
IR (KBr) ν 3599, 3578, 3454, 3061, 1206, 1150, 754, 660, 548, 415 cm ⁻¹ .
_{HRMS (FAB) Calcd for (M} +) C 31 H 14 F 20 O 2: 798.0674, Found 798.0721.

(3) Synthesis of Compound (g4) (6- (Heptadecafluorooctyl) -13- (trifluoromethyl) pentacene) In the synthesis of Compound (e4), except that Compound (e3) was changed to Compound (g3), Compound (g4) was obtained as dark blue crystals (0.19 g, 0.25 mmol, yield 54%).

(result of analysis)
M.M. P. 192 ° C (decomposition).
¹ H NMR (CDCl ₃ ) δ 7.42-7.48 (m, 4H), 7.93-7.97 (m, 4H), 9.03 (s, 2H), 9.13 (s, 2H ).
¹⁹ F NMR (CDCl ₃ ) δ −49.42 (s, 3F), −81.94 (t, J = 9.0 Hz, 3F), −92.79 (brs, 2F), −117.85 (brs) , 2F), −122.50 (m, 4F), −122.93 (m, 2F), −123.82 (m, 2F), −127.26 (brs, 2F).
IR (KBr) [nu] 3061, 1217, 1153, 1106, 735, 672, 646, 630, 554 cm < ^-1 >.
HRMS (FAB) Calcd for (M +) C ₂₉ H ₁₂ F ₁₆ : 664.0684, Found 664.0701.

<Example 8>
(1) Synthesis of Compound (h2) (6- (Henicosafluordecyl) -13- (Trifluoromethyl) -13- (trimethylsilyl) pentacen-6-ol) In the synthesis of Compound (e2), CF ₃ (CF ₂ ) ₂ CF ₂ The target compound (h2) was similarly obtained as a white solid (0.552 g, 0.57 mmol, yield 57%) except that I was changed to CF ₃ (CF ₂ ) ₈ CF ₂ I.

(result of analysis)
M.M. P. 194-195 ° C.
¹ H NMR (CDCl ₃ ) δ 0.15 (s, 9H), 3.30 (s, 1H), 7.60-7.66 (m, 4H), 7.98-8.03 (m, 4H) ), 8.49 (s, 2H), 8.65 (s, 2H).
¹⁹ F NMR (CDCl ₃ ) δ −82.06 (t, J = 9.0 Hz, 3F), −82.14 (s, 3F), −116.58 (brs, 2F), −118.88 (brs) , 2F), −122.83 (brs, 2F), −123.15 (brs, 2F), −124.04 (brs, 8F), −127.44 (brs, 2F).
IR (KBr) ν 3582, 3065, 2955, 2897, 1220, 1173, 848, 747, 547 cm ⁻¹ .
HRMS (FAB) Calcd for (M−H) C ₃₆ H ₂₁ F ₂₄ O ₂ Si: 969.0928, Found 969.960.

(2) Synthesis of Compound (h3) (9- (Henicosafluordecyl) -10- (trifluoromethyl) anthracene-9,10-diol) Except that Compound (e2) was changed to Compound (h2) Similarly, the target compound (h3) was obtained as a white solid (0.598 g, 0.667 mmol, yield 75%).

(result of analysis)
M.M. P. 240-242 ° C.
¹ H NMR (CDCl ₃ ) δ 3.40 (s, 1H), 3.71 (s, 1H), 7.62-7.65 (m, 4H), 8.00-8.04 (m, 4H) ), 8.62-8.64 (m, 4H).
¹⁹ F NMR (CDCl ₃ ) δ −79.86 (s, 3F), −82.07 (t, J = 9.3 Hz, 3F), −119.47 (brs, 2F), −119.09 (brs) , 2F), -123.19 (brs, 10F), -124.04 (brs, 2F), -127.45 (brs, 2F).
IR (KBr) ν 3595, 3477, 3056, 1206, 1155, 657, 646, 554, 450 cm ⁻¹ .
HRMS (FAB) Calcd for (M−H) C ₃₃ H ₁₃ F ₂₄ O ₂ : 897.0533, Found 897.557.

(3) Synthesis of Compound (h4) (6- (Henicosafluordecyl) -13- (trifluoromethyl) pentacene) The same as the synthesis of Compound (e4) except that Compound (e3) was changed to Compound (h3). Compound (h4) was obtained as dark green crystals (0.096 g, 0.112 mmol, yield 24%).

(result of analysis)
M.M. P. 199 ° C (decomposition).
¹ H NMR (CDCl ₃ ) δ 7.26-7.47 (m, 4H), 7.93-7.97 (m, 4H), 9.03 (s, 2H), 9.13 (s, 2H ).
¹⁹ F NMR (CDCl ₃ ) δ −49.42 (s, 3F), −81.97 (t, J = 9.3 Hz, 3F), −92.79 (brs, 2F), −117.86 (brs) , 2F), −122.41 to −123.09 (m, 10F), −123.90 (brs, 2F), −127.34 (brs, 2F).
IR (KBr) [nu] 3061, 1211, 1152, 1105, 744, 558, 455, 418 cm < ^-1 >.
_{HRMS (FAB) Calcd for (M} +) C 33 H 12 F 24: 864.0556, Found 864.0576.

