KR101490104B1 - Novel Naphthalene compound, manufacturing method thereof, and organic electronic device that contains it - Google Patents

Abstract

The organic semiconductor compound of the present invention can produce a novel naphthalene diimide derivative compound by reacting with a naphthalene diimide derivative and an electron donor or an electron donor compound. Further, since the organic semiconductor compound of the present invention exhibits a low band gap of a compound prepared by synthesizing a naphthalene diimide derivative and an unsubstituted or substituted thiophene containing sulfur (S), the organic electronic device comprising the same has a high Efficiency. In addition, the organic semiconductor compound of the present invention can be an organic semiconductor material having excellent thermal stability and physical properties and high intermolecular interaction and excellent electrical characteristics. Accordingly, the organic semiconductor compound of the present invention has an advantage that it can be used in various organic electronic devices in addition to an organic thin film transistor.

Description

TECHNICAL FIELD [0001] The present invention relates to a naphthalene diimide derivative compound, a naphthalene diimide derivative compound, an organic electronic device including the naphthalene diimide derivative compound,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic semiconductor compound, a method of manufacturing the same, and an organic electronic device including the organic semiconductor compound. More particularly, the present invention relates to an organic semiconductor compound including naphthalene diimide.

Organic thin film transistors (OTFTs) are now being targeted for intensive research activities due to their low cost, large size, and the possibility of producing flexible electronic devices. Organic thin film transistors include electrodes (source and drain), substrates and gate electrodes that require high thermal stability, insulators that have high dielectric constant and dielectric constant, and semiconductors that move charges well. There are many problems to be overcome, and the key material is organic semiconductor. Organic semiconductors can be classified into low-molecular organic semiconductors and polymeric organic semiconductors according to molecular weight, and classified into n-type organic semiconductors or p-type organic semiconductors depending on whether electrons or holes are delivered. In general, when a low molecular weight organic semiconductor is used in the formation of an organic semiconductor layer, the low molecular weight organic semiconductor is easy to purify and can remove almost any impurities. A variety of 1,4,5,8-naphthalene tetracarboxylic acid diimides are prepared and used in n-type semiconductors as disclosed in Korean Patent Publication No. 2008-0063803. However, there remains a need for the development of new and improved naphthalene tetracarboxylic acid diimide derivative compounds for transistor materials with excellent electrical properties.

Korean Patent Publication No. 10-2008-0063803

The present invention provides an organic semiconductor compound having solubility and excellent electrical properties.

The present invention also provides a method for producing the organic semiconductor compound of the present invention.

The present invention also provides an organic electronic device comprising the organic semiconductor compound of the present invention.

The present invention relates to a novel organic polymer semiconductor compound characterized by a naphthalene diimide compound and an organic electronic device including the organic semiconductor compound. The organic semiconductor compound according to the present invention is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ are independently from each other selected from (C ₁ -C 50) hydroxyalkyl, (C 1 -C 50) alkoxy and (C 1 -C 50) alkyl;

Z ₁ to Z ₄ independently of one another are hydrogen, halogen, (C 1 -C 50) hydroxyalkyl, (C 1 -C 50) alkyl, (C 1 -C 50) alkoxy, (C 6 -C 50) (C6-C50) aryl (C1-C50) alkyl and (C6-C50) aryloxy;

및

으로 선택되는 하나이상의 치환기로 더 치환될 수 있으며, A₁ 및 A₂는 서로 독립적으로 할로겐, 시아노기 및 (C1-C10)알킬로부터 선택되는 하나이상의 치환기로 더 치환될 수 있다.The above Z ₁ to Z ₄ Alkyl, alkoxy, aryl and heteroaryl are each independently of the other halogen, (C2-C50) heteroaryl, cyano,

And

, And A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl.

The present invention relates to organic semiconductor compounds for organic electronic devices such as organic thin film transistors (OTFTs) and their uses. More specifically, the present invention relates to a novel naphthalene diimide derivative compound which is a novel p-type and n-type organic semiconductor compound through reaction of a naphthalene diimide derivative with an electron donor or an electron donating compound and an organic electronic compound Device.

