JP5390959B2 - Organic semiconductor compound having sulfone structure - Google Patents

Description

The present invention relates to an organic compound that can be developed into an electronic material such as an organic semiconductor.

The organic semiconductor material can be divided into a p-type driving material whose main carrier is a hole and an n-type driving material whose main carrier is an electron. Whether it is p-type or n-type depends on whether the carrier is moved using the highest occupied orbit (HOMO) or the lowest empty orbit (LUMO) of the organic semiconductor compound. Has been.

In general, when a metal having a small work function is used as an electrode, it easily acts as an n-type semiconductor, and when a metal having a large work function is used as an electrode, it is likely to act as a p-type semiconductor. As a metal electrode having a small work function, for example, calcium (about 2.87 eV) is known, but in the atmosphere, the surface is oxidized by oxygen, or a hydroxide is generated by moisture. In order to use it as an organic device, it is necessary to seal the electrode so that it is not affected by moisture or oxygen. On the other hand, as a metal having a large work function, for example, a metal that is stable in the atmosphere, such as gold (about 5.1 eV), is known. When a metal having a large work function is used for the electrode, the performance required for sealing is only physical protection, and thus there is a merit in cost, which is more preferable in the industry. However, when a metal having a large work function such as a gold electrode is used, the number of types of organic semiconductor materials that are n-type driven is much smaller than that of organic semiconductors that are p-type driven under the same conditions.

  To date, examples of compounds that are driven as n-type semiconductors include thiazole derivatives (Non-patent Document 1), pentacene derivatives (Non-patent Documents 2-3), fullerenes and derivatives thereof (Non-patent Document 4), peryleneimide derivatives (non-patent documents 1). Patent Document 5) is known.

S. Ando, R.A. Murakami, J. et al. -I. Nishida, H .; Tada, Y .; Inoue, S .; Tokyo, Y .; Yamashita, J .; Am. Chem. Soc. , 127, 3997 (2005). Y. Sakamoto, T .; Suzuki, M .; Kobayashi, Y. et al. Gao, Y .; Fukai, Y .; Inoue, F.A. Sato, S .; Tokyo, J. et al. Am. Che. Soc. 126, 8138 (2004). K. Okamoto, K .; Ogino, M .; Ikari, Y .; Kunigi, Bull. Chem. Soc. Jpn. 81, 530 (2008). R. C. Haddon, A .; S. Perel, R.A. C. Morris, T .; T.A. M.M. Palstra, A.M. F. Hebard, R.A. M.M. Fleming, Appl. Phys. Lett. 67, 121 (1995). C. Waldauf, P.M. Schilinsky, M.M. Peristutti, J. et al. Hauch, C.I. J. et al. Brabec, Adv. Mater. , 15, 2084 (2003). P. R. L. Malenfant, C.I. D. Dimitrakopoulos, J. et al. D. Gelorme, L.M. L. Kosbar, T .; O. Graham, A .; Curioni, W.M. Andreoni, Appl. Phys. Lett. , 80, 2517 (2002).

As described above, as the n-type semiconductor, the types of compounds are limited, and the selection range is narrow. Further, the pentacene derivative (Non-patent Document 3) has a problem that it is oxidized and deteriorated in the atmosphere.

Therefore, the present inventors have newly synthesized an organic semiconductor material having a new skeleton characterized by having a sulfone structure, and have arrived at an invention having the following configuration. That is, the compound according to claim 1 relating to the present invention is an organic compound characterized by a sulfone structure represented by the general formula (1).

Wherein the substituents R ¹ to R ⁸ are each independently, C androgenic atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a carbonyl group, an ester group, an amide group, an imino group , A sulfide group, a sulfoxide group, a sulfonyl group, a silyl group, a carboxyl group, a hydroxyl group, a nitro group, a nitrile group, and a mercapto group.

Furthermore, the compound according to claim 2 according to the present invention is an organic compound according to claim 1, wherein R ⁿ and R ^{(n + 4) in} the general formula (1 ⁾ are the same substituent. is there. Here, n is an integer of 1 or more and 4 or less.

Furthermore, the compound according to claim 3 according to the present invention is an organic compound characterized by any structure represented by the following general formulas (2) to (7).

