JP2019129160A - Composition for organic semiconductor, radical compound and method of producing the same, and device - Google Patents

Abstract

To provide: a radical compound capable of exhibiting high conductivity, a method of producing the same, and a device; and a composition for an organic semiconductor suitable as a raw material for the radical compound.SOLUTION: A composition for an organic semiconductor contains a polycyclic aromatic compound having an orthoquinone structure, and a boron-containing Lewis acid. A radical compound includes a layer formed using the composition for an organic semiconductor, and is represented by one of the following general formula (I) and the following general formula (II). A device includes a layer containing the radical compound. A method of producing a radical compound includes a step of irradiating the composition for an organic semiconductor with light. In the formulae (I) and (II), R-Reach independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group, or a siloxy group, and Z-Zeach independently represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring.SELECTED DRAWING: None

Description

  The present invention relates to a composition for an organic semiconductor, a radical compound, a production method thereof, and a device.

Polycyclic aromatic compounds with a series of aromatic hydrocarbon rings and aromatic heterocycles are expected to be applied to devices such as organic field effect transistors (OFETs), organic electroluminescence elements (organic EL elements), and organic solar cells. Has been.
For example, Patent Document 1 discloses a thin film transistor including a semiconductor layer formed of a semiconductor material such as phthalocyanine.

JP 2005-277017 A

In recent years, high conductivity is required for OFETs, organic EL elements, organic solar cells and the like.
However, conventional polycyclic aromatic compounds such as phthalocyanine do not always satisfy conductivity at a high level.

  The present invention has been made in view of the above circumstances, and aims to provide a radical compound capable of exhibiting high conductivity, a method for producing the same, a device, and a composition for an organic semiconductor suitable as a raw material for the radical compound To do.

The present invention has the following aspects.
[1] A composition for organic semiconductor, comprising a polycyclic aromatic compound having an orthoquinone structure and a Lewis acid containing boron.
[2] The polycyclic aromatic compound having an orthoquinone structure is at least one member selected from the group consisting of compounds represented by the following general formula (i) and the following general formula (ii), and the Lewis acid The composition for an organic semiconductor according to [1], wherein is a boron trihalide.

In formula (i), Z ¹ and Z ² are each independently an aromatic hydrocarbon ring or an aromatic heterocycle.

In formula (ii), Z ^{3 to} Z ⁵ are each independently an aromatic hydrocarbon ring or an aromatic heterocycle.

[3] A radical compound represented by any one of the following general formula (I) and the following general formula (II).

In formula (I), R ¹ and R ² are each independently a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group, or a siloxy group, and Z ¹ and Z ² are each independently an aromatic An aromatic hydrocarbon ring or an aromatic heterocyclic ring.

In formula (II), R ³ and R ⁴ are each independently a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group, or a siloxy group, and Z ^{3 to} Z ⁵ are each independently an aromatic An aromatic hydrocarbon ring or an aromatic heterocyclic ring.

[4] A method for producing a radical compound, comprising the step of irradiating the composition for organic semiconductor according to [1] or [2] with light.
[5] A device comprising a layer formed using the organic semiconductor composition according to [1] or [2].
[6] A device comprising a layer containing the radical compound according to [3].

  According to the present invention, it is possible to provide a radical compound capable of expressing high conductivity, a method for producing the same, a device, and a composition for an organic semiconductor suitable as a raw material of the radical compound.

In Example 1, it is a figure which shows the ESR spectrum measured in the solid state. In Example 1, it is a figure which shows the ESR spectrum measured in the state of the solution. In Example 2, it is a figure which shows the ESR spectrum measured in the solid state.

"Composition for organic semiconductor"
The composition for organic semiconductors of the present invention contains a polycyclic aromatic compound having an orthoquinone structure and a Lewis acid containing boron.
In the present invention, “organic semiconductor” refers to an organic substance exhibiting properties as a semiconductor. Moreover, "the composition for organic semiconductors" means the raw material for manufacturing an organic semiconductor.

<Polycyclic aromatic compounds>
The polycyclic aromatic compound in the present invention is not particularly limited as long as it has an orthoquinone structure, and examples include compounds represented by the following general formula (i) and the following general formula (ii). Hereinafter, the compound represented by the following general formula (i) is also referred to as “compound (i)”, and the compound represented by the following general formula (ii) is also referred to as “compound (ii)”.

In formula (i), Z ¹ and Z ² are each independently an aromatic hydrocarbon ring or an aromatic heterocycle. Z ¹ and Z ² may be the same or different and may have a structure in which Z ¹ and Z ² are condensed.
In formula (ii), Z ^{3 to} Z ⁵ are each independently an aromatic hydrocarbon ring or an aromatic heterocycle. Z ³ , Z ⁴ and Z ⁵ may be the same or different, and may have a structure in which Z ³ , Z ⁴ and Z ⁵ are condensed.

The aromatic hydrocarbon ring or aromatic heterocyclic ring in Z ^{1 to} Z ⁵ may have a substituent or may not have a substituent.
The number of atoms forming Z ^{1 to} Z ⁵ can be appropriately determined according to the purpose, but it is preferable that the number of atoms is 30 or less in consideration of the influence of the orthoquinone structure on the whole molecule. From the viewpoint of ease of synthesis, the number of atoms forming Z ^{1 to} Z ⁵ is preferably 30 or less.

