JP2008071840A - Organic semiconductor material, organic semiconductor device using it and manufacturing method for organic semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic semiconductor material containing a low molecular compound being proper to a welding process and having a solubility, an organic semiconductor device using the organic semiconductor material and a manufacturing method for the organic semiconductor device. <P>SOLUTION: The organic semiconductor material contains a compound shown by general formula (1). Herein, R<SB>1</SB>and/or R<SB>2</SB>in formula represents a functional group having a soluble effect. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an organic semiconductor material used for photoelectric, optoelectronic, electrical, and electronic components. The present invention relates to an organic semiconductor material including a transistor, a thin film photoelectric conversion element, a dye-sensitized solar cell, and a light emitting device having an organic carrier transport layer using the organic semiconductor material.

  Conventionally, inorganic semiconductor materials containing silicon (Si) or the like have been developed, but in recent years, organic semiconductor materials containing organic compounds have been actively developed.

  An advantage of using an organic semiconductor material is that a welding method can be used as a method for disposing a semiconductor layer containing an organic semiconductor material on a substrate. As a result, paper, plastic, or the like can be used for the substrate, and the organic semiconductor device can be reduced in weight and flexibility. The welding method is a method of disposing a semiconductor layer by applying a solution containing an organic semiconductor material to a substrate, and examples thereof include a coating method, a spin coat method, and an ink jet method. When this method is used, compared to the case of using the conventional vacuum deposition method, the manufacturing process is simplified and the cost required for manufacturing is greatly reduced. Manufacture is possible.

  Conventionally, conjugated polymers and oligomers (such as polythiophene derivatives, PPV derivatives, and copolymers thereof) disclosed in Patent Document 1, or solubilized precursors of pentacene disclosed in Patent Document 2 are used. It was an organic semiconductor material used for typical welding methods.

On the other hand, recently, a compound in which a solubilizing functional group is introduced into a low molecular weight compound has been tried. For example, there is a successful example such as a functionalized highly soluble pentacene derivative disclosed in Patent Document 3. In Non-Patent Document 1, DT-TTF (Dithieno [3 , 4-d] tetrathiafulvalene) has been reported to exhibit high field effect mobility as a field effect transistor and can be used as an organic semiconductor material.
JP-A-2005-158520 JP 2004-221318 A JP 2006-28055 A M. Mas-Torrent; P. Hadley; ST Bromley; X. Ribas; J. Tarres; M. Mas; E. Molins; J. Veciana; C. Rovira,, J. Am. Chem. Soc., 2004, 126 , 8456-8553

  However, since the organic semiconductor materials disclosed in Patent Documents 1 and 2 are polymers and it is difficult to introduce various functional groups into the molecules, it is difficult to improve the organic semiconductor materials. Therefore, there is a drawback that it is difficult to develop a new organic semiconductor material based on the organic semiconductor material.

  In addition, the organic semiconductor material disclosed in Patent Document 3 has not yet been industrially applicable because the steric hindrance of the soluble functional group prevents the semiconductor core portion from overlapping between molecules.

  Furthermore, the organic semiconductor material disclosed in Non-Patent Document 1 has a problem that it cannot be used in a welding method because it is hardly soluble in an organic solvent.

  Conventionally developed organic semiconductor materials have such problems, and the development of organic semiconductor materials suitable for welding methods has not progressed.

  The present invention has been made in view of the above problems, and an object thereof is to provide an organic semiconductor material containing a soluble low-molecular compound suitable for welding, an organic semiconductor device using the same, and a method for producing the same It is to be.

  In order to solve the above problems, the present inventor made a tetrathiafulvalene derivative (hereinafter referred to as TTF derivative) and used it as an organic semiconductor material. Among the TTF derivatives, the pyrrole-fused TTF (hereinafter referred to as pyrrolo TTF). It was found that an organic semiconductor material containing a low-molecular compound having) is an organic semiconductor material suitable for welding, and the present invention has been completed.

  That is, the organic semiconductor material according to the present invention is an organic semiconductor material containing a compound represented by the general formula (1).

General formula (1)
In the formula, R ₁ and / or R ₂ represents a functional group having a solubility effect.

According to the above configuration, the compound is a pyrrolo TTF derivatives as introducing a functional group having a solubility effect represented by the above R _1, R ₂ on the nitrogen atom of the pyrrole ring. A pyrrolo TTF derivative is a low-molecular compound excellent in donor property and conductivity because of its low oxidation potential, and allows high intermolecular interaction while being a low molecule.

  Further, when a compound represented by the general formula (1) is synthesized from pyrrolo TTF, an isomer is not generated, and thus the compound obtained by synthesis is uniform. Therefore, when the organic semiconductor material is disposed in the semiconductor layer, it can be uniformly disposed vertically and horizontally. Therefore, a molecular alignment effect occurs in the organic semiconductor material, and an organic semiconductor device with good performance can be manufactured.

  In addition, the above-mentioned “molecular arrangement effect” means that when molecules adjacent to each other in the upper and lower sides overlap well and / or molecules adjacent to each other in the left and right are arranged well, the π electron orbit of each molecule The above-mentioned interaction works well, and it means an effect that carriers, that is, electrons or holes can move between molecules at high speed.

  Furthermore, although pyrrolo TTF itself is insoluble in an organic solvent, the solubility in an organic solvent can be improved by introducing the functional group. Therefore, the compound can be dissolved in an appropriate organic solvent, and the compound can be disposed on the substrate using a welding method such as spin coating. Therefore, it is possible to simplify the manufacturing process of the organic semiconductor, greatly reduce the cost of the equipment required for manufacturing, and manufacture an organic semiconductor device having a large area.

Moreover, it is preferable that R ₁ and / or R _{2 of the} compound represented by the general formula (1) contained in the organic semiconductor material according to the present invention is a functional group containing a carbon skeleton in the main chain.

  According to the above configuration, by using a functional group containing a carbon skeleton in the main chain, a hydrophobic interaction occurs between the functional group and / or the compound represented by the general formula (1) and the functional group. The generated hydrophobic interaction is particularly effective for dissolving the compound in the organic solvent, and can further improve the solubility in the organic solvent. Therefore, the compound can be dissolved in an appropriate organic solvent, and the compound can be disposed on the substrate using a welding method such as spin coating. Therefore, it is possible to simplify the manufacturing process of the organic semiconductor, greatly reduce the cost of the equipment required for manufacturing, and manufacture an organic semiconductor device having a large area.

Moreover, it is preferable that R < ₁ > and / or R < ₂ > of the compound represented by the said General formula (1) contained in the organic-semiconductor material which concerns on this invention is a C4 or more alkyl group.

  According to the above configuration, by introducing an alkyl group having 4 or more carbon atoms, hydrophobic interaction between the alkyl groups and / or between the alkyl group and pyrroloTTF is improved, and solubility in an organic solvent is further improved. be able to. Therefore, the compound can be dissolved in an appropriate organic solvent, and the compound can be disposed on the substrate using a welding method such as spin coating. Therefore, it is possible to simplify the manufacturing process of the organic semiconductor, greatly reduce the cost of the equipment required for manufacturing, and manufacture an organic semiconductor device having a large area.

  Furthermore, in the compound represented by the general formula (1), the molecular alignment effect is more strongly generated by the interaction between the alkyl groups. Therefore, donor property and conductivity related to the performance of the semiconductor can be improved.

Moreover, it is preferable that R < ₁ > and / or R < ₂ > of the compound represented by the said General formula (1) contained in the organic-semiconductor material which concerns on this invention is a C12 or more linear alkyl group.

  According to the above configuration, by using a linear alkyl group having 12 or more carbon atoms, hydrophobic interaction between the alkyl groups and / or between the alkyl group and pyrroloTTF is further improved, and the general formula (1) The solubility with respect to the organic solvent of the compound represented by can be improved more. In addition, the molecular alignment effect is more intense due to the interaction between the linear alkyl groups. Therefore, when used as a material for a field effect transistor, there is a surprising effect that field effect mobility is excellent.

  Moreover, this invention is also an organic-semiconductor device characterized by including the said organic-semiconductor material.

  According to the said structure, since the organic-semiconductor device concerning this invention contains the organic-semiconductor material concerning this invention, it can be manufactured using a welding method. Therefore, the organic semiconductor device can be characterized by being lightweight, flexible and large in area.

  The organic semiconductor device according to the present invention also includes the organic semiconductor device that is a transistor.

  According to the above configuration, since the transistor according to the present invention includes the organic semiconductor material according to the present invention, the transistor can have characteristics of being lightweight, flexible, and having a large area.

  The organic semiconductor device according to the present invention also includes the above organic semiconductor device which is a light emitting device having an organic carrier transport layer and / or a light emitting layer.

  According to the above configuration, the light-emitting device having the organic carrier transport layer and / or the light-emitting layer according to the present invention includes the organic semiconductor material according to the present invention, and thus has features of being lightweight, flexible, and having a large area. be able to.

  Moreover, this invention also includes the manufacturing method of the organic-semiconductor device including the process of arrange | positioning the said organic-semiconductor material to a board | substrate with a welding method.

  According to the said structure, since the organic-semiconductor material which concerns on this invention is used, the organic-semiconductor device which is low cost, lightweight, flexible, and a large area can be manufactured. Furthermore, when manufacturing an organic semiconductor device, it is possible to simplify the manufacturing process and significantly reduce the cost of equipment required for manufacturing.

As described above, the organic semiconductor material according to the present invention includes a compound represented by the general formula (1). In the formula, R ₁ and / or R ₂ represent a functional group having a solubility effect. The compound represented by the general formula (1) not only has excellent donor properties and conductivity but also has high intermolecular interaction, and acquires high solubility in an organic solvent by introducing a functional group.

  Therefore, an organic semiconductor material containing a low molecular weight compound suitable for a welding method which is one of methods for arranging a semiconductor layer, an organic semiconductor device having a light weight, flexibility and large area using the organic semiconductor material, and a manufacturing method thereof There is an effect that it can be provided.

  An embodiment of the present invention will be described as follows, but the present invention is not limited to this.

  Specifically, the present inventors focused on the following points of a pyrrole-fused TTF derivative (hereinafter referred to as a pyrrolo TTF derivative), which is a TTF derivative, and synthesized a pyrrolo TTF derivative.

  1) Since the molecular skeleton is similar to that of a dithieno TTF that has a high field effect mobility in a field effect transistor in which a semiconductor layer is arranged by a single crystal or vacuum deposition method, it can be expected to be a high-performance organic semiconductor material. .

  2) When two functional groups are introduced on the nitrogen of the pyrrole ring so as not to prevent the interaction between TTFs between molecules, cis and trans isomers do not occur in pyrrolo TTF, so that the molecular alignment effect is expected. it can.

  3) When a functional group that is a linear carbon skeleton is introduced onto the nitrogen of the pyrrole ring, the molecule can take a linearly extended structure. Therefore, π-π between TTFs due to the fastener effect between the functional groups. , And S-S interaction can be expected to be enhanced.

  The pyrrolo TTF derivative introduced with an alkyl group having 4 or more carbon atoms was soluble in an organic solvent. Furthermore, it has been found that when a pyrrolo TTF derivative having an alkyl group having 12 or more carbon atoms introduced therein is used as a material for an organic semiconductor device, the organic semiconductor device exhibits a very high field effect mobility.

In the pyrrolo TTF derivative of the present invention, the pyrrolo TTF composed of the functional groups represented by R ₁ and R ₂ both represented by nC ₄ H ₉ is “JOJeppensen; K, Takimiya; F. Jensen; T. Brimert; K. Nielsen; N. Thorup; J. Becher, J. Org. Chem., 2000, 65, 5794-5805 ”, the above compounds are used as organic semiconductor materials. Is not described at all in the above-mentioned literature, and the finding that the above-mentioned compound is very useful as an organic semiconductor material has been revealed for the first time by the present invention. It can be said that it is difficult for those skilled in the art to predict. Therefore, the use of the above compound as a material for an organic semiconductor is based on new knowledge obtained as a result of intensive studies by the present inventors, and thus the above compound is also included in the present invention.

[Characteristics of organic semiconductor materials]
The organic semiconductor material of the present invention is characterized by containing a compound represented by the general formula (1). The organic semiconductor material may consist only of the compound represented by the general formula (1), or may contain other substances as long as the properties of the compound represented by the general formula (1) are not impaired. .

Examples of the other substances include Lewis acids such as PF ₆ , AsF ₅ and FeCl ₃ ; acids such as hydrochloric acid, sulfuric acid and sulfonic acid; halogen atoms such as iodine and bromine; dopants such as metal atoms such as sodium and potassium Can be mentioned.

  The conductivity of the organic semiconductor material can be adjusted by adding the dopant. The doping method is not particularly limited, and a conventionally known method can be used. Examples include, but are not limited to, gas phase doping, liquid phase doping, solid phase doping, and the like.

The compound represented by the above general formula (1) is a pyrrolo TTF derivative capable of introducing two functional groups represented by R ₁ and R ₂ having solubility. The above-mentioned “R ₁ ” and “R ₂ ” may be the same functional group or may be different functional groups. However, when the functional groups are the same, the molecular alignment effect is superior. This is more preferable.

The “R ₁ ” and “R ₂ ” are not particularly limited as long as they are functional groups having a solubility effect.

  One of the reasons why the compound represented by the general formula (1) is hardly soluble in an organic solvent is that the intermolecular interaction between the compounds is strong and exists in close contact. Furthermore, when the compounds are in close contact with each other, the intermolecular interaction becomes stronger due to the van der Waals force, which makes it more difficult to dissolve in organic solvents.