The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond. For example, benzothiophene is also included in heteroaryl.

In Formula 1 according to an embodiment of the present invention, Z ₂ and Z ₃ are hydrogen, and Z ₁ and Z ₄ may independently be an organic semiconductor compound selected from the following structures.

In the above formula,

Y is O, S, or Se;

또는

이고,X is hydrogen, halogen, cyano,

or

ego,

A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl;

n is an integer of 1 to 3;

The organic semiconductor compound of the present invention can be substituted with a derivative such as the above structural formula to increase the electron density of naphthalene diimide, thereby enhancing intermolecular interaction and exhibiting high mobility.

More specifically, R ₁ and R ₂ in formula (1) may be independently of one another an (C 5 -C 30) hydroxyalkyl, (C 5 -C 30) alkoxy or (C 5 -C 30) alkyl.

More specifically, the organic semiconductor compound of the present invention can increase the solubility and improve the electron characteristics by substituting an alkyl group for an imide group rather than an aryl group.

The organic semiconductor compound according to an embodiment of the present invention may be selected from the following structures.

In the above formula,

R ₁ and R ₂ are independently from each other selected from (C 5 -C 30) hydroxyalkyl, (C 5 -C 30) alkoxy and (C 5 -C 30) alkyl;

X is hydrogen, halogen or cyano;

n is an integer of 1 to 3;

The organic semiconductor compound according to an embodiment of the present invention may be selected from the following structures.

As a method for preparing the organic semiconductor compound according to the present invention, a final compound can be prepared through an alkylation reaction, various coupling reactions, and the like. The organic semiconductor compound according to the present invention is not limited to the following production methods, but may be prepared by conventional organic chemical reactions other than the following production methods.

The solvent used in the production method of the present invention may be any conventional organic solvent but may be any solvent such as chloroform, dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile (MeCN) N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), benzene, 1,4-dioxane (1 , 4-dioxane). acetic acid (AcOH), and oleum. It is preferable to use at least one selected from the group consisting of acetic acid (AcOH) and oleum.

The following Formula 11 according to an embodiment of the present invention may be a method for preparing Formula 12 by reacting with CuCN.

(11)

[Chemical Formula 12]

In the above formulas (11) and (12)

R ₁ and R ₂ are independently from each other selected from (C 5 -C 30) hydroxyalkyl, (C 5 -C 30) alkoxy and (C 5 -C 30) alkyl;

D is halogen;

Y is O, S or Se.

The organic semiconductor compound according to an embodiment of the present invention may be prepared by reacting the compound of formula (3) with the compound of formula (4) to prepare the compound of formula (5), followed by halogenation.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(11)

In the above formulas (3), (4), (5) and (11)

R _1, R _2, and R < _{101 &} Are independently selected from (C5-C30) hydroxyalkyl, (C5-C30) alkoxy and (C5-C30) alkyl;

D is halogen;

Y is O, S or Se.

The organic semiconductor compound according to an embodiment of the present invention may be a method for preparing the compound of Formula 22 by reacting Formula 3 and Formula 21.

(3)

[Chemical Formula 21]

[Chemical Formula 22]

In the above formulas (3), (21) and (22)

R ₁ and R ₂ is Are independently selected from (C5-C30) hydroxyalkyl, (C5-C30) alkoxy and (C5-C30) alkyl;

D is halogen;

Y is O, S or Se;

및

으로 선택되는 하나이상의 치환기로 더 치환될 수 있으며, A₁ 및 A₂는 서로 독립적으로 할로겐, 시아노기 및 (C1-C10)알킬로부터 선택되는 하나이상의 치환기로 더 치환될 수 있으며;X is hydrogen, halogen, (C2-C50) heteroaryl, cyano, aldehyde,

And

And A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl;

n is an integer from 1 to 3;

,

또는

이다.E is -B (OH) _2, BFK _3,

,

or

to be.

The organic semiconductor compound according to an embodiment of the present invention may be a method for preparing the compound of Formula 31 by reacting the following Formula 22 and Formula 23.