Each of Z ^{1 to} Z ⁵ may be monocyclic or polycyclic, but is preferably polycyclic.
The aromatic hydrocarbon ring includes benzene ring, naphthalene ring, anthracene ring, benzoanthracene ring, phenanthrene ring, benzophenanthrene ring, picene ring, tetracene ring, pentacene ring, pyrene ring, chrysene ring, benzochrysene ring, triphenylene ring, benzo ring Triphenylene ring, perylene ring, coronene ring, dibenzoanthracene ring, fluorene ring, benzofluorene ring, dibenzofluorene ring, s-indacene ring, as-indacene ring, fluoranthene ring, benzofluoranthene ring, tetralin ring, etc. The aromatic hydrocarbon ring may have a substituent.

  Examples of the atoms other than carbon constituting the aromatic heterocycle include sulfur atom, nitrogen atom, oxygen atom, silicon atom, selenium atom and the like. Examples of the aromatic heterocyclic ring include acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, quindoline ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, Anthrazine ring, Perimidine ring, Dibenzofuran ring, Dibenzothiophene ring, Tianthrene ring, Phenoxathin ring, Thiophanthrene ring, Benzofuran ring, Benzothiophene ring, Indole ring, Pyridyl ring, Pyrrole ring, Imidazole ring, Triazole ring, Isoquinoline ring The aromatic heterocyclic ring may have a substituent.

  Examples of the substituent that the aromatic hydrocarbon ring or the aromatic heterocyclic ring may have include an alkyl group having 1 to 15 carbon atoms, an alkoxy group, an alkenyl group, and an alkynyl group. Further, these substituents may be bonded via a bond containing a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A preferred example of the compound (i) is a compound in which Z ¹ and Z ² are the same carbon so that the structure of the compound (i) becomes more planar and the physical properties are easily changed even by a structural change caused by a slight twisting strain of the molecule. It has an aromatic hydrocarbon ring of several 6 to 30, and from the viewpoint of further improving the conductivity, one having an aromatic hydrocarbon ring of 10 to 30 carbon atoms is more preferable.
The aromatic hydrocarbon ring is preferably polycyclic so that changes in optical properties can be easily detected in the visible light region, and Z ¹ and Z ² are polycyclic aromatic hydrocarbons in which benzene rings are linked. The compound which is a ring can be mentioned as a suitable example.
Examples of the compound (i) include compounds (i-1) to (i-28) shown below. In compounds (i-1) to (i-12), (i-22) to (i-24) and (i-28), Z ¹ and Z ² in the formula (i) are aromatic hydrocarbons It corresponds to a compound that is a ring. Compounds (i-13) to (i-21) and (i-25) to (i-27) correspond to compounds in which Z ¹ and Z ^{2 in} formula (i) are aromatic heterocycles. Compounds (i-11) to (i-12) correspond to compounds having a structure in which Z ¹ and Z ^{2 in} formula (i) are condensed.

  As compound (i), among the above compounds, compounds (i-1) to (i-12) are preferable. Among these, the compound (i-1), the compound (i-4), and the compound (i-7) are more preferable from the viewpoint of easy stacking due to the π-π interaction.

A preferred example of the compound (ii) is a compound in which Z ³ and Z ⁵ are the same carbon so that the structure of the compound (ii) becomes planar and the physical properties are easily changed even by a structural change caused by a slight twisting strain of the molecule. It has an aromatic hydrocarbon ring of several 6 to 30, and from the viewpoint of further improving the conductivity, one having an aromatic hydrocarbon ring of 10 to 30 carbon atoms is more preferable. As Z ⁴ , one having an aromatic hydrocarbon ring having 6 to 30 carbon atoms is preferable, and one having an aromatic hydrocarbon ring having 6 to 10 carbon atoms is more preferable from the viewpoint of further improving the conductivity.
Further, the aromatic hydrocarbon ring is preferably polycyclic so that a change in optical properties can be easily detected in the visible light region, and in particular, Z ³ and Z ⁵ are polycyclic aromatic carbons in which benzene rings are linked. Compounds having a hydrogen ring can be mentioned as a suitable example.
Examples of compound (ii) include compounds (ii-1) to (ii-26) shown below.

  Among the above compounds, compounds (ii-1) to (ii-4) and (ii-6) to (ii-8) are preferable as the compound (ii). Among these, the compound (ii-2) and the compound (ii-6) to the compound (ii-8) are more preferable from the viewpoint of easy stacking due to π-π interaction.

These polycyclic aromatic compounds may be used individually by 1 type, and may use 2 or more types together.
As the polycyclic aromatic compound, compound (i) is preferred.

It does not specifically limit as a synthesis method of compound (i) and (ii), It can synthesize | combine combining a well-known method.
For example, efficient and highly productive synthesis is possible by synthesizing by a synthesis method that includes a step of coupling reaction with a transition metal catalyst and a step of ring formation reaction with an organic molecular catalyst, starting from petroleum raw materials. It is.

<Lewis acid>
The Lewis acid in the present invention is not particularly limited as long as it contains boron, and, for example, boron trihalide (BX ₃ ), tris (pentafluorophenyl) borane (B (C ₆ F ₅ ) ₃ ), triphenylborane , Trimethoxy borane, triphenoxy borane, trimethyl borane and the like.
These Lewis acids may be used alone or in combination of two or more.

As a Lewis acid, boron trihalide is preferable from the viewpoint of further improving the conductivity. Boron trihalide may form a complex with monoethyl ether, diethyl ether, triethylamine, aniline and the like.
Examples of the boron trihalide include boron trifluoride (BF ₃ ), boron trichloride (BCl ₃ ), and boron tribromide (BBr ₃ ). Among these, boron trifluoride is preferable.