  Therefore, if the intermolecular interaction acting on the compound represented by the general formula (1) can be weakened and / or the intermolecular distance can be increased, the compound can be dissolved in an organic solvent. In other words, the solubility effect described above improves the solubility of the compound in an organic solvent by weakening the intermolecular interaction between the compounds represented by the general formula (1) and / or increasing the distance between the molecules. Refers to the effect of

  Specifically, the above-mentioned “functional group having a solubility effect” means that when introduced into the compound represented by the general formula (1), between the functional groups and / or between the functional group and the compound. It is a functional group that generates an interaction selected from the group consisting of electrostatic interaction, hydrophobic interaction, hydrophilic interaction, and steric interaction.

The above-mentioned electrostatic interaction refers to an interaction that acts between compounds having a charge or compounds that are polarized by an induced effect. Moreover, the said hydrophobic interaction means the interaction which acts between compounds which do not have polarity, such as a hydrocarbon compound. Moreover, the said hydrophilic interaction means the interaction which acts between compounds which have polarity, such as an alcohol group and a carboxyl group.
The steric interaction means an interaction that works between bulky compounds such as a phenyl group having a steric effect.

  One type of interaction may occur, or two or more types of interaction may occur simultaneously.

  Examples of the functional group having a solubility effect include a functional group containing a carbon skeleton in the main chain, an alcohol group, a carbonyl group, a sulfamoyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, a sulfinyl group, an amino group, and a halogen atom. , Cyano group, silyl group and the like, but are not limited thereto. Furthermore, a functional group in which the above compounds are bonded to each other through an ether bond, an amide bond, a thioether bond, a polyether bond, an ester bond, or the like may be used. Moreover, the functional group which can couple | bond with the compound represented by General formula (1) through an ether bond, a thioether bond, a polyether bond, an ester bond, etc. may be sufficient as the said compound.

  Furthermore, considering the fact that the compound is dissolved in an organic solvent and the molecular alignment effect described above, a functional group excellent in hydrophobic interaction is preferable.

  For example, when such a functional group is introduced into the compound represented by the general formula (1), a hydrophobic interaction occurs between the functional groups and / or between the functional group and the compound. The generated hydrophobic interaction increases the distance between the compounds and / or weakens the intermolecular interaction, thereby increasing the solubility of the compound represented by the general formula (1) in an organic solvent.

  From the above viewpoint, the functional group according to the present invention is preferably a functional group containing a carbon skeleton in the main chain.

  The functional group containing a carbon skeleton of the main chain may contain an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom or the like as long as the main chain is a carbon skeleton composed of a carbon atom and a hydrogen atom.

  Examples of the functional group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkyloxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, and an alkoxy group. Examples thereof include, but are not limited to, a carbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a halogenated hydrocarbon group.

  Furthermore, the functional group having the above-described solubility effect is preferably an alkyl group having 4 or more carbon atoms.

  The alkyl group is not particularly limited as long as it is a linear, branched or cyclic alkyl group, but from the viewpoint of molecular alignment effect, n-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -A heptadecyl group, n-octadecyl group, n-nonadecyl group etc. are mentioned, However It is not limited to these.

  Further, among the above linear alkyl groups, a high performance organic semiconductor material can be provided if it is a linear alkyl group having 12 or more carbon atoms.

  Examples of the linear alkyl group having 12 or more carbon atoms include n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n- Nonadecyl group etc. are mentioned, However It is not limited to these.

  As a method for introducing the linear alkyl group, a method using an alkyl bromide is preferable from the viewpoint of ease of synthesis. Generally, alkyl bromides having up to 22 carbon atoms are available, and alcohols or alkyl chlorides that are raw materials for synthesizing alkyl bromides are generally available having up to 30 carbon atoms. is there. In addition, the longer the alkyl bromide, the higher the melting point of the alkyl bromide, making it difficult to handle, and the difficulty of removing the alkyl bromide, making it difficult to purify the compound after the reaction. . Therefore, it can be said that an alkyl bromide having up to 20 carbon atoms is suitable for the synthesis of the organic semiconductor material of the present invention.

  Considering the above, the upper limit of the carbon number of the linear alkyl group is preferably 30, more preferably 22, and particularly preferably 20.

[Synthesis of organic semiconductor materials]
The method for synthesizing the organic semiconductor material is not particularly limited, and Document 1 (JOJeppensen; K, Takimiya; F. Jensen; T. Brimert; K. Nielsen; N. Thorup; J. Becher, J. Org. Chem., 2000, 65, 5794-5805), and a method of synthesizing a tosyl tetrathiafulvalene by alkylation, or reference 2 (Peter J. Skabara and Klaus Mullen, J. Mater. Chem., 1998). , 8 (8), 1719-1724), and a method of synthesizing by coupling an alkyl dithiolopyrrole.

  For example, as a specific example of the method for synthesizing the organic semiconductor material composed of the compound represented by the general formula (1), the organic semiconductor material can be synthesized by the reaction route shown in FIG. Moreover, the number described in the reaction pathway represents the corresponding compound.

Described in Reference 1 after reacting 1,2-dibromoethane (hereinafter referred to as “Compound 2” where appropriate) and carbon disulfide (CS ₂ ) in the presence of a catalyst by a method well known to those skilled in the art 1,3-dithiolane-2-thione (hereinafter referred to as “compound 3” as appropriate) can be synthesized.

In the above reaction, a conventionally known phase transfer catalyst such as tetra n-butylammonium bromide (Bu ₄ NBr) can be suitably used as the catalyst. In addition the basic solution such as aqueous sodium hydroxide to the reaction solution of Compound 2 with carbon disulfide (CS _2), the reaction solution can be promoting the above reaction by basic. The amount of sodium hydroxide contained in the aqueous sodium hydroxide solution is preferably 1.0 to 3.0 mol, and 1.5 to 2.0 mol, relative to 1.0 mol of the compound 2. It is more preferable.

  Next, using the method described in Document 1, 4,5-bis (methoxycarbonyl) -1,3-dithiol-2-thione (hereinafter referred to as “compound 4” as appropriate) can be synthesized from the compound 3. it can.

  Next, according to the method described in “JO Jeppesen, K. Takimiya, N. Thorup, J. Becher; Synthesis 1999, No. 5 803-810”, 4,5-bis (hydroxymethyl) -1,3-dithiol -2-thione (hereinafter referred to as “Compound 5” as appropriate) can be synthesized. That is, compound 5 can be synthesized by reducing compound 4 using a reducing agent.

As the reducing agent, known reducing agents such as sodium borohydride (NaBH ₄ ), hydrazine (NH ₂ —NH ₂ ), lithium aluminum hydroxide (LiAlH ₄ ) can be used, and in particular, sodium borohydride (NaBH) ₄ ) is preferably used. In the above document, the reaction temperature for reduction is room temperature, but the reaction temperature is preferably 0 to −10 ° C., more preferably −5 to −10 ° C. in order to avoid generation of by-products.

  In the above-mentioned document, the reaction time for reduction is 1 hour, but the reaction time is preferably 0.5 to 15 hours, more preferably 5 to 12 hours, in view of avoiding the generation of by-products. 10 hours is more preferable. Further, by adding 2.0 mol of lithium bromide (LiBr) to 1.0 mol of the compound 4 in the above reaction, the ester group can be selectively reduced.

  Further, when the compound 5 is purified, column chromatography is performed using ethyl acetate, and then column chromatography is performed using methylene chloride / ethyl acetate (2: 1 v / v) to increase the yield of compound 5. be able to.

  Next, using the method described in Document 1, 4,5-bis (bromomethyl) -1,3-dithiol-2-thione (hereinafter referred to as “Compound 6” as appropriate) is synthesized from Compound 5 above. Can do.

  The organic semiconductor material which consists of a compound represented by General formula (1) is compoundable by using the tosyl body to which the said compound 6 was tosylated, or the alkylated alkyl body.

<Method of synthesizing tosyl tetrathiafulvalene by alkylation>
Using the method described in Document 1, compound 6 and tosylamide monosodium salt (TsNHNa) were reacted to produce 4,6-dihydro-N-tosyl- (1,3) dithiolo [4,5-c] pyrrole- 2-thione (hereinafter referred to as “compound 7” as appropriate) can be synthesized.

  In the above Reference 1, after completion of the above reaction, Compound 7 is obtained by filtration using dimethylformamide (DMF), but the yield of Compound 7 can be increased by using acetonitrile instead of dimethylformamide (DMF). Can be increased.

  The tosylamide monosodium salt (TsNHNa) can be synthesized by a conventionally known method described in “Sebastiano Pappalado et. Al; J. Org. Chem, 1998, 53, 3521-3529”. That is, metallic sodium is dissolved in ethanol and refluxed, tosylamide is added, and the reaction is further refluxed. As the ethanol, either anhydrous ethanol or ethanol can be suitably used. In particular, when ethanol is used, the amount of the metallic sodium is preferably 1.0 to 1.5 mol, and 1.2 to 1.5 mol with respect to 1.0 mol of tosylamide. It is more preferable.

  After completion of the reaction, the produced white solid is washed with ethanol. The white solid of tosylamide monosodium salt (TsNHNa) can be synthesized by drying the white solid using anhydrous magnesium sulfate or the like.

  Next, using the method described in Document 1, the compound 7 is ketated to 4,6-dihydro-N-tosyl- (1,3) dithiolo [4,5-c] pyrrol-2-one (hereinafter referred to as “the compound 7”). (Hereinafter referred to as “compound 8”).

  Thereafter, using the method described in Document 1, N-tosyl- (1,3) dithiolo [4,5-c] pyrrol-2-one (hereinafter referred to as “Compound 9” as appropriate) is converted from Compound 8 above. Can be synthesized.

As the organic solvent used in the above reaction, hexane (n-C ₆ H ₁₄ ), benzene (C ₆ H ₆ ), toluene (PhCH ₃ ), chloroform (CHCl ₃ ), chlorobenzene (PhCl), or the like is preferably used. However, chlorobenzene (PhCl) is preferably used because the yield of compound 9 is increased.

Furthermore, potassium permanganate as the oxidizing agent _(KMnO 4), a known oxidizing agent such as 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) may be used a conventionally known method.

  Next, using the method described in Document 1, the compounds 9 are coupled together to synthesize bis (N-tosylpyrrolo [3,4-d]) tetrathiafulvalene (hereinafter referred to as “Compound 10” as appropriate). can do.

  Next, bis (pyrrolo [3,4-d]) tetrathiafulvalene (hereinafter, appropriately referred to as “compound 11”) can be synthesized from the compound 10 using the method described in Document 1.

  Next, an organic semiconductor material composed of the compound represented by the general formula (1) can be synthesized by reacting the halogenated alkyl group with the compound 11 using the method described in Document 1.

  A conventionally well-known thing can be used as said halogenated alkyl group. For example, bromomethane, bromoethane, n-bromopropane, fluoromethane, fluoroethane, n-fluoropropane and the like can be used.

<Method of synthesizing alkyl dithiolopyrrole by coupling>
Compound 6 is alkylated to synthesize alkyl dithiolopyrrole. Then, the organic semiconductor material which consists of a compound represented by General formula (1) is compoundable by coupling the dithiolopyrrole of the said alkyl body.

As the alkylation method, an alkylated amine (RNH ₂ ; R represents an arbitrary alkyl group) can be used, but is not limited thereto. Examples of the alkylated amine include, but are not limited to, methylamine (CH ₃ NH ₂ ), ethylamine (C ₂ H ₅ NH ₂ ), n-propylamine (C ₃ H ₇ NH ₂ ), and the like. .

Using the method described in Document 2, compound 6 is reacted with alkylated amine (RNH ₂ ) to give 4,6-dihydro-N-alkyl- (1,3) -dithiolo [4,5-c] pyrrole- 2-thione (4,6-dihydro-N-alkyl- (1,3) -dithiolo [4,5-c] pyrrole-2-thione) (hereinafter referred to as “compound 12” as appropriate) can be synthesized. .

  The reaction temperature of the above reaction is preferably 0 to 10 ° C., more preferably 0 to 5 ° C. for the purpose of increasing the yield of compound 12.

  Here, N-alkyl- (1,3) -dithiolo [4,5-c] pyrrol-2-thione (hereinafter, referred to as “compound 13” as appropriate) was synthesized from compound 12 to give compound 13 An organic semiconductor material composed of the compound represented by the general formula (1) can be synthesized by coupling each other. Any of the above-mentioned reactions can use a conventionally known method.

  In addition, using the method described in Document 2, the compound 12 is ketated, and 4,6 dihydro-N-alkyl- (1,3) -dithiolo [4,5-c] pyrrol-2-one which is a ketone body (Hereinafter referred to as “Compound 14” as appropriate) is synthesized.

  Next, compound 14 can be oxidized to synthesize N-alkyl- (1,3) -dithiolo [4,5-c] pyrrol-2-one (hereinafter referred to as “compound 15” as appropriate).

As the oxidizing agent, a conventionally known oxidizing agent such as potassium permanganate (KMnO ₄ ), 2,3-dichloro-5,6-dicyanobenzoquinoline (DDQ) can be used by a conventionally known method. In particular, when DDQ is used as an oxidizing agent, the reaction solution after completion of the oxidation reaction is washed with a basic solution, whereby unreacted DDQ and 2,3-dichloro-5, which is a reactive product of DDQ, are obtained. 6-Dicyano-1,4-hydroquinone can be removed from the organic layer.

  Further, the yield can be improved by 10% or more by the washing. Examples of the basic solution include, but are not limited to, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonium hydroxide solution.