[Chemical Formula 22]

(23)

(31)

In Formulas 22 and 31,

R ₁ and R ₂ is Are independently selected from (C5-C30) hydroxyalkyl, (C5-C30) alkoxy and (C5-C30) alkyl;

및

으로 선택되는 하나이상의 치환기로 더 치환될 수 있으며, A₁ 및 A₂는 서로 독립적으로 할로겐, 시아노기 및 (C1-C10)알킬로부터 선택되는 하나이상의 치환기로 더 치환될 수 있으며;X is hydrogen, halogen, (C2-C50) heteroaryl, cyano, carboxylic acid group,

And

And A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl;

n is an integer from 1 to 3;

In formula (23)

R < ₅ > is (C1-C10) alkyl;

Y is O, S or Se.

The present invention also provides an organic electronic device comprising the organic semiconductor compound of the present invention.

The organic semiconductor compound of the present invention can produce a novel naphthalene diimide derivative compound by reacting with a naphthalene diimide derivative and an electron donor or an electron donor compound.

Further, since the organic semiconductor compound of the present invention exhibits a low band gap of a compound prepared by synthesizing a naphthalene diimide derivative and an unsubstituted or substituted thiophene containing sulfur (S), the organic electronic device comprising the same has a high Efficiency.

In addition, the organic semiconductor compound of the present invention can be an organic semiconductor material having excellent thermal stability and physical properties and high intermolecular interaction and excellent electrical characteristics.

Accordingly, the organic semiconductor compound of the present invention has an advantage that it can be used in various organic electronic devices in addition to an organic thin film transistor.

1 - Thermogravimetric analysis (TGA) of the organic semiconductor compound prepared in Example 1
2 - Differential calorimetric analysis (DSC) of the organic semiconductor compound prepared in Example 1,
3 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound prepared in Example 1
4 - A cyclic voltammetry curve of the organic semiconductor compound prepared in Example 1
5 - Thermogravimetric analysis (TGA) of the organic semiconductor compound prepared in Example 2
6 - Differential calorimetric analysis (DSC) of the organic semiconductor compound prepared in Example 2
7 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound prepared in Example 2
8 shows a cyclic voltammetry curve of the organic semiconductor compound prepared in Example 2
9 - Thermogravimetric analysis (TGA) of the organic semiconductor compound prepared in Example 3
Fig. 10 - Differential calorimetric analysis (DSC) of the organic semiconductor compound prepared in Example 3
11 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound prepared in Example 3
12 - Cyclic voltammetry curve of the organic semiconductor compound prepared in Example 3
Fig. 13-Thermogravimetric analysis (TGA) of the organic semiconductor compound prepared in Example 4
Fig. 14-Differential calorimetric analysis (DSC) of the organic semiconductor compound prepared in Example 4
15 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound prepared in Example 4
The cyclic voltammetry curve of the organic semiconductor compound prepared in Example 4
17 - Thermogravimetric analysis (TGA) of the organic semiconductor compound prepared in Example 5
18 - Differential calorimetric analysis (DSC) of the organic semiconductor compound prepared in Example 5,
19 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound prepared in Example 5
20 - cyclic voltammetry curve of the organic semiconductor compound prepared in Example 5

Hereinafter, the present invention will be described in detail with reference to examples. However, the following Preparation Examples and Examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Here, unless otherwise defined in the technical terms and the scientific terms used, those having ordinary skill in the art to which the present invention belongs have the same meaning as commonly understood by those skilled in the art. Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

[Production Example 1] Synthesis of 4,9-dibromoisochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone

Add isochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone (17.60 g, 65.64 mmol) to a 500 mL three-neck round bottom flask and dissolve in 100 mL of oleum. Add 1,3-dibromo-1,3,5-triazinane-2,4,6-trione (18.83 g, 65.64 mmol) to another 500 mL three-neck round bottom flask and dissolve in oleum (50 mL). 1,3-dibromo-1,3,5-triazinane-2,4,6-trione dissolved in oleum was dissolved in isochromeno [6,5,4-def] isochromene-1,3, Pour into a flask containing 6,8-tetraone solution and react at 40 ^° C for 5 hours. Add ice water to a 1000-mL beaker, pour the reaction mixture, and stir for at least 1 hour. After washing several times with water, it was washed with methanol, filtered and dried to obtain a light green solid, 4,9-dibromoisochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone (26 g, 94%). The prepared compound could be analyzed by ¹ H NMR and IR.