  The ratio between the Lewis acid and the polycyclic aromatic compound is not particularly limited and may be equimolar, but the Lewis acid may be excessive. Specifically, the molar ratio of the polycyclic aromatic compound: Lewis acid = 1: 2000-1: 5 are preferable, 1: 1000-1: 10 are more preferable, and 1: 500-1: 50 are more preferable.

  The Lewis acid and the polycyclic aromatic compound may be stored in a mixture state, but the Lewis acid and the polycyclic aromatic compound are stored separately until immediately before using the organic semiconductor composition, and immediately before use. It is preferable to mix these. When the Lewis acid and the polycyclic aromatic compound are stored as a mixture, the mixture is preferably stored in a container protected from light.

"Radical compounds"
The radical compound of the present invention is a compound represented by any one of the following general formula (I) and the following general formula (II). Hereinafter, the compound represented by the following general formula (I) is also referred to as “compound (I)”, and the compound represented by the following general formula (II) is also referred to as “compound (II)”.

In formula (I), R ¹ and R ² are each independently a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group, or a siloxy group, and Z ¹ and Z ² are each independently an aromatic An aromatic hydrocarbon ring or an aromatic heterocyclic ring.

In formula (II), R ³ and R ⁴ are each independently a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group, or a siloxy group, and Z ^{3 to} Z ⁵ are each independently an aromatic An aromatic hydrocarbon ring or an aromatic heterocyclic ring.

In the alkyl group, aryl group, alkoxy group and silyl group in R ^{1 to} R ⁴ , at least a part of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms.
As R < ¹ > -R < ⁴ >, a halogen atom and an alkyl group are preferable, and a halogen atom is more preferable from a viewpoint which electroconductivity improves more.
The Z ¹ to Z ^5, include Z ¹ to Z ⁵ exemplified above in the description of polycyclic aromatic compound contained in the organic semiconductor composition.

A preferred example of compound (I) is a compound in which Z ¹ and Z ² are the same carbon so that the structure of compound (I) becomes planar and the physical properties are easily changed even by a structural change caused by a slight twisting strain of the molecule. It has an aromatic hydrocarbon ring of several 6 to 30, and from the viewpoint of further improving the conductivity, one having an aromatic hydrocarbon ring of 10 to 30 carbon atoms is more preferable.
The aromatic hydrocarbon ring is preferably polycyclic so that changes in optical properties can be easily detected in the visible light region, and Z ¹ and Z ² are polycyclic aromatic hydrocarbons in which benzene rings are linked. The compound which is a ring can be mentioned as a suitable example.
Examples of the compound (I) include the compounds (I-1) to (I-34) shown below.

  As the compound (I), among the above compounds, compounds (I-1) to (I-12) are preferable. Among these, the compound (I-1), the compound (I-4), and the compound (I-7) are more preferable from the viewpoint of easy stacking due to the π-π interaction.

A preferred example of compound (II) is a compound in which Z ³ and Z ⁵ are the same carbon so that the structure of compound (II) becomes planar and the physical properties are easily changed even by a structural change caused by a slight twisting strain of the molecule. It has an aromatic hydrocarbon ring of several 6 to 30, and from the viewpoint of further improving the conductivity, one having an aromatic hydrocarbon ring of 10 to 30 carbon atoms is more preferable. As Z ⁴ , one having an aromatic hydrocarbon ring having 6 to 30 carbon atoms is preferable, and one having an aromatic hydrocarbon ring having 6 to 10 carbon atoms is more preferable from the viewpoint of further improving the conductivity.
Further, the aromatic hydrocarbon ring is preferably polycyclic so that a change in optical properties can be easily detected in the visible light region, and in particular, Z ³ and Z ⁵ are polycyclic aromatic carbons in which benzene rings are linked. Compounds having a hydrogen ring can be mentioned as a suitable example.
Examples of compound (II) include compounds (II-1) to (II-29) shown below.

  Among the above compounds, the compounds (II-1) to (II-4) and (II-6) to (II-8) are preferable as the compound (II). Among these, the compound (II-2) and the compound (II-6) to the compound (II-8) are more preferable from the viewpoint of easy stacking due to the π-π interaction.

One of these radical compounds may be used alone, or two or more thereof may be used in combination.
As the radical compound, compound (I) is preferable.

<Method for producing radical compound>
The radical compound is obtained, for example, by irradiating the above-described composition for organic semiconductor with light.
Hereinafter, an example of a method for producing a radical compound will be specifically described.

First, the polycyclic aromatic compound and the Lewis acid are mixed. Subsequently, light is irradiated to the obtained mixture (namely, composition for organic semiconductors) (light irradiation process).
As a polycyclic aromatic compound and a Lewis acid, the polycyclic aromatic compound and Lewis acid which were illustrated previously in description of the composition for organic semiconductors are mentioned.
The ratio of the polycyclic aromatic compound and the Lewis acid is not particularly limited, and may be equimolar, but the Lewis acid may be excessive, specifically, the polycyclic aromatic compound: Lewis acid = 1: 2000-1: 5 are preferable, 1: 1000-1: 10 are more preferable, and 1: 500-1: 50 are more preferable.

  When a polycyclic aromatic compound and a Lewis acid are mixed, a boron atom of the Lewis acid and an oxygen atom of the polycyclic aromatic compound are coordinated. When the mixture is irradiated with light, the polycyclic aromatic compound is excited by light to generate a radical. The generated radical is captured by a boron atom coordinated to an oxygen atom of the polycyclic aromatic compound, and a radical compound (organic radical) in which the radical is localized in the molecule is obtained.