Here, the substituents R ^{1 to} R ¹² are each independently a hydrogen atom and a deuterium atom, a halogen atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a carbonyl group, and an ester group. Amide group, imino group, sulfide group, sulfoxide group, sulfonyl group, silyl group, carboxyl group, hydroxyl group, nitro group, nitrile group, and mercapto group.

Furthermore, the compounds of claim 4 according to the present invention, according to claim 3, the general formula (2) in ~ (4) R ⁿ and R ^{(n + 6)} is characterized in that the same substituents It is an organic compound. Here, n is an integer of 1-6.

Furthermore, the compound according to claim 5 according to the present invention is the organic compound according to any one of claims 1 to 5 in which the substituent R has a function as a polymerizable functional group .

Furthermore, the compound according to claim 6 relating to the present invention is an oligomer or polymer having at least one skeleton of the organic compound according to general formulas 1 to 5.

Furthermore, the invention of claim 7 relating to the present invention is an organic semiconductor comprising the organic compound according to any one of claims 1 to 6 .

Further, the organic semiconductor device of claim 8 according to the present invention is an organic semiconductor device comprising an organic compound according to any one of claims 1-6.

According to the present invention, an organic semiconductor material having a sulfone structure excellent in oxidation resistance is provided. Furthermore, the organic device of the present invention has excellent characteristics.
That is, according to the first aspect of the present invention, an organic compound having excellent light resistance and oxidation resistance is provided. According to invention of Claim 2, the synthesis | combination of a compound (1) can be simplified and efficient manufacture is attained. According to invention of Claim 3, the organic compound excellent in light resistance, oxidation resistance, and heat resistance is provided. According to invention of Claim 4, the synthesis | combination of compound (2)-(7) can be simplified and efficient manufacture becomes possible. According to the invention of claim 5, when manufacturing a device, patterning (separation) of necessary compounds (1) to (7) is facilitated, and overcoating is possible. According to invention of Claim 6, the outstanding film forming property can be provided. According to the seventh aspect of the present invention, excellent electrical functionality can be imparted by forming a thin film. According to invention of Claim 8, the compound of this invention is applicable to an organic device.

UV-visible absorption spectrum of the compound described in Example 1 UV-visible absorption spectrum of the compound described in Example 2 UV-visible absorption spectrum of the compound described in Example 3 Ultraviolet-visible absorption spectrum of pentacene.

The compound of the present invention is a compound having a structure as shown in the general formulas (1) to (7), and the substituents R ^{1 to} R ¹² in the general formulas (1) to (7) are each independently Hydrogen atom and deuterium atom, halogen atom, aryl group, heterocyclic group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, carbonyl group, ester group, amide group, imino group, sulfide group, sulfoxide group, sulfonyl group, It contains at least one of silyl group, carboxyl group, hydroxyl group, nitro group, nitrile group and mercapto group.

Among these, preferred are a hydrogen atom, a deuterium atom, a halogen atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, and an alkoxyl group.
The aryl group, heterocyclic group, alkyl group, alkenyl group, alkynyl group, and alkoxyl group preferably have 1 to 36 carbon atoms. From the viewpoint of ease of synthesis and availability of raw materials, 1 to 18 carbon atoms are more preferable.

As specific examples of the substituents R ^{1 to} R ^{12 in} the general formulas (1) to (7),
For example, a halogen atom such as a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom or iodine atom.
For example, phenyl group, naphthyl group, biphenyl group, terphenyl group, perfluorophenyl group, perfluoronaphthyl group, perfluorobiphenyl group, perfluoroterphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2- Fluorophenyl group, p-tolyl group, p-fluorophenyl group, p-hexylphenyl group, p-cyclopentylphenyl group, m-tolyl group, m-fluorophenyl group, m-hexylphenyl group, m-cyclopentylphenyl group, o-tolyl group, o-fluorophenyl group, o-hexylphenyl group, o-cyclopentylphenyl group, 3,5-dimethylphenyl group, methylnaphthyl group, fluoronaphthyl group, octyloxynaphthyl group, cyclopentyloxynaphthyl group, methyl Biphenyl group, fluorobi Eniru group, an aryl group such as octyloxy biphenyl group, a cyclohexyl biphenyl group, a methyl terphenyl group, an isopropyl terphenyl group, tridecyl terphenyl group, tridecyloxy terphenyl group.