¹ H NMR (300 MHz, CDCl ₃ ,?): 8.71 (s, 2H); IR (KBr, cm ^-1 ): 1786,

[Preparation Example 2] 4,9-dibromo-2,7-dioctylbenzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H ) -tetraone synthesis

Add 4,9-dibromoisochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone (9.50 g, 22.30 mmol) to a 500 mL three-necked round bottom flask and dissolve in acetic acid, glacial 200 mL Then add octylamine (14.78 mL, 89.21 mmol). After reacting at 130 ^° C for 1 hour, water is added to the reaction vessel, stirred, washed with water and filtered. Column chromatography (eluent: dichloromethane / hexane = 1/1 ) as ivory solid 4,9-dibromo-2,7-dioctylbenzo [ lmn] [3,8] phenanthroline-1,3,6,8 (2 H, 7 H ) -tetraone (2.9 g, 20%). The prepared compound could be analyzed by ¹ H NMR. ¹ H NMR (300 MHz, CDCl ₃ ,?): 9.02 (s, 2H), 4.23-4.18 (t, 4H), 1.78-1.73 (m, 4H), 1.44-1.30 t, 6H)

[Production Example 3]

2,7-dioctyl-4,9-di (thiophen-2-yl) benzo [m] [3,8] phenanthroline-1,3,6,8 H , 7 H ) -tetraone

To a 100 mL 2-necked round bottom flask was added tributyl (thiophen-2-yl) stannane (1.99 g, 5.33 mmol), 4,9-dibromo-2,7-dioctylbenzo [ , 8 (2 H, 7 H ) -tetraone (1.38g, 2.13mmol), tetrakis (triphenylphosphino) palladium [Pd (PPh 3) 4] (0.07g, 0.06mmol), put the toluene (25mL) under nitrogen gas stream, 85 ^o C for 24 hours. After the reaction was completed, the reaction mixture was extracted with dichloromethane and separated by column chromatography (eluent: dichloromethane / hexane = 2/1) to obtain red solid 2,7-dioctyl-4,9-di (thiophen- [3,8] phenanthroline-1,3,6,8 (2 H, 7 H) to give the -tetraone (0.96 g, 69%) . The prepared compound could be analyzed by ¹ H NMR. _{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.74 (s, 2H), 7.62-7.61 (d, 2H), 7.33-7.31 (d, 2H), 7.25-7.22 (t, 2H), 4.31- 4.08 (t, 4H), 1.75-1.63 (m, 4H), 1.37-1.30 (m, 20H), 0.92-0.88 (t, 6H).

[Production Example 4]

4,9-bis (5-bromothiophen-2-yl) -2,7-dioctylbenzo [m] [3,8] phenanthroline-1,3,6,8 H , 7H) -tetraone

250mL 3-neck round 2,7-dioctyl-4,9-di ( thiophen-2-yl) bottom flask benzo [lmn] [3,8] phenanthroline -1,3,6,8 (2 H, 7 H) -tetraone (0.67 g, 1.02 mmol) and N- bromosuccinimide (0.38 g, 2.15 mmol), add 20 mL of chloroform and 20 mL of acetic acid and react at room temperature for 24 hours. After the reaction was completed, the solvent was removed and the product was isolated by column chromatography (eluent: dichloromethane / hexane = 2/1) to obtain red solid 4,9-bis (5-bromothiophen-2-yl) -2,7-dioctylbenzo [ [3,8] to give a phenanthroline-1,3,6,8 (2 H, 7 H) -tetraone (0.58 g, 70%). The prepared compound could be analyzed by ¹ H NMR.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.72 (s, 2H), 7.21-7.20 (d, 2H), 7.11-7.10 (d, 2H), 4.14-4.09 (t, 4H), 1.73- 1.65 (m, 4H), 1.38-1.31 (m, 20H), 0.93-0.88 (t, 6H).