  Further, when the basic solution is used for washing, the washing may be carried out only once, but washing is preferably carried out a plurality of times in order to completely remove unreacted DDQ. Moreover, when washing | cleaning over multiple times, you may carry out continuously with the said basic solution, and after washing | cleaning once with the said basic solution, washing with distilled water, and washing with the said basic solution again. You may go intermittently. The concentration of the basic solution is preferably 1 to 20%, more preferably 5 to 10%.

  Next, an organic semiconductor material composed of the compound represented by the general formula (1) can be synthesized by coupling the compounds 15 using the method described in Document 2.

[Organic semiconductor devices]
The present invention can provide an organic semiconductor device in which a semiconductor layer containing the organic semiconductor material of the present invention is disposed on a substrate, and a method for manufacturing the organic semiconductor device.

  Specifically, the organic semiconductor device is an organic semiconductor device including the semiconductor layer disposed on a substrate and two or more electrodes in contact with the semiconductor layer. The semiconductor layer is preferably a thin film, and the film thickness may be appropriately selected according to the structure and size of the device. For example, a film thickness of 20 to 1000 nM is generally used, but is not limited thereto.

  As a method for disposing the semiconductor layer on the substrate, a vacuum deposition method or a welding method can be used. In particular, since the organic semiconductor material of the present invention can be dissolved in an organic solvent, it is preferable to use a welding method. As the welding method, known methods described in JP-A-2006-114701 and JP-A-2006-28055 can be used.

  A specific welding method includes the following steps.

<Step of dissolving the organic semiconductor material of the present invention in an organic solvent>
The organic solvent that can be used in the welding method is not particularly limited as long as the organic semiconductor material of the present invention can be dissolved. For example, chain ether solvents such as diethyl ether and diisopropyl ether; cyclic ether solvents such as tetrahydrofuran and dioxane; ketone solvents such as acetone and methyl ethyl ketone; alkyl halide solvents such as chloroform and 1,2-dichloroethane; toluene Aromatic solvents such as o-dichlorobenzene, nitrobenzene and m-cresol, N-methylpyrrolidone, carbon disulfide and the like can be preferably used. In particular, it is preferable to use toluene because it dissolves the organic semiconductor material of the present invention well and because the organic solvent itself has appropriate volatility. Moreover, as a density | concentration of the organic-semiconductor material of this invention, 0.1-1 wt% is preferable, 0.2-0.5 wt% is more preferable, 0.3-0.4 wt% is further more preferable.

  As the dissolution method, for example, a method of adding an organic semiconductor material to the organic solvent and stirring or suspending can be used. Furthermore, heating or cooling may be performed during the dissolution.

<Process of coating on substrate with organic solvent in which organic semiconductor material is dissolved>
In the welding method, paper, plastic, plastic film, etc. can be used as the substrate material in addition to glass and ceramics. This makes it possible to reduce the weight and flexibility of the organic semiconductor device.

  Examples of the plastic material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC). ), Cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.

  Furthermore, the surface of the substrate can be processed using a compound such as a silane coupling agent such as Octyl trichlorosilane or Hexamethyldisilazane, or an organic polymer such as polystyrene.

  As the coating method, conventionally known methods such as cast coating, spin coating, printing, ink jet method, and ablation method can be suitably used.

<The process of drying the board | substrate obtained as a result of the said process>
The method for drying the substrate obtained as a result of the above step is not particularly limited, and a conventionally known method such as a blow drying method, a vacuum drying method, or a heat drying method can be used.

  The above-mentioned welding method has the advantage that a semiconductor layer can be disposed on a large-area substrate and does not require a complicated process compared to the vacuum evaporation method, so that the manufacturing cost of an organic semiconductor device can be suppressed. With advantages.

<Organic semiconductor devices>
As said organic-semiconductor device, the light emitting device which has a transistor, a diode, a capacitor | condenser, photoelectric conversion, a dye-sensitized solar cell, an organic carrier transport layer, and / or a light emitting layer can be mentioned, for example.

  The transistor may be a unipolar transistor (field effect transistor) or a bipolar transistor. Below, the aspect and manufacturing method of the field effect transistor which concern on this invention are demonstrated.

  In addition, the aspect and manufacturing method of the said bipolar transistor other than using the organic-semiconductor material of this invention can illustrate the well-known thing described in Unexamined-Japanese-Patent No. 10-214044, for example.

  Examples of the field effect transistor according to the present invention and the manufacturing method thereof include those disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-28055 or Japanese Patent Application Laid-Open No. 2006-114701 except that the organic semiconductor material according to the present invention is used. can do. Specifically, the semiconductor device includes a source electrode and a drain electrode that are in contact with a semiconductor layer disposed on the substrate, and a gate electrode that is in contact with the semiconductor layer via a gate insulator layer between the source electrode and the drain electrode. A field effect transistor can be mentioned.

  According to the above configuration, the current flowing between the source electrode and the drain electrode can be controlled by changing the voltage applied to the gate electrode in a state where a constant voltage is applied to the drain electrode. Hereinafter, the field effect transistor having the above configuration will be described in more detail.

  The material of the source electrode, the drain electrode, and the gate electrode is not particularly limited as long as it is a conductive material. A metal such as platinum, gold, silver, nickel, chromium, copper, iron, tin, aluminum, titanium, and magnesium; or these Alloys containing these metals; conductive oxides such as tin oxide, indium oxide and tin (ITO); semiconductors such as silicon and germanium; etc. can be used, but in particular, platinum, gold, silver, copper, aluminum ITO is preferred.

  Alternatively, a known conductive polymer whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used. Among them, those having low electrical resistance at the contact surface with the semiconductor layer are preferable.

  As an electrode placement method, for example, a conductive thin film placed using the above-mentioned materials as a raw material by a method such as vacuum deposition or sputtering, a method using a known photolithography method or a lift-off method, aluminum or copper Etching using a resist such as thermal transfer or ink jet on a metal foil such as

  Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by ink jetting, or may be disposed from the coating film by lithography, laser ablation, or the like. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as a relief printing plate, an intaglio printing plate, a planographic printing plate or a screen printing can be used.

  The thickness of the electrode is not particularly limited as long as it is appropriately selected according to the type and structure of the field effect transistor to be manufactured. For example, in the case of the above transistor, the thickness of the electrode is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.02 μm or more and 0.1 μm or less. When it is 0.01 μm or more, it can function as an electrode, and when it is 0.1 μm or less, smoothness can be maintained. However, the preferred electrode thickness is affected by various factors and is not limited to this.

  As the material for the gate insulator layer, various compounds having insulating properties can be used. For example, an inorganic compound, an inorganic oxide compound, and an organic compound can be mentioned. Examples of the inorganic compound include silicon nitride and aluminum nitride.

  Examples of the inorganic oxide compound include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, and tin oxide. Moreover, as said organic compound, polymers, such as a polyimide, polyamide, polyester, an epoxy resin; Copolymer which combined these; etc. are mentioned, for example.

  Examples of the arrangement method of the gate insulator layer include a wet process such as a vacuum deposition method, a CVD method, a sputtering method, and a patterning method such as printing or inkjet. In particular, the wet process is preferable as a method of disposing a gate insulator layer using an organic compound. The film thickness of these insulator films is preferably 50 nm to 3 μm, and more preferably 100 nm to 1 μm.

  Since the organic semiconductor material of the present invention is excellent in field effect mobility, it can be used for a semiconductor layer of a field effect transistor. In order to dispose the semiconductor layer containing the organic semiconductor material according to the present invention on the substrate, it can be disposed on the substrate by a vacuum deposition method, but it may be disposed on the substrate using a welding method as described above. preferable.

  By using the welding method, a field effect transistor having a light weight, flexibility, and large area can be easily manufactured at low cost.

  The manufacturing method of the field effect transistor according to the present invention is not particularly limited, and may be manufactured by the above-described method using the above-described materials according to the structure.

  For example, it can be manufactured by the following procedure. First, a silicon oxide gate insulator layer is placed on a glass substrate by vacuum deposition. Next, a semiconductor layer containing an organic semiconductor material is disposed on the gate insulator layer by a solution method. Thereafter, a source electrode, a drain electrode, and a gate electrode made of gold are disposed on the substrate using a vacuum deposition method.

  Examples of the embodiment and manufacturing method of the diode other than using the organic semiconductor material of the present invention can include known ones described in JP-A-2002-289878, for example.

  In addition, examples of the above-described capacitor aspect and manufacturing method other than using the organic semiconductor material of the present invention can include known ones described in JP-A-2005-150705.

  Examples of the above-described photoelectric conversion mode and manufacturing method other than the use of the organic semiconductor material of the present invention include known ones described in JP-A-2006-060104.

  Moreover, the aspect and manufacturing method of said dye-sensitized solar cell other than using the organic-semiconductor material of this invention can illustrate the well-known thing described in Unexamined-Japanese-Patent No. 2004-047752, for example.

  Examples of the organic carrier transport layer according to the light emitting device having the organic carrier transport layer and / or the light emitting layer include a hole transport layer and an electron transport layer. The hole transport layer has a function of transporting holes injected from the anode to the light emitting layer, and the electron transport layer has a function of transporting electrons injected from the cathode to the light emitting layer. is there.

  The light emitting layer is a semiconductor layer containing a light emitting material, which can inject holes from the anode side and electrons from the cathode side when a voltage is applied, and provides a field where holes and electrons recombine. It can be done. The light-emitting material includes various low-molecular light-emitting materials and various high-molecular light-emitting materials as described below, and at least one of them can be used. In addition, the light emitting layer may contain the organic semiconductor material of the present invention.

  Examples of the low-molecular light emitting material include benzene compounds such as distyrylbenzene (DSB) and diaminodistyrylbenzene (DADSB), naphthalene compounds such as naphthalene and nile red, and phenanthrene compounds such as phenanthrene. Conventionally known compounds such as

  Examples of the polymer light-emitting material include trans-acetylene, cis-polyacetylene, poly (di-phenylacetylene) (PDPA), polyacetylene-based compounds such as poly (alkyl, phenylacetylene) (PAPA), and poly (para Examples thereof include conventionally known compounds such as -phenvinylene) (PPV) and poly (2,5-dialkoxy-para-phenylenevinylene) (RO-PPV).

  Moreover, the light emitting device which consists of an organic carrier transport layer can be manufactured by including the said luminescent material in an organic carrier transport layer.

  That is, when a light emitting material is included in the hole transport layer, a light emitting device including a hole transport light emitting layer and an electron transport layer is obtained. Further, when a light emitting material is included in the electron transport layer, a light emitting device including an electron transport light emitting layer and a hole transport layer is obtained. In this case, the vicinity of the interface between the hole-transporting light-emitting layer and the electron-transporting layer and the vicinity of the interface between the electron-transporting light-emitting layer and the hole-transporting layer function as the light-emitting layer.

  On the other hand, the light emitting device which consists of a light emitting layer can be manufactured by including the organic-semiconductor material of this invention in a light emitting layer.

  An organic EL element can be illustrated as a specific example of the light emitting device having the organic carrier transport layer and / or the light emitting layer of the present invention. In addition, the aspect and manufacturing method of said organic EL element other than using the organic-semiconductor material of this invention can illustrate the well-known thing described in Unexamined-Japanese-Patent No. 2006-199909, for example.

  Specifically, the organic EL element includes a substrate, an anode layer provided on the substrate, a semiconductor layer including the organic semiconductor material of the present invention provided on the anode, and a cathode provided on the semiconductor layer. It is comprised from the layer and the protective layer provided so that each layer might be covered.

  The semiconductor layer includes an organic carrier transport layer and / or a light emitting layer. Further, the organic carrier transport layer includes two layers of a hole transport layer and an electron transport layer. When the semiconductor layer includes an organic carrier transport layer and a light emitting layer, the semiconductor layer is disposed on the anode in the order of a hole transport layer, a light emitting layer, and an electron transport layer.

  The hole transport layer has a function of transporting holes injected from the anode to the light emitting layer, and the electron transport layer has a function of transporting electrons injected from the cathode to the light emitting layer. is there.

  According to the above configuration, when energization (voltage is applied) between the anode and the cathode, holes move in the hole transport layer, and electrons move in the electron transport layer, so that holes and electrons in the light emitting layer move. And recombine. In the light emitting layer, excitons (excitons) are generated by the energy released upon this recombination, and light is emitted by releasing energy (fluorescence or phosphorescence) when the excitons return to the ground state.

  Further, the semiconductor layer may include an organic carrier transport layer without a light emitting layer. In the case of the said structure, the above-mentioned hole transportable light emitting layer and electron transportable light emitting layer can be used for the said organic carrier transport layer. In this case, the vicinity of the interface between the hole-transporting light-emitting layer and the electron-transporting layer, and the vicinity of the interface between the electron-transporting light-emitting layer and the hole-transporting layer function as a light-emitting layer.

When the hole transporting light emitting layer is used, holes injected from the anode into the hole transporting light emitting layer are confined by the electron transporting layer, and when the electron transporting light emitting layer is used, the cathode Since electrons injected from the electron transporting light-emitting layer into the electron-transporting light-emitting layer are confined in the electron-transporting light-emitting layer, both have the advantage that the recombination efficiency between holes and electrons can be improved.
The semiconductor layer may include a light emitting layer without an organic carrier transport layer. In the case of the above structure, a light emitting layer containing the organic semiconductor material of the present invention and the above light emitting material can be used.

  The said board | substrate becomes a support body of an organic EL element, and each said layer is arrange | positioned on this board | substrate. As a constituent material of the substrate, a material having translucency and good optical characteristics can be used.

  Examples of such materials include various resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate, and various glass materials. And at least one of these can be used.