When Compound (i) is used as a polycyclic aromatic compound, Compound (I) is obtained, and when Compound (ii) is used, Compound (II) is obtained.
Further, for example, when boron trihalide is used as a Lewis acid, a compound in which R ^{1 to} R ⁴ in the general formulas (I) and (II) are a halogen atom can be obtained. When tris (pentafluorophenyl) borane is used as a Lewis acid, a compound in which R ^{1 to} R ⁴ are phenyl groups in which all hydrogen atoms are substituted with fluorine atoms is obtained.

The light irradiated to the mixture is not particularly limited, but from the viewpoint of efficient generation of radicals, a light source having a wavelength corresponding to the maximum absorption at the time of measuring the UV-visible absorption spectrum of the polycyclic aromatic compound is preferred. For example, since the maximum absorption of the compound (i-1) is 406.5 nm, when the compound (i-1) is used as the polycyclic aromatic compound, it is preferable to use a violet LED as the light source. Since the maximum absorption of the compound (i-2) is 478.0 nm, when the compound (i-2) is used as the polycyclic aromatic compound, it is preferable to use a blue LED as a light source.
A fluorescent lamp can be used as the light source.

Although the irradiation time of light is determined according to the kind of polycyclic aromatic compound and the kind of light source, for example, 10 minutes or more are preferable and 30 minutes or more are more preferable. The upper limit of the irradiation time is not particularly limited.
It is preferable to keep the mixture at 10 to 50 ° C., more preferably 20 to 30 ° C. while irradiating light.

The light irradiation step is preferably performed in the presence of an organic solvent.
As the organic solvent, a poor solvent for the generated radical compound is preferable, and examples thereof include dichloromethane, dichloroethane, carbon tetrachloride, hexane, benzene, and acetonitrile.
By performing the light irradiation step in the presence of a poor solvent for the radical compound, crystals of the radical compound are likely to precipitate, and a high-purity radical compound can be obtained by filtering the reaction solution. Note that a radical solvent poor solvent may be added to the reaction solution after the light irradiation step to precipitate radical compound crystals.
Moreover, since the radical compound which did not precipitate melt | dissolves in the filtrate after filtration, a radical compound can be collect | recovered if a filtrate is pressure-reduced and an organic solvent etc. are removed. When the Lewis acid is used in excess relative to the polycyclic aromatic compound, the Lewis acid is also removed by reducing the pressure of the filtrate. At this time, if boron trihalide is used as the Lewis acid, it can be easily removed under reduced pressure. When the poor solvent for the radical compound is not used, the reaction solution may be decompressed to remove excess Lewis acid and the like.

  In the above-described production method, after mixing the polycyclic aromatic compound and the Lewis acid, the resulting mixture is irradiated with light to produce a radical compound. For example, the polycyclic aromatic compound is irradiated with light. While the Lewis acid may be added, the Lewis acid may be added after the polycyclic aromatic compound is irradiated with light. However, in order to produce the target radical compound with high yield, it is preferable to irradiate light to the mixture of polycyclic aromatic compound and Lewis acid.

As described above, by using the boron trihalide as the Lewis acid, the general formula (I), the compound obtained is R ¹ to R ⁴ is a halogen atom in (II), the R ¹ ~ The halogen atom in R ⁴ may be substituted with an alkyl group. The substitution to the alkyl group may be performed before or after the light irradiation step.
Examples of the method for substituting a halogen atom with an alkyl group include an addition reaction using an organic metal reagent and the like.

<Function effect>
In the radical compound of the present invention described above, the radical is trapped by the boron atom coordinated to the oxygen atom, and the radical is localized in the molecule. Furthermore, the radical compound of the present invention is easy to stack due to the π-π interaction, the radical is stably localized, and electricity easily flows. Whether or not radicals are localized in the molecule can be confirmed by measuring electron spin resonance (ESR). Moreover, it can be confirmed by X-ray structural analysis whether it is stacking.

Therefore, if it is a radical compound of the present invention, electric resistance value will become small and can express high conductivity.
In particular, as the number of carbon atoms in Z ^{1 to} Z ³ and Z ⁵ in the general formulas (I) and (II) increases, more specifically, if the number of carbon atoms is 10 or more, stacking becomes easier. In addition, when R ^{1 to} R ⁴ in the general formulas (I) and (II) are halogen atoms, steric hindrance is reduced, and stacking becomes easy. The easier the stacking, the lower the electrical resistance and the better the conductivity.
Further, Z ^{1 to} Z ³ and Z ⁵ in the above general formulas (I) and (II) are, for example, the above compounds (I-1), (I-4), (I-7) and (II). -2) If it is a so-called zigzag structure having three double bonds in all aromatic hydrocarbon rings as shown in compound (II-6) to compound (II-8), the tendency to stack more easily It is in. As a result, radicals are considered to be stably localized over a long period of time.

  Moreover, the composition for organic semiconductors of the present invention described above is suitable as a raw material for radical compounds that can exhibit high conductivity.

<Use>
The composition for organic semiconductor and the radical compound of the present invention can be used, for example, in a device using an organic semiconductor.
As a device using an organic semiconductor, an organic field effect transistor (OFET), an organic electroluminescent element (organic EL element), an organic solar cell, a secondary battery etc. are mentioned, for example.
Hereinafter, an example of the device will be described.

"device"
The device of one embodiment of the present invention is provided with a layer formed using the composition for organic semiconductor of the present invention described above.
When the composition for an organic semiconductor of the present invention is used in a device, the composition for an organic semiconductor is irradiated with light to be used as a radical compound of the present invention. It is preferable that the polycyclic aromatic compound and the Lewis acid contained in the composition for organic semiconductor be mixed immediately before the light irradiation.