[Production Example 5]

4,9-dibromo-2,7-bis (2-decyltetradecyl) benzo [m] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H ) -tetraone

Add 4,9-dibromoisochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone (10 g, 23.47 mmol) to a 500 mL three-neck round bottom flask and dissolve in acetic acid, glacial 200 mL Followed by 2-decyltetradecan-1-amine (20.75 g, 58.68 mmol). After reacting at 130 ^° C for 1 hour, water is added to the reaction vessel, stirred, washed with water and filtered. 4-dibromo-2,7-bis (2-decyltetradecyl) benzo [lmn] [3,8] phenanthroline-1,3, 6,8 (2 H , 7 H ) -tetraone (10.36 g, 40%). The prepared compound could be analyzed by ¹ H NMR and IR.

_{^{1 H NMR (300MHz, CDCl 3}} , δ): 9.01 (s, 2H), 4.16-4.14 (t, 4H), 2.15-2.00 (m, 2H), 1.27 (m, 80H), 0.92-0.88 (t, 12H); IR (KBr, cm- ¹ ): 3048, 2926, 2846, 1710, 1655.

[Production Example 6]

2,7-bis (2-decyltetradecyl) -4,9-di (thiophen-2-yl) benzo [m] [3,8] phenanthroline-1,3,6,8 H , 7 H ) -tetraone

2-tributylstannylthiophene (3.31 g, 8.86 mmol), 4,9-dibromo-2,7-bis (2-decyltetradecyl) benzo [i] [3,8] phenanthroline- 1,3,6 , 8 (2 H, 7 H ) -tetraone (3.89g, 3.55mmol), tetrakis (triphenylphosphino) palladium [Pd (PPh 3) 4] (0.12g, 0.11mmol), put the toluene (70mL) under nitrogen gas stream, 85 ^o C for 24 hours. After the reaction was completed, the reaction mixture was extracted with dichloromethane and separated by column chromatography (eluent: dichloromethane / hexane = 1/1) to obtain 2-decyltetradecyl-4,9-di (thiophen- to obtain a benzo [lmn] [3,8] phenanthroline -1,3,6,8 (2 H, 7 H) -tetraone (2.52 g, 71%). The prepared compound could be analyzed by ¹ H NMR.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.77 (s, 2H), 7.62-7.60 (d, 2H), 7.33-7.32 (d, 2H), 7.25-7.22 (t, 2H), 4.08- 4.06 (d, 4H), 1.97-1.94 (m, 2H), 1.26 (m, 80H), 0.92-0.88 (m, 12H).

[Production Example 7]

4,9-bis (5-bromothiophen-2-yl) -2,7-bis (2-decyltetradecyl) benzo [m] [3,8] phenanthroline-1,3,6,8 H , 7 H ) -tetraone

To a 250 mL three-neck round bottom flask was added 2,7-bis (2-decyltetradecyl) -4,9-di (thiophen-2-yl) benzo [1nn] [3,8] phenanthroline- 1,3,6,8 H, 7 H) - put tetraone (2.00g, 1.81mmol), N -bromosuccinimide (0.65g, 3.62mmol) , insert the chloroform 10 mL, 10 mL of acetic acid and then reacted at room temperature for 24 hours. After the reaction was completed, the solvent was removed and the product was isolated by column chromatography (eluent: dichloromethane / hexane = 1/1) to obtain red solid 4,9-bis (5-bromothiophen- decyltetradecyl) benzo was obtained [lmn] [3,8] phenanthroline- 1,3,6,8 (2 H, 7 H) -tetraone (0.61 g, 87%). The prepared compound could be analyzed by ¹ H NMR.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.72 (s, 2H), 7.21-7.20 (d, 2H), 7.12-7.11 (d, 2H), 4.10-4.07 (d, 4H), 2.04 ( m, 2H), 1.27 (m, 80H), 0.92-0.88 (m, 12H).