  Although the thickness of the said board | substrate is not specifically limited, It is preferable that it is 0.1-30 mm, and it is more preferable that it is 0.1-10 mm.

  The anode is an electrode that injects holes into the hole transport layer. The anode is substantially transparent (colorless transparent, colored transparent, translucent) so that light emission from the light emitting layer can be visually recognized.

Examples of such an anode material include ITO (Indium Tin Oxide), SnO ₂ , Sb-containing SnO ₂ , oxides such as Al-containing ZnO, Au, Pt, Ag, Cu, or alloys containing these, and the like. At least one of these can be used.

  Although the thickness of an anode is not specifically limited, It is preferable that it is about 10-200 nm, and it is more preferable that it is about 50-150 nm. If the thickness of the anode is too thin, the function as the anode may not be sufficiently exhibited. On the other hand, if the anode is too thick, depending on the type of anode material, etc., the light transmittance may be significantly reduced, which is practical. May not be suitable.

  On the other hand, the cathode is an electrode for injecting electrons into the electron transport layer. As the cathode material, it is preferable to use a material having a small work function. Examples of such cathode materials include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing these, and the like. At least one of them can be used.

  The thickness of the cathode is preferably 1 nm to 1 μm, and more preferably 100 to 400 nm. If the thickness of the cathode is too thin, the function as the cathode may not be sufficiently exhibited. On the other hand, if the cathode is too thick, the light emission efficiency of the organic EL element may be reduced.

  Since the organic semiconductor material of the present invention has excellent donor properties, it is easy to inject holes from the electrode, and can be used for the hole transport layer of the semiconductor layer and each layer of the light emitting layer. Accordingly, the light-emitting device having the organic carrier transport layer and / or the light-emitting layer of the present invention includes one disposed in any one of the semiconductor layers, or one disposed in each layer.

  In order to arrange the organic semiconductor material of the present invention in each layer of the above-mentioned semiconductor layer, it can be arranged by a vacuum vapor deposition method, but it is preferable to arrange it in each layer of the semiconductor layer using the above-described welding method.

  By using the above-described welding method, an organic EL element having a light weight, flexibility and large area can be easily produced at low cost.

  An arbitrary target layer may be provided between the layers. For example, a hole injection layer that improves the efficiency of hole injection from the anode can be provided between the hole transport layer and the anode. In addition, an electron injection layer or the like that improves the efficiency of electron injection from the cathode can be provided between the electron transport layer and the cathode. Thus, when providing a positive hole injection layer and an electron injection layer in an organic EL element, the organic-semiconductor material of this invention can be used as a constituent material of this positive hole injection layer and an electron injection layer.

  The protective layer is provided so as to cover each layer constituting the organic EL element. This protective layer has a function of hermetically sealing each layer constituting the organic EL element and blocking oxygen and moisture. By providing the protective layer, the effects of improving the reliability of the organic EL element and preventing deterioration and deterioration can be obtained.

  Examples of the constituent material of the protective layer include Al, Au, Cr, Nb, Ta, Ti, alloys containing these, silicon oxide, and various resin materials. In addition, when using the material which has electroconductivity as a constituent material of a protective layer, in order to prevent a short circuit, it is preferable to provide an insulating film between a protective layer and each layer as needed.

  Such an organic EL element can be manufactured as follows, for example.

First, a polyethylene terephthalate substrate is prepared, and an SnO ₂ anode is disposed on the substrate. The vapor anode is, for example, a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, a dry plating method such as vacuum deposition, sputtering, or ion plating, or a wet method such as electrolytic plating, immersion plating, or electroless plating. It can arrange | position using the plating method, the thermal spraying method, the sol-gel method, the MOD method, joining of metal foil, etc.

  Next, the hole transport layer containing the organic semiconductor material of the present invention is disposed on the anode using a welding method.

  Thereafter, a light emitting layer containing distyrylbenzene (DSB) is disposed on the hole transport layer by a welding method.

  Next, the electron transport layer containing the organic semiconductor material of the present invention is disposed on the light emitting layer using a welding method.

  Further, an Mg cathode is disposed on the electron transport layer. The cathode can be disposed using, for example, vacuum deposition, sputtering, metal foil bonding, or the like.

  Finally, a silicon oxide protective layer is disposed so as to cover the anode, the semiconductor layer, and the cathode.

  The protective layer can be disposed, for example, by bonding a box-shaped protective cover made of the material as described above with various curable resins (adhesives). As the curable resin, any of a thermosetting resin, a photocurable resin, a reactive curable resin, and an anaerobic curable resin can be used.

  An organic EL element is manufactured through the above steps.

  Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

  Further, NMR (manufactured by Hitachi, Ltd .; RS1200, or JEOL; LAMBDA400 model number) and mass spectrometry (MS) (manufactured by Shimadzu; GC-MS5050, or Shimadzu) used for structural analysis of the compound; (KRATOS ANALYTICAL KOMPACT MALDI) was performed by a conventionally known method. Moreover, melting | fusing point was measured by the conventionally well-known method using the trace amount melting | fusing point measuring apparatus (the Yanagimoto Seisakusho make; MP-S3 type).

(Synthesis example)
The synthesis of the compounds according to the present invention showed reaction routes at the beginning of each. Moreover, the number described in the reaction pathway represents the corresponding compound.

4,5 Bis (bromomethyl) -1,3-dithiole-2-thione (4,5-Bis (bromomethyl) -1,3-dithiole-2-thione); Synthesis of Compound 6 FIG. As shown, reaction route 1 for synthesizing compound 6 is shown. Below, the reaction path | route 1 is demonstrated.

<(A) 1,3-Dithiolane-2-thione; Synthesis of Compound 3>
1,2-dibromoethane; compound 2 (40 mL, 0.32 mol), carbon disulfide (CS ₂ ) (60 mL, 0.99 mol), tetra n-butylammonium bromide (Bu ₄ NBr) (10 g, 0.03 mol) , NaOH (40 g, 0.5 mol) and H ₂ O (200 mL) were allowed to stir well at room temperature for 3 days.

  The organic layer was taken out, and after removing the solvent and residual dibromoethane by vacuum concentration and vacuum drying, the mixture was allowed to stand in a cold place for crystallization. The obtained yellow crystals were dissolved in a minimum amount of methylene chloride using an ice bath, and then recrystallized by adding 2-3 mL of hexane. The crystals were washed with hexane and cold hexane / methylene chloride (1: 1) to obtain yellow plate crystals.

Further, the mother liquor was concentrated to obtain secondary crystals in the same manner. Compound 3 obtained by this synthesis had a total yield of 31.82 g and a yield of 73%. The structure of the compound 3 was analyzed by ¹ H NMR (CDCl ₃ ) and found to be δ = 3.99 (s). From this result, it was revealed that the compound (3) was the compound 3.

<(B) 4,5-Bis (methoxycarbonyl) -1,3-dithiol-2-thione (4,5-Bis (methoxycarbonyl) -1,3-dithole-2-thione); Synthesis of Compound 4>
Compound 3 (32.8 g, 0.241 mol) and dimethyl acetylenecarboxylate (34.2 g, 29.6 mL, 0.241 mol) were dissolved in toluene (160 mL) and refluxed for 20 hours. After cooling to room temperature, 200 mL of hexane was added and allowed to crystallize in a cold place, and a yellow precipitate was collected by filtration using cold hexane. The obtained crystals were purified by recrystallization with methylene chloride and hexane about three times to obtain yellow plate crystals (yield 32.7 g, yield 54%).

Further, all the recrystallized mother liquors were collected, and after removing roughly black by-products with a minimum amount of silica gel, secondary crystals (13.4 g, yield 22%) were obtained by recrystallization. These are accurate enough to be used in the next reaction, but can be further purified by recrystallization using ethanol. Structural analysis of the obtained crystal by ¹ H NMR (CDCl ₃ ) revealed that δ = 3.93 (s). From this result, it was revealed that the crystal was Compound 4.

<(C) 4,5-Bis (hydroxymethyl) -1,3-dithiole-2-thione (4,5-Bis (hydroxymethyl) -1,3-dithiole-2-thione); Synthesis of Compound 5>
Under a nitrogen atmosphere, compound 4 (2.5 g, 10.0 mol) and lithium bromide (LiBr) (1.74 g, 20.0 mol) are dissolved in a mixed solution of anhydrous THF (20 mL) and anhydrous EtOH (10 mL), and acetone is added. - ice (1: 1) was allowed to cool to -10 ° C. or less with bath, sodium borohydride _{(NaBH 4) (0.78g, 20.6mol} ) was added slowly over 20 minutes. Thereafter, the temperature was maintained at -5 ° C to -10 ° C and the mixture was stirred for 10 hours.

After completion of the reaction, ice water (100 mL) was added to the solution and quenched with 4N HCl until no H ₂ gas was generated. The mixed solution was extracted with ethyl acetate (10 mL × 8), dried over anhydrous magnesium sulfate, concentrated, passed through column chromatography (silica gel, 3 cmΦ, 4 cm) using ethyl acetate, then methylene chloride / ethyl acetate. (2: 1) was used for separation and purification by column chromatography (silica gel, 3 cmΦ, 6 cm, Rf = 0.3). If purification was insufficient, the column was once again run with methylene chloride / ethyl acetate (1: 1). The target eluent was concentrated to give a dark orange to yellow solid. Recrystallization from methylene chloride and hexane gave orange plate crystals (yield 1.58 g, yield 81%).

When the obtained crystal was subjected to structural analysis by ¹ H NMR (60 MHz DMSO-d ⁶ ), δ = 4.42 (d, J = 5.6 Hz, 4H), 5.82 (t, J = 5.6 Hz, 2H). From this result, it was revealed that the crystal was Compound 5.

<(D) 4,5-bis (bromomethyl) -1,3-dithiole-2-thione (4,5-Bis (bromomethyl) [1,3] dithiole-2-thione); Synthesis of Compound 6>
Under a nitrogen atmosphere, a solution of compound 5 (5.25 g, 27 mmol) in anhydrous THF was cooled to 0 ° C. with an ice bath, phosphorus tribromide (PBr 3) (5.13 mL, 54 mmol) was added, and the temperature was close to 0 ° C. over 30 minutes. The mixture was kept at room temperature and then stirred at room temperature for 16 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure and dried in vacuo. The precipitated yellow crystals were collected by filtration using carbon tetrachloride, and an appropriate amount (about 50 mL) of carbon tetrachloride was added to the mother liquor, and the mixture was left in a refrigerator for about 1 hour. Then, crystals precipitated and were similarly collected by filtration (6.28 g, yield 73%).

  This mother liquor was subjected to column chromatography (methylene chloride, 4 cmΦ, 5 cm, Rf = 0.9) to obtain yellow needle crystals (yield 0.427 g, yield 5%). Therefore, when the crystals obtained by cooling in the refrigerator and the crystals recovered from the column chromatography are combined, the total yield is 6.71 g and the yield is 78%.

A structural analysis of the obtained crystal by ¹ H NMR (60 MHz CDCl ₃ ) revealed that δ = 4.29 (s). From this result, it was revealed that the crystal was Compound 6.

  Dithieno (3,4-d) tetrathiafulvalene (Dithieno (3,4-d) tetrathiafulvalene, DT-TTF); Synthesis of Compound 16 FIG. 3 shows a method of coupling thiones with Compound 6 as a starting material ( The reaction route 2 for synthesizing the compound 16 by two kinds of routes (route 1) and a method of coupling ketone bodies (route 2) is shown. Below, the reaction path | route 2 is demonstrated.

<(E) 4,6-Dihydrothieno [3,4-d] -1,3-dithiol-2-thione (4,6-Dihydrothieno [3,4-d] -1,3-dithiole-2-thione) Synthesis of Compound 17>
Under a nitrogen atmosphere, compound 6 (2.00 g, 6.25 mol) in THF- ethanol (250mL, 4: 1 v / v) solution and 2 sodium sulfide nonahydrate _{(Na 2 S · 9H 2 O} ) (1 .50 g, 6.25 mol) of H ₂ O-ethanol (250 mL, 4: 1 v / v) was added dropwise into 200 mL of ethanol simultaneously over 45 minutes.

After stirring at room temperature for 1.5 hours, the reaction solution was concentrated to remove the solvent, dissolved in methylene chloride (100 mL), and the remaining solid was removed by filtration. The mixture was transferred to a separatory funnel, washed with H ₂ O (50 mL × 3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a yellow solid (yield 1.02 g, yield 85%).

Structural analysis of the obtained individual by ¹ H NMR (60 MHz CDCl ₃ ) revealed that δ = 4.05 (s). From this result, it was revealed that the solid was Compound 17.

<Synthesis of (f) Thieno [3,4-d] -1,3-dithiole-2-thione (Compound 18)>
Under a nitrogen atmosphere, a solution of Compound 17 (1.00 g, 5.20 mol) dissolved in toluene (100 mL) was refluxed with DDQ (2,3-dichloro-5,6-dicyanobenzoquinoline (2,3-Dichlorobenzoate). -5,6-dicyanobenzoquinone), 1.30 g, 5.72 mmol) in toluene (50 mL). After refluxing for 1.5 h, the reaction solution was concentrated under reduced pressure to obtain a solid.

The obtained solid was dissolved in methylene chloride, and impurities were removed by filtration. The filtrate was transferred to a separatory funnel, and then washed with 4M NaOH (30 mL × 2), NaHCO ₃ (30 mL × 2), and H ₂ O (30 mL × 1) in this order to remove reduced DDQ. After drying with magnesium sulfate, the solution was concentrated under reduced pressure to obtain a dark yellow solid. This was separated and purified by column chromatography (silica gel, methylene chloride / hexane (1: 1 v / v), 4 cmΦ, 6 cm, Rf = 0.5), and recrystallized (ethyl acetate / hexane) to give yellow needle crystals. (Yield 0.73 g, yield 74%) was obtained.