A device according to another embodiment of the present invention includes a layer containing the above-described radical compound of the present invention.
Examples of the layer containing a radical compound include a semiconductor layer of an OFET, a conductive layer of an organic EL element, a photoactive layer of an organic solar cell, an electrolyte layer of a secondary cell, and the like.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
In Synthesis Examples 1 and 2, all reactions were observed by thin layer chromatography. (Merck 60 F 254 precoated silica gel plates (0.25 mm thickness)). The melting point was measured by a trace melting point measuring apparatus manufactured by Yanako Technical Silences Co., Ltd. FT-IR (infrared spectroscopy) was measured with FTIR-8400 manufactured by Shimadzu Corporation after producing KBr tablets. ¹ H-NMR and ¹³ C-NMR were observed with an ECX500FT-NMR nuclear magnetic resonance apparatus manufactured by JASCO Corporation. ESIMS and HRESIMS were measured by Thermo Fisher Scientific Exactive spectrometer and LCMS-2020 manufactured by Shimadzu Corporation. Silica gel 60N manufactured by Kanto Chemical Co., Ltd. was used for column chromatography for purification.

"Synthesis Example 1: Synthesis of picene-13,14-dione"
Picen-13,14-dione was synthesized according to the following synthetic route.

[1] Synthesis of 1-formylnaphthalen-2-yl trifluoromethanesulfonate (4) 2-hydroxy-1-naphthaldehyde (3) (2.00 g, 0.0116 mol) cooled to 0 ° C. under argon atmosphere Trifluoromethanesulfonic anhydride (2.3 mL, 0.0139 mol) was slowly added to a solution of 4-N, N-dimethylaminopyridine (DMAP, 2.84 g, 0.0232 mol) in dichloromethane (50 mL). The reaction mixture was stirred for 30 minutes at a reaction temperature of 0 ° C. Subsequently, the reaction temperature was raised to room temperature and stirred for further 4 hours. Distilled water (50 mL) was added to the reaction solution to stop the reaction, and the organic layer was extracted with dichloromethane (50 mL). This operation was repeated a total of 3 times, and all the organic layers obtained were washed twice with about 100 mL of 1M hydrochloric acid and a saturated aqueous sodium chloride solution. The organic layer was dried by adding an appropriate amount of magnesium sulfate, and then the magnesium sulfate was removed by filtration. The organic solvent was removed from the dried organic layer by distillation under reduced pressure. The obtained yellow oily substance is purified by silica gel column chromatography (developing solvent: 50% chloroform / hexane) to obtain the target 1-formylnaphthalen-2-yl trifluoromethanesulfonate (4) as a white solid ( The yield was 76% (2.7 g).

Physical property data; m. p. (CHCl ₃ ) 45.0-45.5 ° C .; ¹ H-NMR (500 MHz, CDCl ₃ ) δ 10.80 (s, 1 H), 9.18 (d, J = 8.5 Hz, 1 H), 8.19 (D, J = 8.5 Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7.77 (t, J = 7.5 Hz, 1 H), 7.66 (t, J = 7.5 Hz, 1 H), 7.49 (d, J = 9.0 Hz, 1 H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ 188.7, 151.8, 137.4, 132.8, 131. 0, 130.7, 128.7, 128.1, 125.7, 122.8, 119.6, 118.8 (q, J = 320.7 Hz); IR _{max max} 1693, 1578, 1516, 1410, 1061,949,872,764,704cm < ^-1 >.

Synthesis of [2] [2,2′-binaphthalene] -1,1′-dicarbaldehyde (5) Bis (triphenylphosphine) palladium (II) dichloride (PdCl ₂ (PPh ₃ ) ₂ , 0 under argon atmosphere Compound (4) (1.00 g, 3.29 mmol) in which 231 g (0.329 mmol) was cooled to 0 ° C., potassium carbonate (1.363 g, 9.86 mmol) and bispinacol diboron (0.501 g, It was added to a solution of 97 mmol) in dioxane (15 mL) / distilled water (0.178 mL, 9.86 mmol). The reaction mixture was allowed to warm to 90 ° C. for 1 hour at room temperature and was allowed to react for 1 hour. After the reaction solution was cooled to room temperature, solids in the reaction system were removed by filtration using a silica gel pad. At this time, the reaction mixture was eluted with a 50% ethyl acetate / hexane solution. The organic solvent of the collected filtrate was evaporated under reduced pressure to obtain a crude product. The crude product is purified by silica gel column chromatography (developing solvent: 50% benzene / hexane) to obtain the target [2,2′-binaphthalene] -1,1′-dicarbaldehyde (5) as a yellow solid ( The yield was 92% (0.469 g).

Physical property data; m. p. (CHCl ₃ ) 185.0 to 186.5 ° C .; ¹ H-NMR (500 MHz, CDCl ₃ ) δ 10.24 (s, 2H), 9.31 (d, J = 8.5, 2H), 8.13 (D, J = 8.0 Hz, 2 H), 7.99 (d, J = 9.0 Hz, 2 H), 7.78 (t, J = 8.3 Hz, 2 H), 7.67 (t, J = 7.5 Hz, 2H), 7.50 (d, J = 8.0 Hz, 2H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ 193.1, 145.3, 134.1, 133.7, 130. 6, 130.2, 129.8, 128.8, 128.7, 127.6, 126.0; IR (film KBr)? _Max 1666, 1587, 1501, 1427, 1340, 1177, 1059, 883, 833 , 750,709,650cm ^-1; HR ^{S (ESI) [M + Na} ] + calculated for [C 22 H 14 Na 1 O 2] +: 333.08915, found: 333.08924.