[Production Example 8]

5,5 '- (2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [m] [3,8] phenanthroline-4,9-diyl ) bis (thiophene-2-carbaldehyde)

3,9,8-phenanthroline-1,3,6,8 ( 2H , 7H) -tetraone (0.88 g, 1.36 mmol) was added to a 100 mL 2-necked round bottom flask, (5-formylthiophen-2-yl) boronicacid (0.53 g, 3.4 mmol), 15 mL of toluene and 2.72 mL of 2MK ₂ CO ₃ were slowly added and stirred for 30 minutes under a stream of nitrogen. Then, tetrakis (triphenylphosphino) palladium [Pd ₃ ) ₄ ] (0.01 g, 0.01 mmol) was added and reacted at 85 ^° C for 24 hours. After the reaction was completed, the solvent was removed, and the reaction mixture was extracted with chloroform and then subjected to column chromatography (eluent: dichloromethane / hexane = 5/1) to obtain 5,5 '- (2,7-dioctyl-1,3,6,8-tetraoxo -1,2,3,6,7,7-hexahydrobenzo [l, mn] [3,8] phenanthroline-4,9-diyl) bis (thiophene-2-carbaldehyde) (0.49 g, 51%). The prepared compound could be analyzed by ¹ H NMR.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 10.04 (s, 2H), 8.74 (s, 2H), 7.95-7.90 (d, 2H), 7.36-7.35 (d, 2H), 4.19-4.07 ( t, 4H), 1.73-1.65 (m, 4H), 1.48-1.30 (m, 20H), 0.92-0.90 (t, 6H).

[Example 1]

4,9-di ([2,2'-bithiophen] -5-yl) -2,7-dioctylbenzo [m] [3,8] phenanthroline-1,3,6,8 H , 7 H ) -tetraone

2,7-dioctylbenzo [l, 3] phenanthroline-1,3,6,8 (2H, 7H) -tetraone (1 g, 1.54 mmol) was added to a 100 mL two- (1.13 g, 3.85 mmol), tetrakis (triphenylphosphino) -palladium [Pd (2, 2'-bithiophen-5-yl) -4,4,5,5-tetramethyl- 1,3,2- dioxaborolane PPh ₃ ] ₄ ] (0.05 g, 0.05 mmol) and toluene (20 mL) were added and stirred for 30 minutes under a nitrogen stream. 4 mL of 2M K ₂ CO ₃ was slowly added and reacted at 85 ^° C for 24 hours. After the reaction was completed, the reaction mixture was extracted with dichloromethane and separated by column chromatography (eluent: dichloromethane / hexane = 3/1) to obtain a dark blue solid 4,9-di ([2,2'-bithiophen] -dioctylbenzo [lmn] [3,8] phenanthroline -1,3,6,8 (2 H, 7 H) to give the -tetraone (1.08 g, 86%) . The prepared compound can be analyzed by ¹ H NMR and mass spectrum.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.78 (s, 2H), 7.37-7.31 (m, 8H), 7.14-7.11 (m, 2H), 4.16-4.11 (t, 4H), 1.77- 1.65 (m, 4H), 1.41-1.30 (m, 20H), 0.92-0.91 (t, 6H); HR-MS (EI) m / z calcd for C 46 H 46 N 2 O 4 S 4 (M +): 818.2340; found 818.2342.

The prepared compounds exhibited physical properties as shown in the following table.

[Example 2]

4,9-bis (benzo [ b ] thiophen-2-yl) -2,7-dioctylbenzo [m] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H ) -tetraone