Structural analysis of the obtained crystal by ¹ H NMR (CDCl ₃ ) was δ = 7.25 (s). From this result, it was revealed that the crystal was Compound 18.

<(G) Dithieno [3,4-d] tetrathiafulvalene (Synthesis of Compound 16 (Route 1)>
Under a nitrogen atmosphere, a mixture of compound 18 (0.38 g, 2.00 mmol) and trimethyl phosphite (P (OMe) ₃ ) (5.7 mL, 48.4 mol) was refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then allowed to stand for about 1 hour in a freezer (4 ° C.) to precipitate crystals. The crystals were collected by filtration to obtain yellow plate crystals (yield 0.09 g, yield 28%).

A structural analysis of the obtained crystal by ¹ H NMR (60 MHz CDCl ₃ ) revealed that δ = 6.89 (s). From this result, it was revealed that the crystal was Compound 16.

<(H) Thieno [3,4-d] -1,3-dithiol-2-one; Synthesis of Compound 19>
Under a nitrogen atmosphere, compound _{18 (0.38g, 2mmol) CHCl 3} (70mL) was added Macuric Acetate of _{(Hg (OAc) 2) (} 2.13g, 6.67mmol) was added dropwise CHCl ₃ solution. After stirring at room temperature for 2 days, the reaction solution was filtered, and the filtrate was washed with H ₂ O (20 mL × 5). After drying with magnesium sulfate, the residue was purified by column chromatography (silica gel, ethyl acetate / methylene chloride (1: 1) 3 cmΦ, 6 cm) to obtain a white solid (yield 0.117 g, yield 34%).

Structural analysis of the obtained solid by ¹ H NMR (400 MHz CDCl ₃ ) revealed that δ = 7.31 (s, 2H). In addition, since the melting point was 108 to 109 ° C., it was consistent with the value of the document “Long-Young Chiang; Paul Shu; Dennis Holt; Dwaine Cowan, J. Org. Chem. 1983, 48, 4713-4717”. The solid was found to be compound 19.

<(I) Dithieno [3,4-d] tetrathiafulvalene; Synthesis of Compound 16 (Route 2)>
Under a nitrogen atmosphere, a mixture of compound 19 (120 mg, 0.67 mmol) and trimethyl phosphite (P (OMe) ₃ ) (2.0 ml, 16 mmol) was refluxed overnight. The reaction mixture was allowed to stand in a freezer for about 1 hour, and the precipitated yellow plate crystals were collected by filtration (yield 15 mg, yield 14%).

Structural analysis of the obtained crystal by ¹ H NMR (60 MHz CDCl ₃ ) revealed that δ = 6.89 (s). From this result, it was revealed that the crystal was Compound 16.

  Dithieno [3,4-d] tetrathiafulvalene; To synthesize compound 16, two methods, route 1 and route 2, were tried. As a result, it was possible to synthesize dithieno [3,4-d] tetrathiafulvalene with a yield of 28% using the route 1 method, whereas the yield was 14% using the route 2 method. And half.

  Moreover, the compound 16 obtained by the method of the route 1 was so pure that there was no need for column purification. Therefore, when synthesizing the compound 16, it can be said that the method of the route 1, that is, the method of synthesizing by coupling the thione compounds 18 to each other may be adopted.

Synthesis of Bis (N-butylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-Butylpyrrolo [3,4-d]) tetrathiafulvalene) Compound 1-c FIG. 4 shows a thione compound starting from Compound 6 The reaction route 4 for synthesizing the compound 1-c is shown by two kinds of routes, a method of coupling each other (route 3) and a method of coupling ketone bodies (route 4). Below, the reaction path | route 4 is demonstrated.

<(J) 4,6-dihydro-N-butyl- (1,3) -dithiolo [4,5-c] pyrrol-2-thione (4,6-dihydro- N-Buthyl- (1,3)- dithiolo [4,5-c] pyrrole-2-thione); Synthesis of Compound 20>
Under a nitrogen atmosphere, a suspension of cesium carbonate (13.4 g, 41.2 mmol) in anhydrous THF-acetonitrile (1: 2 v / v, 300 mL) was cooled to 0 ° C., and compound 6 (3.30 g, 10.3 mmol) was cooled. ) Was quickly added, but butylamine (BuNH ₂ ) (0.75 g, 1.03 mL, 10.3 mmol) was added in one portion, kept at 0 ° C. for 30 minutes, and then stirred at room temperature for 3 hours.

The reaction solution was filtered through celite using methylene chloride, the solution was washed with H ₂ O (80 ml × 5), dried over anhydrous magnesium sulfate, and then column chromatography (methylene chloride, 3 cmΦ, 6 cm, Rf = 0.0). The dark orange liquid obtained by purification according to 2) was allowed to stand in a cold place to give a brown solid (0.53 g, 46% yield).

When the obtained solid was subjected to structural analysis by ¹ H NMR (60 MHz CDCl ₃ ), δ = 0.93 (multi, 3H), 1.35 (4H, multi), 2.73 (t, 2H), 3. 81 (s, 4H). From this result, it was revealed that the solid was Compound 20.

<(K) N-butyl- (1,3) -dithiolo [4,5-c] pyrrol-2-thione (N-Buthyl-4,6-dihydro- (1,3) -dithiolo [4,5- c] pyrrole-2-thione); Synthesis of Compound 21>
Under a nitrogen atmosphere, a suspension of cesium carbonate (13.4 g, 41.2 mmol) in anhydrous THF-acetonitrile (1: 2 v / v, 300 mL) was cooled to 0 ° C., and compound 20 (3.30 g, 10.3 mmol) was cooled. ) Was added rapidly, but butylamine (0.75 g, 1.03 mL, 10.3 mmol) was added in one portion, kept at 0 ° C. for 30 minutes, and then allowed to stir at room temperature for 3 hours. The reaction solution was filtered through Celite using methylene chloride, the solution was washed with H ₂ O (80 mL × 5), dried over anhydrous magnesium sulfate, and then column chromatography (methylene chloride, 3 cmΦ, 6 cm, Rf = 0.0). The dark orange liquid obtained by purification according to 2) was left in a cold place to give a brown solid (0.53 g, 46%).

When the obtained solid was subjected to structural analysis by ¹ H NMR (60 MHz CDCl ₃ ), δ = 0.93 (multi, 3H), 1.35 (4H, multi), 2.73 (t, 2H), 3. 81 (s, 4H). From this result, it was revealed that the solid was Compound 21.

<(L) Bis (N-butylpyrrolo [3,4-d]) tetrathiafulvalene (Synthesis of Compound 1-c (Route 3)>
Compound 1-c was synthesized using a method of coupling thione compounds 21 to each other (route 3). Specifically, a mixed solution of compound 21 (0.32 g, 1.4 mmol) and trimethyl phosphite (P (OMe) ₃ ) (4 mL) was added at 90 ° C. for 4 hours and at 135 ° C. for 6 hours under a nitrogen atmosphere. Refluxed.

  After completion of the reaction, the reaction solution was concentrated under reduced pressure and passed through column chromatography (silica gel, methylene chloride / hexane (1: 1 v / v), 2 cmΦ, 4 cm) to give a yellow solid (yield 0.064 g, yield 23%). Got. Furthermore, a high-purity target product was obtained by recrystallization (toluene / hexane). Further, sublimation purification (180 ° C., yield 60%) was performed for device preparation by vacuum deposition.

When the obtained crystal was subjected to structural analysis by ¹ H NMR (400 MHz DMSO-d ⁶ ), δ = 0.87 (t, J = 7.4 Hz, 6H), 1.21 (sext, J = 7. 4 Hz, 4H), 1.64 (t, J = 7.4 Hz, 4H), 3.84 (t, J = 7.4 Hz, 4H), 6.81 (s, 4H). Furthermore, when mass spectrometry was performed by MS (DI), it was m / z = 394 (M ^<+> ). From this result, it was found that the molecular weight was 394.64 (M ⁺ ). From the above results, it was revealed that the crystal was compound 1-c.

<(M) 4,6Dihydro-N-butyl- (1,3) -dithiolo [4,5-c] pyrrol-2-one (4,6-Dihydro-N-Buthyl-4,6-dihydro- ( 1,3) -dithiolo [4,5-c] pyrrole-2-one); >
Under a nitrogen atmosphere, a mixed solution of Compound 20 (1.40 g, 6.05 mmol), chloroform (100 mL), and acetic acid (0.6 mL) was added to Macroacetate (Hg (OAc) ₂ ) (3.65 g, 11.5 mmol). Was added with a spoonful and stirred at room temperature for 4 hours. After completion of the reaction, celite (1 cm) was filtered and washed thoroughly with methylene chloride. The filtrate was washed with NaHCO ₃ (30 mL × 5) and H ₂ O (30 mL × 1), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained solid was subjected to column chromatography (silica gel, methylene chloride / ethyl acetate). Purification (2: 1 v / v), 3 cmΦ, 6 cm, Rf = 0.6) gave a colorless and transparent oily liquid (yield 0.62 g, yield 43%).

When the obtained liquid was structurally analyzed by ¹ H NMR (400 MHz CDCl ₃ ), δ = 0.94 (t, J = 7.3 Hz, 3H), 1.4 (sext, J = 7.3 Hz, 2H) 1.5 (quint, J = 7.3 Hz, 2H), 2.7 (t, J = 7.3 Hz, 2H), 3.9 (s, 4H). Further, structural analysis by ¹³ C NMR (400 MHz CDCl ₃ ) showed δ = 13.9, 20.2, 31.0, 55.9, 58.6, 125.6, 196.2.

Furthermore, it was m / z = 215 (M ^<+> ) when the mass spectrometry was performed by MS (DI). From this result, it was found that the molecular weight was 215.34. Moreover, it was 1693 (C = O) cm < ^-1 > when the infrared spectrum was analyzed by IR (neat). From the above results, it was revealed that the liquid was the compound 22.

<(N) N-Butyl- (1,3) -dithiolo [4,5-c] pyrrol-2-one (N-Buthyl-4,6-dihydro- (1,3) -dithiolo [4,5- c] pyrrole-2-one); Synthesis of Compound 23>
Under a nitrogen atmosphere, Compound 22 (0.43 g, 2.00 mmol) and DDQ (0.68 g, 3.0 mmol) were dissolved in toluene (25 mL) and refluxed at 120 ° C. for 1 hour. The reaction mixture was filtered through celite using methylene chloride, and the filtrate was washed with 10% NaOHaq (20 mL × 4), followed by H ₂ O (20 mL × 2), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, Column chromatography (silica gel, methylene chloride / hexane (1: 1 v / v), 2 cmΦ, 10 cm, Rf = 0.4) was performed to obtain a colorless and transparent oily liquid (yield 0.36 g, yield 84). %).

When the obtained liquid was subjected to structural analysis by ¹ H NMR (400 MHz CDCl ₃ ), δ = 0.94 (t, J = 7.6 Hz, 3H), 1.3 (sext, J = 7.6 Hz, 2H) 1.7 (quant, J = 7.6 Hz, 2H), 3.9 (t, J = 7.6 Hz, 2H), 6.7 (s, 2H). Further, structural analysis by ¹³ C NMR (400 MHz CDCl ₃ ) showed δ = 13.5, 19.7, 33.5, 50.5, 111.9, 113.5, 196.7.

Furthermore, when mass spectrometry was performed by MS (DI), it was m / z = 213 (M ^<+> ). From this result, it was found that the molecular weight was 213.32. Moreover, when an infrared spectrum was analyzed by IR (neat), it was 1682 (C = O) cm < ^-1 >. From the above results, it was revealed that the liquid was Compound 23.

<(O) Bis (N-butylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-Butylpyrrolo [3,4-d]) tetrathiafulvalene); Synthesis of Compound 1-c (Route 4)>
Compound 1-c was synthesized using a method of coupling compounds 23 which are ketone bodies. Specifically, a mixed solution of Compound 23 (1.32 g, 6.20 mmol) and trimethyl phosphite (P (OMe) ₃ ) (5 mL) was refluxed at 135 ° C. for 2 days under a nitrogen atmosphere.

  The reaction solution was concentrated under reduced pressure, and a yellow solid (75 mg, yield 26%) precipitated by adding about 20 mL of carbon tetrachloride was collected by filtration. The filtrate was subjected to column chromatography (silica gel, methylene chloride / hexane (1: 1 v / v), Rf = 0.5) to further obtain the desired yellow solid (yield 16 mg, yield 5%). . Therefore, when the precipitate generated by the addition of carbon tetrachloride and the solid recovered by column chromatography are combined, the compound 1-c obtained in the synthesis is a total yield of 91 mg and a yield of 31%.

When structural analysis of the obtained compound 1-c was performed by ¹ H NMR (400 MHz DMSO-d ⁶ ), δ = 0.87 (t, J = 7.4 Hz, 6H), 1.21 (sext, J = 7.4 Hz, 4H), 1.64 (t, J = 7.4 Hz, 4H), 3.84 (t, J = 7.4 Hz, 4H), 6.81 (s, 4H). Furthermore, when mass spectrometry was performed by MS (DI), it was m / z = 394 (M ^<+> ). From this result, it was found that the molecular weight was 394.64 (M ⁺ ). From the above results, it was revealed that the solid was Compound 1-c.