For example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, bipyridyl group, quinolyl group, 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, oxazolyl group, isoxazolyl group, thiazolyl Group, fluoropyridyl group, fluorobipyridyl group, fluoroquinolyl group, fluorothienyl group, fluorofuryl group, fluorooxazolyl group, fluoroisoxazolyl group, fluorothiazolyl group, methylpyridyl group, methylbipyridyl group, Methylquinolyl group, methylthienyl group, methylfuryl group, methyloxazolyl group, methylthiazolyl group, ethylpyridyl group, ethylbipyridyl group, ethylquinolyl group, ethylthienyl group, propylpyridyl group, propylbipyridyl group, propylquinolyl group, propylthienyl group Group, propyl-free Group, propyloxazolyl group, propylisoxazolyl group, propylthiazolyl group cyclopentylpyridyl group, cyclopentylbipyridyl group, cyclopentylquinolyl group, cyclopentylthienyl group, cyclopentylfuryl group, cyclopentyloxazolyl group, cyclopentylisoxa Zolyl, cyclopentylthiazolyl octylpyridyl, octylbipyridyl, octylquinolyl, octylthienyl, furyl, octyloxazolyl, octylisoxazolyl, octylthiazolyl tridecylpyridyl Substituted heterocycles such as tridecylbipyridyl, tridecylquinolyl, tridecylthienyl, tridecylfuryl, tridecyloxazolyl, tridecylisoxazolyl, tridecylthiazolyl It is.

For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, cycloheptyl group, 2-methylhexyl group 3-propylpentyl 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-heptadecyl group Group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-triacontyl group, n-hexatriacone An unsubstituted alkyl group such as a thiol group, trifluoromethyl group, pentafluoroethyl group, trifluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorocyclopentyl group, perfluorohexyl group, perfluorohexyl group Fluorocyclohexyl, perfluoroheptyl, perfluorononyl, perfluorodecyl, perfluoroundecyl, perfluorododecyl, perfluorotridecyl, perfluorotetradecyl, perfluoropentadecyl, perfluoro Alkyl such as hexadecyl group, perfluoroheptadecyl group, perfluorooctadecyl group, perfluorononadecyl group, perfluoroicosyl group, perfluorotriacontyl group, perfluorohexatriacontyl group, etc. It is.

For example, ethenyl group, methylethenyl group, isopropylethenyl group, (n-butyl) ethenyl group, (cyclopentyl) ethenyl group, (n-octyl) ethenyl group, (n-tridecyl) ethenyl group, (1,2-difluorophenyl) ) Ethenyl group, (trifluoromethyl) ethenyl group, phenylethenyl group, perfluorophenylethenyl group, (4- (n-octyl) phenyl) ethenyl group, 4-trifluoromethylphenylethenyl group, 4-par An alkenyl group such as a fluorooctylphenylethenyl group, a biphenylethenyl group, a terphenylethenyl group, a naphthylethenyl group, a cyanoethenyl group, a dicyanoethenyl group;

For example, methylethynyl group, isopropylethynyl group, tert-butylethynyl group, (n-pentyl) ethynyl group, (n-cyclohexyl) ethynyl group, (n-octyl) ethynyl group, (n-tridecyl) ethynyl group, (n -Octadecyl) ethynyl group, (trifluoromethyl) ethynyl group, (n-perfluorobutyl) ethynyl group, (perfluorooctyl) ethynyl group, phenylethynyl group, perfluorophenylethynyl group, (p-octylphenyl) ethynyl group , Biphenylethynyl group, naphthylethynyl group, (p-methylphenyl) ethynyl group, (m-methylphenyl) ethynyl group, (o-methylphenyl) ethynyl group, (p-isopropylphenyl) ethynyl group, (m-cyclopentylphenyl) ) Substituted ethynyl groups, etc. Is a group.

For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group Tert-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 1-methylpentyloxy group, 4-methyl-2-pentyloxy group, 3,3-dimethylbutyloxy group, 2-ethyl Butyloxy group, n-heptyloxy group, cycloheptyloxy group, 2-methylhexyloxy group, 3-propylpentyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy Group, n-tridecyloxy group, n-tetradecyloxy group, -Pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-triacontyloxy group, n-hexatriacontyl group An alkoxy group such as an oxy group.