2,7-dioctylbenzo [l, 3] phenanthroline-1,3,6,8 (2H, 7H) -tetraone (1 g, 1.54 mmol) was added to a 100 mL two- benzo [b] thiophen-2- ylboronicacid (0.69g, 3.86mmol), tetrakis (triphenylphosphino) palladium [Pd (PPh 3) 4] (0.05g, 0.05mmol), put the toluene (20mL) for 30 minutes in a nitrogen atmosphere After stirring, 4 mL of 2M K ₂ CO ₃ is slowly added and reacted at 85 ^° C for 24 hours. After the reaction was completed, the reaction mixture was extracted with dichloromethane and separated by column chromatography (eluent: dichloromethane / hexane = 2/1) to obtain an indigo solid of 4,9-bis (benzo [ b ] thiophen- lmn] to give the [3,8] phenanthroline-1,3,6,8 (2 H, 7 H) -tetraone (0.99 g, 85%). The prepared compound can be analyzed by ¹ H NMR and mass spectrum.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.84 (s, 2H), 7.98-7.92 (m, 4H), 7.50-7.46 (m, 6H), 4.13-4.08 (t, 4H), 1.74- 1.64 (m, 4H), 1.36-1.29 (m, 20H), 0.91-0.86 (t, 6H); HR-MS (EI) m / z calcd for C ₄₆ H ₄₆ N ₂ O ₄ S ₂ (M ⁺ ): 754.2899; found 754.2898.

The prepared compounds exhibited physical properties as shown in the following table.

[Example 3]

5,5 '- (2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [m] [3,8] phenanthroline-4,9-diyl ) Synthesis of bis (thiophene-2-carbonitrile)

2 gu 100mL round bottom flask, 4,9-bis (5-bromothiophen- 2-yl) -2,7-dioctylbenzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H, 7 H ) -tetraone (0.58 g, 0.71 mmol), cyanocopper (0.64 g, 7.14 mmol) and 20 mL of DMF were added, and the mixture was refluxed at 150 ^° C. After the reaction was completed, the solvent was removed, and the mixture was extracted with chloroform. The extract was subjected to column chromatography (dichloromethane) to obtain a yellow solid 5,5 '- (2,7-dioctyl-1,3,6,8-tetraoxo-1 , 2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4,9-diyl) bis (thiophene-2-carbonitrile) was obtained (0.4 g, 80%). The prepared compound could be analyzed by ¹ H NMR.

_{^{1 HNMR (300MHz, CD 2 Cl}} 2, δ): 8.73 (s, 2H), 7.78-7.76 (d, 2H), 7.27-7.26 (d, 2H), 4.13-4.08 (t, 4H), 1.69-1.67 (m, 4H), 1.36-1.30 (m, 20H), 0.91-0.88 (t, 6H).

The prepared compounds exhibited physical properties as shown in the following table.

[Example 4]

5,5 '- (2,7-bis (2-decyltetradecyl) -1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [m] [3,8] phenanthroline- 4,9-diyl) bis (thiophene-2-carbonitrile)

To a 100 mL 2-necked round bottom flask was added 4,9-bis (5-bromothiophen-2-yl) -2,7-bis (2-decyltetradecyl) benzo [1nn] [3,8] phenanthroline- (2 H , 7 H ) -tetraone (1 g, 0.79 mmol), cyanocopper (0.21 g, 2.38 mmol) and 20 mL of DMF were added and refluxed at 150 ^° C. After the reaction was completed, the solvent was removed and the reaction mixture was extracted with dichloromethane and then separated by column chromatography (eluent: dichloromethane / hexane = 2/1) to obtain a yellow solid 5,5 '- (2,7- bis (2-decyltetradecyl) 1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4,9-diyl) bis (thiophene-2-carbonitrile) 0.6 g, 66%). The prepared compound could be analyzed by ¹ H NMR.

_{^{1 H NMR (300MHz, CD 2}} Cl 2, δ): 8.83 (s, 2H), 7.77-7.75 (d, 2H), 7.27-7.26 (d, 2H), 4.19-4.05 (d, 4H), 1.93 ( m, 2H), 1.26 (m, 80H), 0.92-0.88 (t, 12H).

The prepared compounds exhibited physical properties as shown in the following table.