  Bis (N-butylpyrrolo [3,4-d]) tetrathiafulvalene; Two methods, route 3 and route 4, were tried to synthesize compound 1-c. As a result, compound 1-c could be synthesized in a yield of 23% using the route 3 method, whereas the yield was 31% using the route 4 method. Although the yield is slightly better using the route 4 method, the synthesis requires one more step than the case where the route 3 method is used, and a reaction time of 50 hours or more is required. In addition, it can be mentioned as a disadvantage that it takes time to purify the final product.

  Therefore, when synthesizing compound 1-c, it can be said that the method of route 3, that is, a method of synthesizing compounds of thione compounds 21 with each other is preferably employed.

Bis (pyrrolo [3,4-d]) tetrathiafulvalene (Bis (pyrrolo [3,4-d]) tetrathiafulvalne); Compound 11, bis (N-methylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-methylpyrrolo [3,4-d]) tetrathiafulvalne); Compound 1-a, bis (N-octylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-octylpyrrolo [3,4-d]) ) tetrathiafulvalne); compound 1-c, bis (N-dodecylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-dodecylpyrrolo [3,4-d]) tetrathiafulvalne); compound 1-d, bis ( N-cetylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-cetylpyrrolo [3,4-d]) tetrathiafulvalene; compound 1-e (bis (N-icosylpyrrolo [3,4-d]) tetrathiaful) Synthesis of Valene (Bis (N-icosylpyrrolo [3,4-d]) tetrathiafulvalene; Compound 1-f)) Figure 5 shows Compound 6 as starting material , Reaction pathway 5 for synthesizing compound 1-a, compound 1-c, compound 1-d, compound 1-e and compound 1-f.

  Since the synthesis of the compound 1-c was a low yield of about 20% in both the routes 3 and 4, the compound 1-a, the compound 1-c, the compound 1-d, the compound 1-e and the compound 1 The synthesis of -f was performed by a method via a tosyl group as shown in the reaction route 5 of FIG.

In this case, the tosyl group plays two roles: activating the nitrogen atom in the ring-closing reaction and protecting pyrrole under severe coupling conditions with trimethyl phosphite (P (OMe) ₃ ). The tosyl group can be removed quantitatively, and then a pyrrole-ring-out TTF into which various alkyl groups have been introduced can be synthesized by selecting a reagent.

<Synthesis of (p) Tosylamide monosodium salt (hereinafter also referred to as “TsNHNa”)>
First, the reagent tosylamide monosodium salt was synthesized. In the literature (Sebastiano Pappalado et. Al; J. Org. Chem, 1998, 53, 3521-3529), absolute ethanol was used, but by using more sodium, the target product was obtained in a sufficient yield with ordinary ethanol. was gotten.

  Specifically, metallic sodium (Na) (2.76 g, 0.12 mol) was dissolved in ethanol (140 mL) under a nitrogen atmosphere and refluxed to obtain tosylamide (17.2 g, 0.10 mol). And allowed to react for approximately 2 hours. After completion of the reaction, the produced white solid was washed with ethanol and dried to obtain the desired white solid (yield 17.7 g, yield 92%).

When the obtained solid was subjected to structural analysis by ¹ H NMR (60 MHz DMSO-d ⁶ ), δ = 2.3 (s, 3H), 3.3 (bs), 7.1 (d, J = 7 0.9 Hz, 2H), 7.5 (d, J = 7.9 Hz, 2H). The infrared spectrum was analyzed by IR (KBr) and found to be 3209 (N—H) cm ⁻¹ . From the above results, it was revealed that the solid was tosylamide monosodium salt.

<(Q) 4,6-Dihydro-N-tosyl- (1,3) dithiolo [4,5-c] pyrrol-2-thione (4,6-Dihydro-N-tosyl- (1,3) -dithiolo [4,5-c] pyrrole-2-thione); Synthesis of Compound 7>
Under a nitrogen atmosphere, tosylamide monosodium salt (TsNHNa) (2.0 g, 10.4 mmol) was suspended in 50 mL of acetonitrile and kept at 80 ° C. with an oil bath, and this suspension was dissolved in 5 mL of dimethylformamide (DMF). The compound 6 was slowly added dropwise over 20 minutes. About 10 minutes after the addition, and after completion of the reaction, hot celite filtration is performed using acetonitrile to recover the precipitate formed in the mixed solution. The precipitate was then washed with a small amount of acetonitrile.

Thereafter, the distillation apparatus was assembled and the precipitate was concentrated under reduced pressure, and then acetonitrile was completely removed by vacuum drying. The obtained solid was dissolved in about 100 mL of methylene chloride, washed with H ₂ O (50 mL × 3) and an aqueous sodium chloride solution (50 mL × 1), and then dried over anhydrous magnesium sulfate. The pale yellow solid reprecipitated by adding hexane was collected by filtration and fractionated by column chromatography (silica gel, methylene chloride, 10 cmΦ, minimum amount). The objective fraction was recrystallized (toluene / hexane) to obtain yellow needle crystals (until secondary crystals, yield 1.30 g, yield 80%).

When the obtained crystal was subjected to structural analysis by ¹ H NMR (60 MHz CDCl ₃ ), δ = 2.4 (s, 3H), 4.4 (s, 4H), 7.3 (d, J = 8.3 Hz, 2H) and 7.6 (d, J = 8.3 Hz). Moreover, melting | fusing point (mp) was 235-235.5. The melting point value described in the literature is 234 ° C. From the above results, it was revealed that the crystal was compound 7.

<(R) 4,6-Dihydro-N-tosyl- (1,3) dithiolo [4,5-c] pyrrol-2-one (4,6-Dihydro-N-tosyl- (1,3) -dithiolo [4,5-c] pyrrole-2-one); Synthesis of Compound 8>
Under a nitrogen atmosphere, a solution of Compound 7 (3.00 g, 9.10 mmol) suspended in chloroform (160 mL) and glacial acetic acid (16 mL) was charged with Macroacetate (Hg (OAc) ₂ ) (5.49 g, 17.2 mmol). ) And stirred at room temperature for 4 hours. After completion of the reaction, the mixture was passed through Celite (1 cm) and thoroughly washed with methylene chloride. The extract was washed with NaHCO ₃ (200 mL × 4) and H ₂ O (200 mL × 1), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and vacuum dried in a desiccator to obtain a white solid (yield 2.27 g, yield 80%). )

When the obtained solid was subjected to structural analysis by ¹ H NMR (60 MHz CDCl ₃ ), δ = 2.4 (s, 3H), 4.4 (s, 4H), 7.3 (d, J = 8.3 Hz, 2H) and 7.6 (d, J = 8.3 Hz). Furthermore, when the infrared spectrum was analyzed by IR (KBr), it was 1693 (C = O) cm- ¹ . From the above results, it was revealed that the solid was Compound 8.

<(S) N-tosyl- (1,3) -dithiolo [4,5-c] pyrrol-2-one (N-tosyl- (1,3) -dithiolo [4,5-c] pyrrole-2-one ); Synthesis of Compound 9>
Under a nitrogen atmosphere, Compound 8 (2.27 g, 6.89 g) and DDQ (3.44 g, 15.2 g) were dissolved in about 100 mL of chlorobenzene and refluxed for 2 hours. After completion of the reaction, celite filtration was performed using methylene chloride, and the filtrate was washed with 10% NaOHaq (50 mL × 3), followed by H ₂ O (50 mL × 2), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure and vacuum drying, the solvent was removed, and the residue was purified by column chromatography (silica gel, developing solvent; methylene chloride, Rf = 0.5, 6 cmΦ, 4 cm) to give a white solid (yield 2.29 g, yield 97). %).

When the obtained solid was subjected to structural analysis by ¹ H NMR (60 MHz CDCl ₃ ), δ = 2.4 (s, 3H), 4.4 (s, 4H), 7.3 (d, J = 8 .3 Hz, 2H), 7.6 (d, J = 8.3 Hz). From this result, it was revealed that the solid was Compound 9.

<(T) Bis (N-tosylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-tosylpyrrolo [3,4-d]) tetrathiafulvalene); Synthesis of Compound 10>
Under a nitrogen atmosphere, a mixture of compound 9 (2.09 g, 6.70 mmol) and trimethyl phosphite (P (OMe) ₃ ) (75 mL, 0.63 mol) was refluxed at 120 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, anhydrous MeOH (100 mL) was added, and the formed precipitate was collected by filtration and washed well with MeOH. The solid was dried in vacuo to give a yellow powder (yield 1.60 g, 81% yield).

When the obtained powder was subjected to structural analysis by ¹ H NMR (400 MHz DMSO-d ⁶ ), δ = 2.36 (s, 3H), 7.36 (s, 4H), 7.44 (d, J = 8.6 Hz, 2H), 7.80 (d, J = 8.6 Hz, 2H). From this result, it was revealed that the powder was Compound 10.

<(U) Bis (pyrrolo [3,4-d]) tetrathiafulvalene (Bis (pyrrolo [3,4-d]) tetrathiafulvalene); Synthesis of Compound 11>
Under a nitrogen atmosphere, compound 10 (0.65 g, 1.10 mmol) was dissolved in a mixed solvent of THF-MeOH (1: 1) (90 mL) and cooled to 0 ° C. using an ice bath. After degassing by bubbling with argon for approximately 15 minutes, 30% sodium methoxide solution (NaOMe) (Na 0.76 g, MeOH 6.5 mL) prepared in another flask was added using a transfer tube. . The mixture was refluxed for 30 minutes or more, and after confirming that the raw material disappeared, the mixture was cooled to room temperature, evaporated to about 30 mL and concentrated.

Thereafter, 150 mL of H ₂ O was added, and the produced yellow precipitate was collected by filtration and washed with water. After vacuum drying, purification was performed by column chromatography (4% low activity Al ₂ O ₃ , THF-MeOH 50: 1 v / v, 4 cmΦ, 3 cm), and yellow solid (yield 0.294 g, yield 88%). ) In the case of producing an FET element, sublimation purification was performed at 170-190 ° C. after recrystallization with THF / water.

The obtained solid was subjected to structural analysis by ¹ H NMR (400 MHz DMSO-d ⁶ ) and found to be δ = 6.79 (s, 4H), 11.1 (bs, 2H). From this result, it was revealed that the solid was Compound 11.

<(V) Bis (N-methylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-methylpyrrolo [3,4-d]) tetrathiafulvalene); Synthesis of Compound 1-a>
Under a nitrogen atmosphere, Compound 11 (0.434 g, 1.54 mmol) was dissolved in dimethylformamide (DMF) (50 mL) and cooled to 0 ° C. using an ice bath. After degassing by bubbling argon gas for approximately 15 minutes, iodomethane (CH ₃ I) (2.19 g, 15.4 mmol, 0.96 mL) was added and sodium hydride (NaH) (55%, 0.3%). 485 g, 11.1 mmol) was added. After reacting at 0 ° C. for 1 hour, it was quenched by careful addition of brine (200 mL), and suction filtered with H ₂ O followed by MeOH. After vacuum drying in a desiccator, column chromatography (silica gel, methylene chloride, 6 cmΦ, 3 cm, Rf = 0.7) was performed to obtain a yellow solid (yield 0.468 g, yield 98%). Further, by sublimation purification (210 ° C., yield 22%), the final target product (20 mg, 3 times) was obtained.

Structural analysis of the obtained solid by ¹ H NMR (400 MHz DMSO-d ⁶ ) revealed that δ = 3.60 (s, 6H) and 6.76 (s, 3H). From this result, it was revealed that the solid was Compound 1-a.

<Synthesis of (w) Bis (N-octylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-octylpyrrolo [3,4-d]) tetrathiafulvalene; Compound 1-c)>
Under a nitrogen atmosphere, Compound 11 (0.434 g, 1.54 mmol) was dissolved in dimethylformamide (DMF) (50 mL) and cooled to 0 ° C. using an ice bath. After degassing by bubbling argon gas for about 15 minutes, 1-bromooctane (n-C ₈ H ₁₇ Br) (2.19 g, 15.4 mmol, 0.96 mL) was added and washed with hexane. Sodium hydride (NaH) (55%, 0.485 g, 11.1 mmol) was added.

After reacting at 0 ° C. for 1 hour, it was quenched by careful addition of brine (200 mL), and suction filtered with H ₂ O followed by methanol. After vacuum drying in a desiccator, column chromatography (silica gel, methylene chloride, 6 cmΦ, 3 cm, Rf = 0.7) was performed to obtain a yellow solid. This was recrystallized using hexane to obtain yellow needle crystals (yield 380 mg, yield 75%). Further, high-purity crystals can be obtained by repeating recrystallization.

When the obtained solid was subjected to structural analysis by ¹ H NMR (400 MHz CDCl ₃ ), δ = 0.874 (t, 6H), 1.26 (m, 20H), 1.71 (t, 4H), 3 .79 (bs, 4H), 6.43 (s, 4H). Furthermore, when structural analysis was performed by ¹³ C NMR (400 MHz CDCl ₃ ), δ = 14.2, 22.8, 26.7, 29.3, 31.6, 50.9, 77.4, 112.3. 118.7. It is considered that δ is shifted to 77.4 because the central double bond has a single bond property due to oxidation by the solvent.

Further, when mass spectrometry was performed by MS (EI / DI), m / z = 506 (100, M ⁺ ), 507 (30, M ⁺ +1), 508 (20, M ⁺ +2), 509 (trace, M ⁺ +3), 253 (trace, 1/2 M ⁺ fragment). From the above results, it was revealed that the solid was compound 1-c.