Of these, preferred are a hydrogen atom, a deuterium atom, a halogen atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, and an alkoxy group.
Moreover, as for carbon number of an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, and an alkoxyl group, 1-36 are preferable, and from a viewpoint of manufacturing cost, More preferably, it is C1-C18.

When R ⁿ and R ^{(n + 4} ) in the general formula (1) are the same substituent (where n is an integer of 1 or more and 4 or less), or in the general formulas (2) to (7) When R ^m and R ^{(m + 6)} are the same substituent (where m is an integer of 1 or more and 6 or less), the synthesis can be simplified and efficient production becomes possible, which is preferable.

A method for producing the compounds represented by the general formulas (1) to (4) of the present invention will be described.
The compounds represented by the general formulas (1) to (4) of the present invention can be produced by oxidizing a benzothienobenzothiophene derivative with an oxidizing agent or an electrode. The benzothienobenzothiophene derivative can be produced with reference to known methods (for example, Patent Documents 1 to 4 and Non-Patent Document 6).
WO2006 / 0777888 A1 Japanese Patent Application No. 2009-004142 Japanese Patent Application No. 2009-106387 JP2009-021390 S. Y. Zherdeva, A .; Barudi, A .; Y. Zheltov, B.M. I. Stepanov, Zh. Organi. Khimi. 16, 430 (1980).

Examples of the oxidizing agent that can be used include hydrogen peroxide, peracid, hydroperoxide, halogen, halogenating agent, ozone, oxygen and transition metal catalyst, potassium peroxy, potassium permanganate, tetraoxide Examples include dinitrogen, sodium metaperiodate, and nitric acid. Further, oxidation using an electrode can also be used.

As the peracid, formic acid, peracetic acid, perbenzoic acid, perphthalic acid and derivatives thereof can be used. As hydroperoxides, p-cymene hydroperoxide, cumene hydroperoxide, diphenylmethyl hydroperoxide, 9-fluorenyl hydroperoxide, Sec-butyl hydroperoxide, tert-butyl hydroperoxide, cyclohexyl hydroperoxide, 1-methylcyclohexyl hydroperoxide Etc. can be used.
As the halogen, chlorine, bromine, iodine and the like can be used.

As the halogenating agent, N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide and the like can be used. Transition metal catalysts include WO ₃ , KMnO ₄ , RuO ₂ , Na ₂ WO ₄ , Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Ni (cod) ₂ , Ni (CO) ₄ , Cp ₂ Fe Fe (CO) ₅ , Mo (CO) ₆ , RuCl ₂ (PCy ₃ ) ₂ , RhCl (PPh ₃ ) _{3 and the} like can be used.

According to the present invention, the compound according to claim 5 having a polymerization function facilitates patterning (separation) of necessary compounds (1) to (7) when a device is produced, so that overcoating can be performed. It becomes possible. Here, having a polymerization function means having a polymerizable functional group. For example, a compound having one or more diyne structures in one molecule. Examples thereof include compounds having two or more halogen atoms, vinyl groups, methacryl groups, epoxy groups, amino groups, carboxyl groups and the like in one molecule.

Polymers (oligomers and polymers) obtained as a result of polymerizing polymerizable functional groups are also included in the present invention. As a method for polymerizing a polymerizable functional group, any of heat, light, and acid may be used.

Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited by these examples.

A 200 ml flask was charged with 0.6 g of benzothienobenzothiophene, 60 ml of acetic acid and 60 ml of acetic anhydride, and the reaction solution was heated to 60 ° C. in an oil bath. Thereafter, 25 ml of hydrogen peroxide solution was slowly dropped, and when the heat generation was confirmed, the oil bath was removed and a time was allowed until the heat generation stopped. Thereafter, the mixture was stirred overnight at 100 ° C. again in an oil bath. This was cooled to room temperature, the precipitated crystals were collected by filtration, dissolved in 1,2-dichloromethane, and purified using column chromatography to obtain a yellow solid.
_{^{1 H NMR (400MHz, CDCl 3}} , δppm) 8.22-8.27 (m, 2H), 7.82-7.92 (m, 6H).