<Solubility test>
In order to examine the applicability of the compounds (e4) to (h4) obtained in Examples 5 to 8 to the wet process, solubility tests in various solvents were conducted. Specifically, 20 mg of a sample was weighed, and the solubility (0.2% by weight) in 10 g of solvent at room temperature was judged visually. Four types of solvents were used: toluene, tetrahydrofuran (THF), chloroform and o-dichlorobenzene. As a comparative example, the results of the solubility test of pentacene (Comparative Example 1), which is a condensed polycyclic compound and has five rings having the same number of rings, are also shown.

As a result of the solubility test, it was found that the compound has higher solubility in organic solvents than pentacene. This is presumably because the compound has a perfluoroalkyl group.
This makes it difficult to apply to devices other than the vapor deposition method in which pentacene is a dry process, while compounds (e4) to (h4) can be applied to wet processes such as coating, spin coating, and inkjet methods. It can be said that.

<Ionization potential measurement>
The ionization potentials of the compounds (e4) to (h4) obtained in Examples 5 to 8 were measured using an atmospheric photoelectron spectrometer (AC-1 manufactured by Riken Keiki Co., Ltd.). A measurement sample was obtained by vacuum-depositing compounds (e4) to (h4) on a silicon substrate (back pressure to 10 ⁻⁴ Pa, deposition rate 0.1 Å / s, substrate temperature 25 ° C., film thickness: 70 nm). Made. The pentacene vapor deposition film produced similarly was used as a comparative example.
The measurement results are shown in Table 2 below.

As a result of measuring the ionization potential, it was found that the compounds (e4) to (h4) had a low HOMO level and excellent oxidation resistance. This is considered to be caused by the electron withdrawing properties of the fluorine atoms of the compounds (e4) to (h4).

<Characteristics of organic semiconductor materials>
In order to evaluate the characteristics of the compounds (e4) to (g4) as an organic semiconductor material, a deposited field effect transistor (deposited FET) element was fabricated, and field effect mobility (carrier mobility) was obtained. A method for producing a vapor-deposited FET element and a method for evaluating semiconductor characteristics are shown below.

The cleaned silicon substrate with a silicon oxide film was immersed in a toluene solution of n-octyltrichlorosilane to treat the surface of the silicon oxide film. With respect to the substrate, the compounds (e4) to (g4) obtained in Examples 5 to 7 were vacuum-deposited (back pressure to 10 ⁻⁴ Pa, deposition rate 0.1 Å / s, substrate temperature 25 ° C., film thickness: 70 nm), an organic semiconductor layer was formed.

Gold was vacuum-deposited on this organic semiconductor layer using a shadow mask (back pressure˜10 ⁻⁴ Pa, deposition rate 1˜2 Å / s, film thickness: 50 nm) to form source and drain electrodes (channel length 50 μm). , Channel width 1 mm). The organic semiconductor layer and the silicon oxide film at portions different from the electrodes were scraped, and a conductive paste (Dotite D-550, manufactured by Fujikura Kasei Co., Ltd.) was attached to the portions, and the solvent was dried. Thus, a field effect transistor (FET) element having a top contact / bottom gate structure was produced.

The electrical characteristics of the obtained vapor-deposited FET element were evaluated in vacuum (<5 × 10 ⁻³ Pa) using a semiconductor device analyzer B1500A manufactured by Agilent. Using the silicon substrate of the vapor deposition FET element thus produced as a gate electrode, a voltage was applied to the silicon substrate, and the current / voltage curve between the source and drain electrodes was measured by scanning the gate voltage.
As a result, on / off operation of the drain current due to the gate voltage of the deposited FET element was observed, and the field effect mobility (carrier mobility) was obtained from the slope of the drain current / gate voltage. Organic semiconductor elements formed using the compounds (e4) to (g4) exhibited characteristics as p-type transistor elements. Carrier mobility was determined from the saturation region in the current-voltage characteristics of the organic thin film transistor.
The measurement results are shown in Table 3 below.
Moreover, the result of the output characteristic of a compound (e4) is shown in FIG.
From these results, it can be seen that the compounds (e4) to (g4) have high carrier mobility and show sufficient semiconductor characteristics.

<Thin film X-ray diffraction>
Out-of-plane X-ray diffraction pattern measurement (diffraction by a lattice plane parallel to the substrate surface) of the vapor-deposited thin film of compound (e4) obtained in Example 5 was performed. Out-of-plane X-ray diffraction measurement was performed by oblique incidence measurement using TTR-III manufactured by Rigaku. The measurement results are shown in FIG. In general, a sample of a thin film having a highly ordered orientation shows a diffraction line at 2θ = 5 ° or less, and a sample with a particularly high order also shows a high-order diffraction line. In the deposited thin film of the compound (e4), two diffraction lines were confirmed at 2θ = 4.7 ° (d = 18.8 °) and 2θ = 14.1 ° (d = 6.2 °), and the compound (e4) Was found to have highly ordered orientation and crystallinity in the thin film.