<Synthesis of (x) Bis (N-dodecylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-dodecylpyrrolo [3,4-d]) tetrathiafulvalene; Compound 1-d))>
Under a nitrogen atmosphere, Compound 11 (204 mg, 0.7 mmol) was dissolved in dimethylformamide (DMF) (20 mL) and cooled to 0 ° C. using an ice bath. After degassing by bubbling argon gas for about 15 minutes, 1-bromododecane (n-C ₁₂ H ₂₅ Br) (1.92 g, 1.72 mL) was added, and sodium hydride (NaH) washed with hexane was added. ) (55%, 350 mg, 10.55 mmol) was added.

After reacting at 0 ° C. for 1 hour, the solution was quenched by careful addition of brine (100 mL), and suction filtered using H ₂ O. After vacuum drying in a desiccator, column chromatography (silica gel, methylene chloride, 6 cmΦ, 3 cm, Rf = 0.7) was performed, and the yellow solid was recrystallized from hexane to obtain powdery crystals (yield 205 mg, yield 45). %).

When the obtained crystal was subjected to structural analysis by ¹ H NMR (400 MHz CDCl ₃ ), δ = 0.877 (t, 6H), 1.247 (m, 38H), 1.71 (s, 6H), 3.79 (bs, 4H) and 6.43 (s, 4H). Furthermore, when structural analysis was performed by ¹³ C NMR (400 MHz CDCl ₃ ), δ = 14.3, 22.8, 26.7, 29.3, 29.5, 29.6, 29.7, 29.8. 31.6, 32.1, 50.9, 77.4, 112.3, 118.7. It is considered that δ is shifted to 77.4 because the central double bond has a single bond property due to oxidation by the solvent.

Moreover, when mass spectrometry was performed by MS (EI / DI), it was m / z = 618 (M ^<+> ), 310 (1/2 M ^<+> fragment). From the above results, it was revealed that the solid was compound 1-d.

<Synthesis of (y) bis (N-cetylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-cetylpyrrolo [3,4-d]) tetrathiafulvalene; Compound 1-e)>
Under a nitrogen atmosphere, Compound 11 (204 mg, 0.7 mmol) was dissolved in dimethylformamide (DMF) (20 mL) and cooled to 0 ° C. using an ice bath. After degassing by bubbling argon gas for about 15 minutes, 1-bromocetane (n-C ₁₆ H ₃₃ Br) (1.92 g, 1.72 mL) was added, and sodium hydride (NaH) washed with hexane was added. (55%, 350 mg, 10.55 mmol) was added.

After reacting at 0 ° C. for 1 hour, the solution was quenched by careful addition of brine (100 mL), and suction filtered using H ₂ O. After vacuum drying in a desiccator, column chromatography (silica gel, methylene chloride, 6 cmΦ, 3 cm, Rf = 0.7) was performed, the yellow solid was recrystallized from hexane, and powdered crystals (yield 205 mg, yield 82) %).

Structural analysis of the obtained crystal by ¹ H NMR (400 MHz CDCl ₃ ) revealed that δ = 0.88 (t, 6H), 1.25 (m, 56H), 1.71 (s, 6H), 3 .79 (bs, 4H), 6.43 (s, 4H). Furthermore, when structural analysis was performed by ¹³ C NMR (C ₆ D ₆ ), δ = 14.4, 23.1, 26.7, 29.5, 29.9 (× 2), 30.08, 30. 16 (× 2), 30.22 (× 4), 31.5, 32.4, 50.4, 112.3, 119.4, and 120.8.

Moreover, it was m / z = 730 (M ^<+> ) when the mass spectrometry was performed by MS (EI, 70 eV). From the above results, it was revealed that the solid was Compound 1-e.

<Synthesis of (z) (Bis (N-icosylpyrrolo [3,4-d]) tetrathiafulvalene; Compound 1-f))>
Under a nitrogen atmosphere, Compound 11 (282 mg, 1.0 mmol) was dissolved in dimethylformamide (DMF) (30 mL) and cooled to 0 ° C. using an ice bath. After degassing by bubbling argon gas for about 15 minutes, 1-bromoicosane (n-C ₂₀ H ₄₁ Br) (3.61 g, 10 mmol) was added, and sodium hydride (NaH) (55) washed with hexane was added. %, 183 mg, 7.6 mmol).

After reacting at 0 ° C. for 1 hour, the solution was quenched by careful addition of brine (100 mL), and suction filtered using H ₂ O. After vacuum drying in a desiccator, recrystallization was performed using hexane (700 mL) to separate and remove unreacted icosyl bromide. Column chromatography (silica gel, methylene chloride, 6 cmΦ, 3 cm, Rf = 0.7) was performed, and the yellow solid was recrystallized with hexane to obtain powdery crystals (yield 448 mg, 53%).

The melting point of the obtained crystal was measured and found to be mp = 120.7-121.7 ° C. Further, structural analysis of the obtained crystal by ¹ H NMR (400 MHz CDCl ₃ ) revealed that δ = 0.88 (t, J = 6.8 Hz, 6H), 1.25 (m, 68H), 1. 71 (t, J = 6.8 Hz, 4H), 3.79 (t, J = 6.8 Hz, 4H), 6.43 (s, 4H). Further, structural analysis was performed by ¹³ C NMR (400 MHz C ₆ D ₆ ). As a result, δ = 14.3, 23.1, 26.8, 29.5, 29.82, 29.84, 30.05, 30. 13 (2C), 30.21 (8C), 50.4, 112.3, 119.6, and 120.9.

Moreover, when mass spectrometry was performed by TOF-MS (MALDI), m / z = 842.51 (M ^<+> ); Anal. _{Calcd for (C 50 H 86 N} 2 S 4): C, 71.20; H, 10.28; N, 3.32%. Found: C, 71.06; H, 10.25; N, 3.21%. Met. From the above results, it was revealed that the solid was Compound 1-f.

〔Example〕
<Measurement of FET (Field Effect Transistor) element characteristics>
FIG. 6 is a schematic diagram of an FET element used for measuring field effect transistor element characteristics (FET element characteristics) of the organic semiconductor material of the present invention.

The FET element was produced by the following method. Specifically, pure silicon is obtained by cutting a silicon substrate having an oxide film (SiO ₂ ) of 0.2 μm on one side into an area of about 1 × 1 cm and treating the non-oxidized side with hydrofluoric acid. And a gate electrode was disposed by vacuum-depositing Au.

Further, a substrate having this SiO ₂ oxide film (hereinafter referred to as an untreated substrate).
A normal element was fabricated by directly placing a semiconductor layer containing the organic semiconductor material of the present invention on the semiconductor layer. In addition, by placing the semiconductor layer on a substrate (hereinafter referred to as an OTS substrate) on which the oxide film has been subjected to Octyl trichlorosilane treatment, the Octyl trichlorosilane element and Hexamethyldisilazane surface-treated substrate (hereinafter referred to as HMDS) are disposed. A Hexamethyldisilazane element was fabricated by arranging a semiconductor layer.

  In the case of the vacuum vapor deposition method, the vapor deposition rate was 1.0-1.5 Å / sec. In the case of spin coating, the organic films were produced at a substrate rotation speed of 2000 rpm and a rotation time of 30 sec. Finally, Au was vacuum-deposited as a source and drain electrode to obtain a top FET element.

The formula shown below was used for calculation of field effect mobility (Mobility).
μ = 2L · I _D / C ₀ · W (V _g −V _th ) ²
Here, μ is field effect mobility [cm ² V ⁻¹ S ⁻¹ ], L is channel length [cm], W is channel width [cm], C ₀ is gate capacitance, V _g is gate voltage, V _“th” is a threshold voltage, and “ _ID” is a current amount at V _g . The device fabricated this time has L = 0.05 mm and W = 1.5 mm. A threshold voltage V _th (threshold voltage) is obtained by _calculating a linear approximation line of a straight line portion of a plot of V _g −I _d ^1/2 (I _d ^1/2 is a square root of the current value), and from there, I _d = the V _g at the time of 0 to become was determined as a threshold voltage.

The on / off ratio was calculated as follows. That is, the state where the gate voltage (V _g ) is 0 or sufficiently low and the current (I _d ) between the source and drain is the lowest is the off state, and the state where the current between the source and drain is the largest when the gate is applied The ratio of the current between the source and drain (I _d ) between the on state and the off state was calculated as the on / off ratio.

If the field effect mobility (μ) and the on / off ratio (I _on / I _off ) are large, it can be said that the FET element has high performance. Generally, a FET element having high performance has a field effect mobility (μ) value of 1 × 10 ⁻³ or more or an on / off ratio (I _on / I _off ) value of 1 × 10 ³ .

The solution used for spin coating was obtained by simple distillation in the case of chloroform and passing through an alumina column, and in the case of toluene by drying and distillation with CaH ₂ . The target product was diluted with these solutions to a predetermined concentration, and then a small amount of dust was removed by suction filtration, followed by spin coating.

1) Evaluation of FET element of bis (N-butylpyrrolo [3,4-d]) tetrathiafulvalene (1-b) Compound of the present invention by spin coating An FET element was fabricated by placing a semiconductor layer containing 1-b on an untreated substrate. A 0.4 wt% toluene solution or a 0.4 wt% chloroform solution was used as the solution used for the spin coating, respectively. The “0.4 wt% toluene solution” means a toluene solution in which the compound 1-b of the present invention is added to a final concentration of 0.4 wt%. Further, when the above two solutions were used, a semiconductor layer could not be disposed on the OTS and HMDS substrates.

Table 1 shows a current amount (I _d ), a threshold voltage (V _th ), a field effect mobility (μ), and an on / off ratio (Ion / Ioff) in the FET element. Table 1 shows that in the case of 0.4 wt% toluene, the values of field effect mobility (μ) and on / off ratio (Ion / Ioff) are low. On the other hand, in the case of 0.4 wt% chloroform, field effect mobility (μ) and on / off ratio (Ion / Ioff) could not be measured. Moreover, the thin film was not arrange | positioned by vacuum evaporation.

In FIG. 7 (a) 0.4 wt% toluene, indicates _V d -I _d curve in the FET element in which a semiconductor layer is disposed on Normal substrate, _V g -I _d curve in FIG. 7 (b) the FET element Is shown.

The V _d -I _d curve represents the relationship between the source-drain voltage (V _d ) and the current (I _d ) when the gate voltage (V _g ) is changed stepwise. _That, V d -I _d curve shows the output characteristics of the FET device (output characteristics). In the FET element, the V _d -I _d curve shows that the current (I _d ) in the high source-drain voltage (V _d ) region is saturated (saturation current) and the low source at any V _g . - to show that the voltage between the drain (V _d) area of the current (I _d) is up linearly, good output characteristics, the FET device can be said to be high.

_Also, V g -I _d curve at the output characteristics, the current _{(I d)} is a source to be the value that causes a saturation current - when the fixed voltage _{(V d)} between the drain, the gate voltage _{(V g} ) And current (I _d ). _That, V g -I _d curve shows the transfer characteristics of the FET device (transfer characteristic). In the V _g -I _d curve, the more rapid the rise from the off state to the on state, it indicates that the switching characteristics are good, it can be said that the transistor characteristics are excellent. Further, since the on / off ratio increases as the off current is lower and the on current is higher, it can be said that the transistor is a good transistor. Furthermore, it can be said that it is practical that Vg is close to 0V.

According to FIG. 7 (a), the source - but at a region with a high voltage (V _d) of the drain is saturation current observation, V _d -I _d curve in the lower region, not in a straight line. Further, according to FIG. 7B, the rise of the current (I _d ) due to the application of the gate voltage (V _g ) is gentle. Therefore, the performance of the FET element is considered to be low.

2) Evaluation of FET device of bis (N-octylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-octylpyrrolo [3,4-d]) tetrathiafulvalene); Compound 1-c) An FET element was fabricated by disposing a semiconductor layer containing Compound 1-c. As the solution used for the spin coating, 0.2 wt%, 0.4 wt%, and 1.0 wt% toluene solutions were used, respectively. The field effect mobility (μ) and the on / off ratio (I _on / I _off ) in the FET device could not be measured.

3) FET element evaluation of bis (N-dodecylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-dodecylpyrrolo [3,4-d]) tetrathiafulvalene); compound 1-d) A FET layer was produced by placing a semiconductor layer containing Compound 1-d on an untreated substrate or an OTS substrate. As the solution used for the spin coating, 0.2 wt%, 0.4 wt%, and 1.0 wt% toluene solutions were used, respectively. In addition, an FET element was also fabricated using a method in which a semiconductor layer containing Compound 1-c dissolved in a 0.4 wt% toluene solution and an untreated substrate were annealed at 60 ° C.

  In the EFT element which is an OTS substrate, solid deposition was observed in the semiconductor layer. A semiconductor layer could not be disposed on the HMDS substrate.

Table 2 shows the amount of current (I _d ), threshold voltage (V _th ), field effect mobility (μ), and on / off ratio (I _on / I _off ) in the above element. From Table 2, it can be seen that the field effect mobility (μ) and the on / off ratio (I _on / I _off ) are high when a 0.4 wt% toluene solution is used. Therefore, it can be said that the FET element in which the semiconductor layer containing the compound 1-d using a 0.4 wt% toluene solution is arranged on an untreated substrate has very high performance. FIG. 8A shows 0.4 wt. % in the FET element which is coated with a toluene _solution, showed a V d -I _d curve, FIG. 8 (b) shows the _V g -I _d curve in the FET element.

According to FIG. 8 (a), the source - in the area of high voltage (V _d) between the drain saturation current is observed, furthermore, the V _d -I _d curve in the lower region, has become a straight line. Further, according to FIG. 8B, the rise of the current (I _d ) due to the application of the gate voltage (V _g ) is steep. Therefore, the performance of the FET element is considered high.