[Example 5]

2,2 '- ((5,5' - (2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [ 4,9-diyl) bis (thiophene-5,2-diyl)) bis (methanylylene)) dimalononitrile

To a 100 mL 2-necked round bottom flask was added 5,5 '- (2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [ (0.49 g, 0.69 mmol), malononitile (0.11 g, 1.66 mmol), dichloromethane (10 mL) and piperidine (1 drop) were added to the reaction mixture and reacted at room temperature for 3 hours. (5,5 '- (2,7-dioctyl-1,3,6,8-tetraoxo (2-ethylhexyloxy) ethyl) acetate was obtained by extracting with dichloromethane and separating by column chromatography (eluent: hexane / ethyl acetate = Bis (thiophene-5,2-diyl)) bis (methanylidene)) dimalononitrile was obtained 0.22 g, 40%). The prepared compound could be analyzed by ¹ H NMR. _{^{1 HNMR (300MHz, CD 2 Cl}} 2, δ): 8.74 (s, 2H), 7.72 (s, 2H), 7.63-7.61 (d, 2H), 7.33-7.31 (d, 2H), 4.13-4.08 (t , 4H), 1.72-1.67 (m, 4H), 1.37-1.30 (m, 20H), 0.92-0.88 (6H).

The prepared compounds exhibited physical properties as shown in the following table.

Claims (10)

1. An organic semiconductor compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ are independently from each other selected from (C ₁ -C 50) hydroxyalkyl, (C 1 -C 50) alkoxy and (C 1 -C 50) alkyl;
Z ₁ to Z ₄ are each independently selected from hydrogen or the following structure;

In the above structure,
Y is O, S, or Se;
X is hydrogen, halogen, cyano

or

ego,
A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl;
n is an integer of 1 to 3; delete The method according to claim 1,
Wherein R ₁ and R ₂ are independently of each other (C 5 -C 30) hydroxyalkyl, (C 5 -C 30) alkoxy or (C 5 -C 30) alkyl. The method according to claim 1,
An organic semiconductor compound selected from the following structures.

In the above structure,
R ₁ and R ₂ are independently from each other selected from (C 5 -C 30) hydroxyalkyl, (C 5 -C 30) alkoxy and (C 5 -C 30) alkyl;
X is a cyano group;
n is an integer of 1 to 3; The method according to claim 1,
An organic semiconductor compound selected from the following structures.

Reacting the following formula (11) with CuCN to prepare the compound of formula (12).
(11)

[Chemical Formula 12]

In the above formulas (11) and (12)
R ₁ and R ₂ are independently from each other selected from (C 5 -C 30) hydroxyalkyl, (C 5 -C 30) alkoxy and (C 5 -C 30) alkyl;
D is halogen;
Y is O, S, or Se. The method according to claim 6,
(3) and (4) to prepare a compound of formula (5), followed by halogenation
(11).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

(11)

In the above formulas (3), (4), (5) and (11)
R _1, R _2, and R < _{101 &} Are independently selected from (C5-C30) hydroxyalkyl, (C5-C30) alkoxy and (C5-C30) alkyl;
D is halogen;
Y is O, S or Se. Reacting Formula (3) with Formula (21) to prepare Formula (22).
(3)

[Chemical Formula 21]

[Chemical Formula 22]

In the above formulas (3), (21) and (22)
R ₁ and R ₂ is Are independently selected from (C5-C30) hydroxyalkyl, (C5-C30) alkoxy and (C5-C30) alkyl;
D is halogen;
Y is O, S, or Se;
X is hydrogen, halogen, (C2-C50) heteroaryl, cyano, aldehyde,

And

And A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl;
n is an integer from 1 to 3;
E is -B (OH) _2, BFK _3,

,

or

to be. Reacting a compound represented by the formula (22) and a compound represented by the formula (23).
[Chemical Formula 22]

(23)

(31)

In Formulas 22 and 31,
R ₁ and R ₂ is Are independently selected from (C5-C30) hydroxyalkyl, (C5-C30) alkoxy and (C5-C30) alkyl;
X is hydrogen, halogen, (C2-C50) heteroaryl, cyano, carboxylic acid group,

And

And A ₁ and A ₂ may be further substituted with one or more substituents independently selected from halogen, cyano group and (C 1 -C 10) alkyl;
n is an integer from 1 to 3;
In formula (23)
R < ₅ > is (C1-C10) alkyl;
Y is O, S or Se. An organic electronic device comprising an organic semiconductor compound according to any one of claims 1 to 5.

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