Further, In-plane X-ray diffraction pattern measurement (diffraction by a lattice plane perpendicular to the substrate surface) of the deposited thin film of the compound (e4) obtained in Example 5 was performed. In-plane X-ray diffraction measurement was evaluated using ATX-G manufactured by Rigaku. A diffraction line derived from the packing of the perfluoroalkyl group is observed at 2θχ / φ = 16 °, and 2θχ / φ = 23 ° (d = 3.8Å), which is a diffraction line caused by π-π stacking between molecules. Compound (e4) formed π-π stacking in the thin film, and the thin film was found to have crystallinity.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on January 28, 2013 (Japanese Patent Application No. 2013-013179), the contents of which are incorporated herein by reference.

The present invention provides an organic semiconductor material containing a fluorine-containing aromatic compound that can be used in either a dry process or a wet process and is expected to have high mobility.
According to the present invention, a fluorine-containing aromatic compound that is soluble in an organic solvent and has high carrier mobility as an organic semiconductor material by introducing a perfluoroalkyl group with an acene compound that is a condensed aromatic ring compound as a core. Is obtained.
The organic semiconductor material containing the compound of the present invention can be used for organic semiconductor (thin film) transistors, organic EL elements for next-generation flat panel displays, and organic thin film solar cells as lightweight and flexible power sources.

Claims

A fluorine-containing aromatic compound represented by the following formula (1).

[In the above formula, R f1 and R f2 are groups different from each other, R f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is a group.
R may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. It is a group. When a hydrogen atom bonded to a carbon atom is present in the R, at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be substituted with a group selected from a perfluoroalkyl group and a phenyl group.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6. ]
The fluorine-containing aromatic compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

[However, the symbols in the formula have the same meaning as described above. ]
The fluorine-containing aromatic compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-11).

[However, the symbols in the formula have the same meaning as described above. ]
An organic semiconductor material comprising the fluorine-containing aromatic compound according to any one of claims 1 to 3.
An organic semiconductor thin film comprising the organic semiconductor material according to claim 4.
An organic semiconductor thin film made of the organic semiconductor material according to claim 4 and having crystallinity.
An organic semiconductor element in which the organic semiconductor thin film according to claim 5 or 6 is formed on a substrate.
A transistor comprising a gate electrode, a dielectric layer, a source electrode, a drain electrode, and a semiconductor layer, wherein the semiconductor layer is composed of the organic semiconductor thin film according to claim 5 or 6.
A compound represented by the following formula (2) is reacted with a compound represented by the formula R f1 —Si (CH 3 ) 3 to obtain a compound represented by the following formula (3). ) And a compound represented by the formula R f2 —X are reacted to obtain a compound represented by the following formula (4). Next, in the compound represented by the formula (4) A method for producing a fluorine-containing aromatic compound represented by the following formula (1), wherein a deprotection reaction and an aromatization reaction are performed.

[In the above formula, R f1 and R f2 are groups different from each other, R f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is a group.
R may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. It is a group. When a hydrogen atom bonded to a carbon atom is present in the R, at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be substituted with a group selected from a perfluoroalkyl group and a phenyl group.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6.
X is an iodine atom or a bromine atom. ]
A compound represented by the following formula (2A) is reacted with a compound represented by the formula R f1 —Si (CH 3 ) 3 to obtain a compound represented by the following formula (3A). The compound represented by the following formula (4A) is obtained by reacting the compound represented by 3A) with the compound represented by the formula R f2 -X. Next, in the compound represented by the formula (4A) A deprotection reaction and an aromatization reaction are performed to obtain a compound represented by the following formula (1A), and then R A which is a halogen atom in the compound represented by the formula (1A) is substituted with R B A process for producing a compound represented by the following formula (1B):

[In the above formula, R f1 and R f2 are groups different from each other, R f1 is a linear perfluoroalkyl group having 1 to 3 carbon atoms, and R f2 is a linear perfluoroalkyl group having 2 to 12 carbon atoms. It is a group.
R A may be the same or different and is selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group, a monovalent heteroaromatic group, a halogen atom, and a hydrogen atom. One or more of R A represents a halogen atom. When a hydrogen atom bonded to a carbon atom is present in the RA , at least one of the hydrogen atoms is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A perfluoroalkyl group and a group selected from phenyl groups.
R B is a group corresponding to R A, is R B corresponding to R A is a halogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, monovalent aromatic hydrocarbon group, a monovalent heteroaromatic And a group selected from a halogen atom. The If there is a hydrogen atom bonded to the carbon atom in R B, 1 or more alkyl groups of 1 to 6 carbon atoms hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, 1 to 6 carbon atoms A perfluoroalkyl group and a group selected from phenyl groups.
R B corresponding to R A other than a halogen atom is the same group as R A.
A and B are symbols for distinguishing benzene rings, and the order in which the benzene ring structure A attached with A and the benzene ring structure B attached with B are bonded is not limited.
m is the repeating number of the benzene ring structure A, n is the repeating number of the benzene ring structure B, m is an integer of 0 or more, n is an integer of 1 or more, and m + n is 3-6.
X is an iodine atom or a bromine atom. ]