[3] Synthesis of picene-13,14-dione (1) [2,2′-binaphthalene] -1,1′-dicarbaldehyde (5) (10.0 mg, 0) cooled to 0 ° C. in an argon atmosphere 1,032-diazobicyclo [5.4.3] in a solution of 3-ethyl-5- (2-hydroxy) -4-methylthiazolinium bromide (1.6 mg, 0.00644 mmol) in dimethylformamide (500 μL). 0] Undec-7-ene (DBU, 4.8 μL, 0.0322 mmol) was added. The reaction mixture was warmed to room temperature and stirred for 1.5 hours. After cooling to 0 ° C., the reaction was quenched with 1 M aqueous hydrochloric acid (5 mL) and ethyl acetate (5 mL) was added. Transfer to a separatory funnel, extract, then extract the aqueous layer twice with ethyl acetate (5 mL). The combined organic layer was dried by adding an appropriate amount of magnesium sulfate, and then the magnesium sulfate was removed by filtration. The organic solvent was removed from the dried organic layer by distillation under reduced pressure. The resulting crude product was purified by silica gel column chromatography (developing solvent: 100% benzene) to obtain the desired picene-13,14-dione (1) quantitatively (10 mg) as red crystals.

Physical property data; m. p. (CHCl _{3 /} MeOH) 293.0 to 298.0 ° C .; ¹ H-NMR (500 MHz, CDCl ₃ ) δ 9.34 (d, J = 8.5 Hz, 2 H), 8.21 (d, J = 8. 5 Hz, 2H), 8.16 (d, J = 8.5 Hz, 2H), 7.85 (d, J = 8.0 Hz, 2H), 7.71 (dt, J = 1.2, 7.8 Hz) , 2H), 7.57 (dt, J = 1.2, 7.5 Hz, 2H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ 187.2, 138.7, 137.2, 133.9, 131 .8, 130.9, 128.7, 127.9, 127.0, 125.5, 122.4; IR (film KBr)? _Max 1659, 1589, 1508, 1356, 1223, 1082, 824, 731, 640cm ^-1; UV / Vis (CHC ^{_{3): λ max 244.5,300.5,406.5nm; HRMS}} (ESI) [M + Na] + calculated for [C 22 H 12 Na 1 O 2 +: 331.07350, found: 331.07155.

Synthesis Example 2: Synthesis of pentaphen-6,7-dione
Pentaphen-6,7-dione was synthesized according to the following synthesis route.

[4] Synthesis of dimethyl [2,2'-binaphthalene] -3,3'-dicarboxylate (8) Methyl 3-hydroxy-1-naphthoate (6) (2.00 g) cooled to 0 ° C. under argon atmosphere Trifluoromethanesulfonic anhydride (2.0 mL, 0.0119 mol) was slowly added to a solution (100 mL) of a solution of 4-N, N-dimethylaminopyridine (DMAP, 2.42 g, 0.0198 mol) in dichloromethane added. The reaction mixture was stirred for 30 minutes at a reaction temperature of 0 ° C. Subsequently, the reaction temperature was raised to room temperature and stirred for a further 42 hours. Distilled water (50 mL) was added to the reaction solution to stop the reaction, and the organic layer was extracted with dichloromethane (50 mL). This operation was repeated a total of 3 times, and all the organic layers obtained were washed twice with about 100 mL of 1M hydrochloric acid and a saturated aqueous sodium chloride solution. The organic layer was dried by adding an appropriate amount of magnesium sulfate, and then the magnesium sulfate was removed by filtration. The organic solvent was removed from the dried organic layer by distillation under reduced pressure. The crude product (7) obtained was used as it was for the next reaction.

Crude product (7) obtained by cooling bis (triphenylphosphine) palladium (II) dichloride (PdCl ₂ (PPh ₃ ) ₂ , 0.69 g, 0.000989 mol) under argon atmosphere to 0 ° C., potassium carbonate (4. It was added to a solution of 10 g (0.0297 mol) and bispinacol diboron (0.501 g, 1.97 mmol) in dioxane (80 mL) / distilled water (0.534 mL, 0.0297 mmol). The reaction mixture was allowed to warm to 90 ° C. for 1 hour at room temperature and was allowed to react for 22 hours. The reaction solution was allowed to cool to room temperature, and the solid in the reaction system was removed by filtration using a silica gel pad. At this time, the reaction mixture was eluted with a 50% ethyl acetate / hexane solution. The organic solvent of the collected filtrate was evaporated under reduced pressure to obtain a crude product. The crude product is purified by silica gel column chromatography (developing solvent: gradient of 50% chloroform / hexane to 100% chloroform), and the target dimethyl [2,2'-binaphthalene] -3,3'-dicarboxylate ( 8) was obtained as a yellow solid (yield 95% (6.98 g)).

Physical property data; m. p. (CHCl ₃ ) 172.0-176.0 ° C .; ¹ H-NMR (500 MHz, CDCl ₃ ) δ 8.62 (s, 2H), 7.99 (d, J = 8.0, 2H), 7.86 (D, J = 8.5 Hz, 2H), 7.77 (s, 2H), 7.61 (t, J = 8.3 Hz, 2H), 7.56 (t, J = 7.5 Hz, 2H) , 3.67 (s, 3 H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ 167.9, 140.0, 135.1, 1321, 1, 131.4, 129.9, 129.3, 128. 7, 128.5, 128.1, 127.0, 52.3; IR (film KBr)? _Max 2949, 1724, 1628, 1441, 1285, 1198, 1134, 1097, 1063, 907, 795, 750, 671 cm ^-1; HRMS (ESI _{^{[M + Na] + calculated for}} [C 24 H 118 Na 1 O 4] +: 393.11028, found: 393.11032.