Further, in FIG. 9 (a) the FET element after 3 days from the _formation, shows the V d -I _d curve, FIG. 9 (b) shows the _V g -I _d curve in the FET element. The above-mentioned “FET element 3 days after production” is an FET element in which the EFT element is stored for 3 days in a normal storage state in a plastic case.

According to FIG. 9 (a), the source - in the area of high voltage (V _d) between the drain it is not saturation current observed, whereas V _d -I _d curve in the lower region is a straight line. Further, according to FIG. 9B, the rise of the current (I _d ) due to the application of the gate voltage (V _g ) is gentle. It shows that the performance of the FET element is clearly degraded. It seems to be extremely susceptible to oxidation by air.

4) Bis (N-cetylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-cetylpyrrolo [3,4-d]) tetrathiafulvalene); FET device evaluation of compound 1-e Compound of the present invention by spin coating An FET element was fabricated by placing a semiconductor layer containing 1-e on an untreated substrate. 0.4 wt%, 0.6 wt%, and 1.0 wt% toluene solutions were used as solutions for the spin coating, respectively.

Table 3 shows the amount of current (I _d ), threshold voltage (V _th ), field effect mobility (μ), and on / off ratio (I _on / I _off ) in the above element. It can be seen from Table 3 that the field effect mobility (μ) and the on / off ratio (I _on / I _off ) are high when 0.4 wt% and 0.6 wt% toluene solutions are used.

5) FET device evaluation of bis (N-icosylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-icosylpyrrolo [3,4-d]) tetrathiafulvalene; compound 1-f))
An FET element was fabricated by placing a semiconductor layer containing Compound 1-f of the present invention on an untreated substrate by spin coating. A 0.2 wt% hot chlorobenzene solution was used as a solution for the spin coating.

Table 4 shows the field effect mobility (μ) and the on / off ratio (I _on / I _off ) of the above element.

Table 4 is a table summarizing the field effect mobility (μ) and the on / off ratio (I _on / I _off ) values of the FET elements in which the semiconductor layers containing the respective compounds are arranged. In addition, compounds of Comparative Examples described later were also collected together for comparison.

  Since compound 1-b was sufficiently soluble in toluene, the semiconductor layer could be disposed by a welding method by spin coating. Compound 1-c, compound 1-d, and compound 1-e also have high solubility in the same manner, and it can be said that the improvement of the solubility by extension of the alkyl chain was successful.

  As a result of the measurement of the FET characteristics, the field effect mobility and the on / off ratio of the compound 11 and the compound 1-a of the comparative example were very low. Therefore, the performance of the pyrrole-fused TTF itself as an FET seems to be low. The same applies to compound 1-b. Nevertheless, very high field effect mobility was obtained in Compound 1-d, Compound 1-e, and Compound 1-f. This value is a good value for an FET element using a welding method, and indicates that a pyrrole-fused TTF derivative can be suitably used as an organic semiconductor material for a soluble field effect transistor.

<Evaluation of electrochemical characteristics (CV: cyclic voltammetry)>
A silver / silver chloride (Ag / AgCl) electrode is used as a reference electrode, platinum (Pt) is used as a working electrode and a control electrode, tetra-N-butylhexafluorophosphate is added as an electrolyte to acetonitrile, and the target compound is 10 ⁻³ M CV of the target compound was measured. At this time, the target compound was dissolved by heating with a dryer, and the measurement was carried out promptly.

  Table 5 shows the oxidation potential as a result of CV measurement for Compound 1-c and Compound 1-d. The oxidation potentials of Compound 11, Compound 1-a and Compound 1-b are described in “JOJeppensen; K, Takimiya; F. Jensen; T. Brimert; K. Nielsen; N. Thorup; J. Becher, J. Org. Chem., 2000, 65, 5794-5805 ”. The oxidation potential of Compound 16 is described in “T. Jigami, K. Takimiya, T. Otsubo; J. Org. Chem., 1998, 63, 8865-8872”.

  According to Table 5, the oxidation potentials of Compound 1-c and Compound 1-d were almost the same as those of Compound 11, Compound 1-a and Compound 1-b. Therefore, it was found that the oxidation potential of the pyrrole fused ring compound was not affected by the length of the alkyl chain. Further, as a comparative example, it can be seen that the oxidation potential is low and the donor property is very high as compared with Compound 16.

<Evaluation of physical properties in solid state>
The physical properties of the organic semiconductor material of the present invention in the solid state were examined by performing DSC (differential thermal scanning calorimetry) and XRD (X-ray diffraction) measurements.

DSC (Differential Thermal Scanning Calorimetry) was performed by a conventionally known method using EXSTAR6000 DSC6200 manufactured by Seiko Instruments Inc.
XRD (X-ray diffraction) measurement was performed by a conventionally known method using M18XHF manufactured by Mac Science.

  Table 6 is a table | surface which shows each phase transition temperature and melting | fusing point of the result of having performed DSC (differential thermal scanning calorimetry) about compound 1-b, compound 1-c, and compound 1-d. In the butyl compound (Compound 1-b), a sharp endothermic peak that was considered to be a transition of the crystalline state was observed at a low temperature, and decomposition occurred with melting. In the octyl compound (Compound 1-c), one broad endotherm that was considered to be a glass transition was observed, and in the dodecyl compound (Compound 1-d), three sharp endothermic peak phase transitions were observed.

  FIG. 10A is a diagram in which an XRD measurement is performed on the substrate in a room temperature state after a semiconductor layer including a dodecyl body (compound 1-d) is disposed on the substrate. FIG. 10B is a diagram in which the substrate is heated to about 60 ° C. and then XRD measurement is performed. Comparing FIG. 10 (a) and FIG. 10 (b), it can be seen that the peak changes. Since a reversible endothermic peak obtained from this DSC measurement and diffraction are observed even after heating, it is considered that some change in crystal structure has occurred.

  Table 7 shows the diffraction peaks before heating, 2Theta means the position of the reflection peak in the X-ray diffraction experiment, and d means the interlayer distance. Table 10 shows the diffraction peaks after heating. According to Table 7, the interlayer distance d is 25 mm from the diffraction peak before heating. This value corresponds to the linear distance between the alkyl chain half and the TTF skeleton calculated from the optimized structure of the molecule by PM3. This is thought to be due to the fact that the stacking of layers occurs as if alkyl groups overlap.

  Further, according to Table 8, the diffraction peak after heating shows d = 17, which is considerably small from the viewpoint of the molecular length. I'm expecting that the alkyl chains will disappear and the molecule will lie on its side more than half, but the current results are not enough.

  Further, it can be seen from Table 8 that the endothermic peak is shifted to the high temperature side in the order of increasing the chain length of the alkyl chain (in the order of butyl, octyl, and dodecyl). This suggests that the butyl body (compound 1-b) and the octyl body (compound 1-c) before the phase transition temperature (endothermic peak) also have a crystal structure in which alkyl chains are overlapped in the same manner. is doing. In other words, the longer the alkyl chain, the stronger the fastener effect between the alkyl chains, so the temperature required for the phase transition may be higher.

[Comparative example]
6) Bis (pyrrolo [3,4-d]) tetrathiafulvalene (Bis (pyrrolo [3,4-d]) tetrathiafulvalene); FET device evaluation of compound 11 A semiconductor layer containing compound 11 of the present invention was formed by vacuum deposition. The FET element was produced by arrange | positioning on an untreated board | substrate, an OTS board | substrate, and a HMDS board | substrate. Table 9 shows the amount of current (I _d ), threshold voltage (V _th ), field-effect mobility (μ) and field-effect mobility in each FET element when using untreated OTS and HMDS as the substrate of the FET element. It is the table _| surface which showed on / off ratio ( _Ion / _Ioff ). Table 9 shows that the field effect mobility (μ) and the on / off ratio (I _on / I _off ) are low.

7) Bis (N-methylpyrrolo [3,4-d]) tetrathiafulvalene (Bis (N-methylpyrrolo [3,4-d]) tetrathiafulvalene); FET device evaluation of compound 1-a Sublimation-purified compound of the present invention 1-a was purified by sublimation, and a FET layer was prepared by disposing a semiconductor layer containing the compound 1-a on an untreated substrate and an OTS substrate by vacuum deposition. Table 10 is a table showing the current amount (I _d ), threshold voltage (V _th ), field effect mobility (μ), and on / off ratio (I _on / I _off ) in the FET element.

From Table 10, it can be seen that the FET element has a p-type FET response, but the field effect mobility (μ) and the on / off ratio (I _on / I _off ) are very low. Moreover, although the measurement was performed in a vacuum, little change was observed.

8) Dithieno [3,4-d] tetrathiafulvalene (Dithieno [3,4-d] tetrathiafulvalene); FET device evaluation of synthesis of compound 16 By vacuum deposition, the document "M. Mas-Torrent; P. Hadley; ST Bromley X. Ribas; J. Tarres; M. Mas; E. Molins; J. Veciana; C. Rovira, J. Am. Chem. Soc., 2004, 126, 8456-8553 " An FET element was fabricated by disposing on an untreated substrate, an OTS substrate, and an HMDS substrate. Table 11 shows the current amount (I _d ), threshold voltage (V _th ), field effect mobility (μ), and on / off ratio (I _on / I _off ) in the FET element.

Further, FIG. 11 (a) using a 0.4 wt% toluene solution, showed a _V d -I _d curve in the FET element in which a semiconductor layer is disposed HDMS substrate, in FIG. 11 (b) the FET element It shows the V _g -I _d curve.

According to FIG. 11 (a), the source - in the area of high voltage (V _d) between the drain saturated current observation, the V _d -I _d curve in the lower region, has become a straight line. Further, according to FIG. 11B, the rise of the current (I _d ) due to the application of the gate voltage (V _g ) is steep.

According to Table 11, the field effect mobility (μ) and the on / off ratio (I _on / I _off ) of the FET element are high, and the maximum field effect mobility is 0 particularly in a substrate treated with HMDS. .338 cm ² V ⁻¹ s ⁻¹ and an _on / off ratio (I _on / I _off) of 10 ⁶ . Therefore, it can be said that the FET element has high performance. FIG. 11 also shows that the FET element has high performance. In addition, when the measurement was performed in a low vacuum of about 2 Pa, the performance decreased.

  According to the present invention, an organic semiconductor material that can be used in a welding method, an organic semiconductor device that uses the organic semiconductor material, and a method for synthesizing an organic semiconductor device that uses the organic semiconductor material Can be provided.

  Therefore, the present invention can be used in the synthesis or sales industry of electrical and electronic equipment such as transistors, liquid crystal displays, organic EL displays, and electronic paper.

FIG. 1 is a diagram showing a reaction path 1 for synthesizing the organic semiconductor material of the present invention. FIG. 2 is a diagram showing reaction pathway 2 for synthesizing compound 6 from compound 2 in the examples of the present invention. FIG. 3 is a diagram showing reaction pathway 3 for synthesizing compound 16 from compound 6 in the examples of the present invention. FIG. 4 is a diagram showing reaction pathway 4 for synthesizing compound 1-b from compound 6 in the examples of the present invention. FIG. 5 is a diagram showing reaction pathway 5 for synthesizing compound 1-a, compound 1-c, compound 1-d, and compound 1-e from compound 6 in the examples of the present invention. FIG. 6 is a schematic diagram of the structure of the FET element used in the example of the present invention, (a) is a legislative view of the FET element, and (b) is a top view. Figure 7 is in the embodiment of the present invention, a _V d -I _d curve in the case of performing FET device evaluation of Compound 1-b (a) and _V g -I _d curve (b). Figure 8 is in the embodiment of the present invention, a _V d -I _d curve in the case of performing FET device evaluation of Compound 1-d (a) and _V g -I _d curve (b). 9 in an embodiment of the present invention, a _V d -I _d curve in the case of performing FET device evaluation of Compound 1-d after 3 days from the formation (a) and _V g -I _d curve (b). FIG. 10 shows the XRD measurement result (a) of compound 1-d at room temperature and the XRD measurement result (b) of compound 1-d after heating at 60 ° C. in the examples of the present invention. 11 in the comparative example of the present invention, a _V d -I _d curve in the case of performing FET element evaluation of compounds 16 (a) and _V g -I _d curve (b).

Explanation of symbols

1 FET element semiconductor layer 13 SiO ₂ oxide film 14 gate electrode 15 channel length 16 channel width comprising 10 source electrode 11 drain electrode 12 organic semiconductor material

Claims (8)

The organic-semiconductor material containing the compound represented by General formula (1).

General formula (1)
(Wherein R ₁ and / or R ₂ represents a functional group having a solubility effect.) _2. The organic semiconductor material according to claim 1, wherein R ₁ and / or R _{2 of the} compound represented by the general formula (1) is a functional group containing a carbon skeleton in the main chain. _2. The organic semiconductor material according to claim 1, wherein R ₁ and / or R _{2 of the} compound represented by the general formula (1) is an alkyl group having 4 or more carbon atoms.   The organic semiconductor material according to claim 3, wherein the alkyl group is a linear alkyl group having 12 or more carbon atoms.   An organic semiconductor device comprising the organic semiconductor material according to claim 1.   The organic semiconductor device according to claim 5, wherein the organic semiconductor device is a transistor.   The organic semiconductor device according to claim 5, wherein the organic semiconductor device is a light emitting device having an organic carrier transport layer and / or a light emitting layer.   The manufacturing method of the organic-semiconductor device including the process of arrange | positioning the organic-semiconductor material in any one of Claim 1 to 4 to a board | substrate with a welding method.

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