2.0 g of 2-tridecane benzothienobenzothiophene and 100 ml of 1,2-dichloroethane were charged into a 200 ml flask, and the reaction solution was heated to the reflux temperature in an oil bath at 85 ° C. Thereafter, 6.0 g of m-chloroperbenzoic acid dissolved in 70 ml of 1,2-dichloroethane was added dropwise to the reaction solution. After dropping, the mixture was heated and stirred at 85 ° C. for 24 hours. The reaction solution was poured into 350 ml of dichloromethane, dissolved uniformly, and then purified by column chromatography to obtain yellow fine crystals.
¹ H NMR (400 MHz, CDCl ₃ , δ ppm) 7.80-7.85 (m, 1H), 7.60-7.80 (m, 5H), 7.48-7.51 (dd, 1H), 2.75 (t, 2H), 1.66 (m, 2H), 1.20-1.40 (m, 20H), 0.88 (t, 3H).

Dinaphtho [2,1-b: 2 ′, 1′-f] thieno [3,2-b] thiophene 0.50 g and 1,2-dichloroethane 50 ml are charged into a 100 ml flask and reacted in an oil bath at 85 ° C. The solution was heated to reflux temperature. Thereafter, 1.10 g of m-chloroperbenzoic acid dissolved in 20 ml of 1,2-dichloroethane was added dropwise to the reaction solution. After dropping, the mixture was heated and stirred at 85 ° C. for 24 hours. Thereafter, the reaction solution was air-cooled, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 1,2-dichloromethane and purified by column chromatography using silica gel to obtain a red powder.
The mass spectrum of the obtained compound is shown in the figure below.

FIG. 1 to FIG. 3 show the time-dependent changes in the ultraviolet-visible absorption spectrum for 12 hours and 24 hours immediately after the compounds of Examples 1 to 3 were dissolved in an organic solvent (1,1,2,2-tetrachloroethane). Indicated. From FIG. 4, the shape of the spectrum of pentacene changes greatly due to oxidative degradation immediately after the solution preparation and after 24 hours. On the other hand, the spectrum of the compound, which is a specific example of the compound of the present invention, is almost the same immediately after the preparation of the solution and 24 hours later, indicating that it is stable in the solution state.

Immediately after pentacene was dissolved in an organic solvent (1,1,2,2-tetrachloroethane), the time-dependent changes in the ultraviolet-visible absorption spectrum for 12 hours and 24 hours are shown in the figure. The shape of the spectrum immediately after preparation of the solution and after 24 hours has changed greatly due to oxidative degradation. On the other hand, the spectrum of the compound, which is a specific example of the compound of the present invention, is almost the same immediately after the preparation of the solution and 24 hours later, indicating that it is stable in the solution state.

ADVANTAGE OF THE INVENTION According to this invention, even if it melt | dissolves in an organic solvent, it becomes possible to provide the n-type organic semiconductor excellent in light resistance and oxidation resistance, patterning and recoating are possible, and the device which has the outstanding electrical property Demand for production will be greatly increased.

Claims (8)

An organic compound characterized by a sulfone structure represented by the following general formula (1).
Wherein the substituents R ¹ to R ⁸ are each independently, C androgenic atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a carbonyl group, an ester group, an amide group, an imino group , A sulfide group, a sulfoxide group, a sulfonyl group, a silyl group, a carboxyl group, a hydroxyl group, a nitro group, a nitrile group, and a mercapto group. The organic compound according to claim 1, wherein R ⁿ and R ^{(n + 4) in the} general formula (1) are the same substituent. Here, n is an integer of 1 or more and 4 or less. An organic compound characterized by any structure represented by the following general formulas (2) to (7).
Here, the substituents R ^{1 to} R ¹² are each independently a hydrogen atom and a deuterium atom, a halogen atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a carbonyl group, and an ester group. Amide group, imino group, sulfide group, sulfoxide group, sulfonyl group, silyl group, carboxyl group, hydroxyl group, nitro group, nitrile group, and mercapto group. The organic compound according to claim 3 , wherein R ⁿ and R ^{(n + 6) in the} general formulas (2) to (4) are the same substituent. Here, n is an integer of 1-6. The organic compound according to claim 1, wherein the substituent R has a function as a polymerizable functional group . 6. An oligomer or polymer having at least one skeleton of the organic compound according to claim 1. The organic semiconductor formed of an organic compound according to any one of claims 1-6. The organic semiconductor device comprising an organic compound according to any one of claims 1-6.