[5] Synthesis of [2,2′-binaphthalene] -3,3′-dicarbaldehyde (10) Dimethyl [2,2′-binaphthalene] -3,3′-dicarboxylate (8) under argon atmosphere (1.39 g, 0.00375 mol) was dissolved in 50 mL of dry tetrahydrofuran. After cooling to 0 ° C., diisobutylaluminum hydride (DIBAL, 30.9 mL, 0.0315 mmol) was added. The reaction mixture was warmed to room temperature and stirred for 45 hours. The reaction solution was carefully added to 4 M aqueous hydrochloric acid (100 mL) cooled to 0 ° C. The solution was stirred for 30 minutes and the resulting needles were collected by filtration. The resulting crystals (9) were washed with water (50 mL) and ether (10 mL). Crude crystal (9) was used in the next reaction as it was.

  Under an argon atmosphere, manganese oxide (6.50 g, 0.0750 mol) was added to a dichloromethane solution (200 mL) of crude crystals (9), and the mixture was stirred at room temperature for 23 hours. The reaction mixture was filtered through a silica gel pad and eluted with chloroform. The organic solvent was distilled off under reduced pressure to obtain 10 crude products. The crude product was purified by silica gel column chromatography (developing solvent: 50% chloroform / benzene) to give the desired [2,2′-binaphthalene] -3,3′-dicarbaldehyde (10) as a yellow solid ( A yield of 52% (0.61 g) was obtained.

Physical property data; m. p. (CHCl ₃ ) 202.0 to 204.5 ° C .; ¹ H-NMR (500 MHz, CDCl ₃ ) δ ¹ 0.01 (s, 2 H), 8.54 (s, 2 H), 8.09 (d, J = 8 0.0 Hz, 2H), 7.90 (d, J = 8.0 Hz, 2H), 7.83 (s, 2H), 7.69 (dt, J = 1.2, 7.5 Hz, 2H), 7 .64 (dt, J = 1.2, 7.5 Hz, 2H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ 191.7, 136.7, 135.5, 133.0, 132.9, 132. 3, 131.0, 129.8 (2C), 128.1, 127.5; IR (film KBr)? _Max 2833, 2723, 1693, 1622, 1589, 1441, 1256, 1155, 903, 750 cm- ¹ ; HRMS (ESI) [M + Na] ^{_{+ Calculated for [C 22 H 14}} Na 1 O 2] +: 333.08915, found: 333.09016.

[6] Synthesis of pentaphen-6,7-dione (11) [2,2′-binaphthalene] -3,3′-dicarbaldehyde (10) (50.0 mg, 0) cooled to 0 ° C. under argon atmosphere 161 mmol) and 3-ethyl-5- (2-hydroxy) -4-methylthiazolinium bromide (8.1 mg, 0.0.322 mmol) in dimethylformamide (5 mL) in 1,8-diazabicyclo [5. 4.0] Undec-7-ene (DBU, 24.0 μL, 0.161 mmol) was added. The reaction mixture was warmed to room temperature and stirred for 2 hours. After cooling to 0 ° C., the reaction was quenched with 1M aqueous hydrochloric acid (10 mL) and ethyl acetate (10 mL) was added. Transfered to a separatory funnel and extracted, followed by extraction of the aqueous layer twice with ethyl acetate (10 mL). The combined organic layer was dried by adding an appropriate amount of magnesium sulfate, and then the magnesium sulfate was removed by filtration. The organic solvent was removed from the dried organic layer by distillation under reduced pressure. The resulting crude product was purified by silica gel column chromatography (developing solvent: 100% benzene) to obtain the desired pentaphen-6,7-dione (11) as red crystals (73% (36.3 mg)). .

Physical property data; m. p. (CHCl ₃ / MeOH) 345-348 ° C .; ¹ H-NMR (500 MHz, CDCl ₃ ) δ 8.84 (s, 2H), 8.64 (s, 2H), 8.00 (d, J = 3.5 Hz , 2H), 7.98 (d, J = 3.5Hz, 2H), 7.68 (t, J = 7.5Hz, 2H), 7.58 (t, J = 7.8Hz, 2H); 13 C-NMR (125 MHz, CDCl ₃ ) δ 181.3, 137.1, 133.5, 132.9, 131.5, 130.5 (2C), 129.2, 128.7, 128.1, 123. 9; IR (film KBr) ν max 3051,1670,1618,1585,1441,1339,1273,1120,1173,1020,905,818,743cm -1; UV / Vis (CHCl 3): λ max 264 5 (sh), 282.0,292.0,305.0,324.5,378.0,478.0nm; fluorescence (CHCl 3, λ ex 371nm): λ max 602nm; HRMS (ESI) [M + Na] ⁺ Calculated for [C ₂₂ H ₁₂ Na ₁ O ₂ ] ⁺ : 331.07350, found: 331.07283.

"Example 1"
According to the following synthesis route, a composition for an organic semiconductor containing a polycyclic aromatic compound and a Lewis acid was irradiated with light to synthesize a radical compound (12).

[7] Synthesis of radical compound (12) In a test tube under an argon atmosphere, boron trifluoride diethyl etherate (BF ₃ · Et ₂ O, 20 mL, 0.1602 mol) is added, and picene-13,14-dione ( 1) A dichloromethane solution (30 mL) of (100.0 mg, 0.3243 mmol) was slowly added using a pipette. By the above operation, the two-layer system of the dichloromethane layer and the diethyl ether layer could be created in the test tube. Subsequently, it was irradiated with light of 405 nm for 29.5 hours using a violet LED at 23 ° C. The precipitated crystals were filtered when the dichloromethane layer turned from orange to deep green. The obtained crystals were washed with diethyl ether to obtain the target radical compound (12) as a deep green solid (yield 67% (78.0 mg)). The structure was confirmed by an X-ray crystal structure analyzer (manufactured by Bruker, "Smart APEX II ultra").

Physical data; melting point: decomposition at 210 ° C., UV / Vis (CH ₂ Cl ₂ ): λ _max 262.0, 288.5, 314.0, 330.5, 385.0, 448.5, 481.5, 674.5 nm.

  About the obtained radical compound (12), the amount of residual radicals was measured using ESR apparatus (The Nippon Denshi Co., Ltd. make, "JES-TE200"). The sample mass was 1 mg. The ESR spectrum is shown in FIG.

Separately, 0.0022 mg of the radical compound (12) was dissolved in dichloromethane (10 mL) to prepare a sample solution.
About the obtained sample solution, the amount of residual radicals was measured using the ESR apparatus (the JEOL Co., Ltd. make, "JES-TE200"). The ESR spectrum is shown in FIG.

  Moreover, about the radical compound (12), the specific resistance (electrical resistivity) was measured by the two-terminal method using the electrometer (the product made by ADC Corporation, "8252"). The results are shown in Table 1.

"Example 2"
According to the following synthesis route, a composition for an organic semiconductor containing a polycyclic aromatic compound and a Lewis acid was irradiated with light to synthesize a radical compound (13).

[8] Synthesis of radical compound (13) In a test tube under an argon atmosphere, boron trifluoride diethyl etherate (BF ₃ · Et ₂ O, 4 mL, 0.03204 mol) is added, and pentaphen-6,7-dione ( 11) (10.0 mg, 0.03243 mmol) in dichloromethane (13 mL) was slowly added using a pipette. By the above operation, the two-layer system of the dichloromethane layer and the diethyl ether layer could be created in the test tube. Subsequently, it was irradiated with light of 470 nm for 19 hours at 23 ° C. using a blue LED. When the dichloromethane layer changed from orange to dark green, the precipitated solid was filtered under an argon atmosphere. The target radical compound (12) was obtained as a deep green solid (yield 86% (10.0 mg)).

Physical property data; melting point: decomposition at 100 ° C., UV / Vis (BF ₃ .Et ₂ O): λ _max 227.5, 255.0, 313.0, 328.5, 343.5, 406.0, 428. 5, 501.0, 573.0, 607.5 nm.

  With respect to the obtained radical compound (13), the amount of residual radicals was measured in the same manner as in Example 1. The ESR spectrum is shown in FIG.

"Comparative example 1"
The specific resistance of naphthalene was measured in the same manner as in Example 1. The results are shown in Table 1.

"Comparative example 2"
The resistivity of biolanthrene was measured in the same manner as in Example 1. The results are shown in Table 1.

"Comparative example 3"
The specific resistance of phthalocyanine was measured in the same manner as in Example 1. The results are shown in Table 1.

As is clear from the results in Table 1, the radical compound obtained in Example 1 had a small specific resistance and excellent conductivity as compared with the polycyclic aromatic compounds used in Comparative Examples 1 to 3.
Moreover, as is clear from FIGS. 1 and 3, it was confirmed that the radicals obtained in Examples 1 and 2 were localized. In particular, as apparent from FIG. 2, in the radical compound obtained in Example 1, the signal does not split even when ESR is measured in the state of being dissolved in an organic solvent, and the radical is stably localized. I was able to confirm.
In addition, when the radical compound obtained in Example 1 was allowed to stand in air for 1 year and then its ESR was measured, the same signal as in FIG. 1 was observed. This means that the radical is stably localized even if the radical compound is left in the air for one year.
Moreover, when the X-ray structural analysis was performed about the radical compound obtained in Example 1, it has confirmed that it was stacking between molecules. The intermolecular distance was 3.4 mm.

  The radical compound of the present invention has a localized radical and is useful as an organic semiconductor. The present invention can be used in a device using an organic semiconductor, specifically, an organic field effect transistor (OFET), an organic electroluminescence element (organic EL element), an organic solar battery, a secondary battery, and the like.

Claims (6)

  An organic semiconductor composition comprising a polycyclic aromatic compound having an orthoquinone structure and a Lewis acid containing boron. The polycyclic aromatic compound having an orthoquinone structure is at least one member selected from the group consisting of compounds represented by the following general formula (i) and the following general formula (ii), and the Lewis acid is a three-halogen compound The composition for organic semiconductors according to claim 1, which is boron fluoride.

(In formula (i), Z ¹ and Z ² are each independently an aromatic hydrocarbon ring or an aromatic heterocyclic ring.)

(In formula (ii), Z ^{3 to} Z ⁵ are each independently an aromatic hydrocarbon ring or an aromatic heterocyclic ring.) Radical compounds represented by the following general formula (I) and the following general formula (II).

(In formula (I), R ¹ and R ² each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group or a siloxy group, and Z ¹ and Z ² each independently represent An aromatic hydrocarbon ring or an aromatic heterocyclic ring)

(In formula (II), R ³ and R ⁴ each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group or a siloxy group, and Z ^{3 to} Z ⁵ each independently represent An aromatic hydrocarbon ring or an aromatic heterocyclic ring)   The manufacturing method of the radical compound which has the process of irradiating light to the composition for organic semiconductors of Claim 1 or 2.   The device provided with the layer formed using the composition for organic semiconductors of Claim 1 or 2.   A device comprising a layer containing the radical compound according to claim 3.

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