WO2015012456A1 - Novel electron-acceptor-donor-acceptor type naphthalene diimide small molecules and an organic electronic device using same - Google Patents

Abstract

An organic semiconductor compound of the present invention can be made into a novel naphthalene diimide derivative compound in which an electron donor compound is introduced between two naphthalene diimides. In addition, the organic semiconductor compound of the present invention, which is synthesized from the naphthalene diimide derivative and unsubstituted or substituted thiophene containing sulfur (S), exhibits a low energy band gap, and thus an organic electronic device comprising the same is highly efficient. In addition, the organic semiconductor compound of the present invention may be an organic semiconductor material in which the thermal stability and physical properties are excellent and the interaction between molecules is high, thereby exhibiting excellent electrical properties. Thus, the organic semiconductor compound of the present invention can be used for all of various organic electronic devices including an organic thin film semiconductor transistor.

Description

A Novel Molecule of Naphthalene Diimide of Novel Electronic Drag-Cell-Drag Type and Organic Electronic Device Using the Same

The present invention relates to an organic semiconductor compound and an organic electronic device comprising the same, and more particularly, to an organic semiconductor compound having an electron donor substituent introduced between a naphthalene diimide derivative or two naphthalene diimide derivatives. It is about.

Organic semiconductor materials, in particular organic semiconductor materials that are soluble in organic solvents and can be applied to large areas by much less expensive processes such as spin-coating, dip-coating and microcontact printing, are simpler to process. In addition, organic materials can be deposited at lower temperatures, allowing the development of a wide range of substrate materials, including plastics for soluble electronics. Therefore, thin film transistors made of organic materials can be used to verify the memory circuitry and identity of plastic circuits in display drivers, portable computers, radio call receivers, commerce cards, where ease of manufacture, mechanical availability and / or proper operating temperature are important considerations. It can be considered as a potential key technology in tags. Therefore, organic thin film transistors (OTFTs) are currently subject to intensive research activities due to the low manufacturing cost, large size, and the possibility of manufacturing flexible electronic devices. The components of the organic thin film transistor include electrodes (source and drain), substrates and gate electrodes requiring high thermal stability, insulators having high insulation and dielectric constant, and semiconductors that transfer charges well. There are many problems to overcome, and the key material is organic semiconductor. Organic semiconductors can be classified into low molecular organic semiconductors and high molecular organic semiconductors according to molecular weight, and are classified into n-type organic semiconductors or p-type organic semiconductors according to whether electrons or holes are transferred. In general, in the case of using a low molecular organic semiconductor when forming the organic semiconductor layer, the low molecular organic semiconductor is easy to purify and can almost remove impurities, and thus has excellent charge transfer characteristics. In addition, aromatic tetracarboxylic diimides based on naphthalene aromatic skeletons are n-type semiconductors, and have an n-channel mobility of 0.16 cm ² / Vs or less using a device in a top-contact configuration in which a source electrode and a drain electrode are present on the semiconductor. Proven to provide. Accordingly, various 1,4,5,8-naphthalene tetracarboxylic acid diimides have been produced and used for n-type semiconductors. However, there is still a need for the development of new and improved naphthalene tetracarboxylic acid diimide derivative compounds for transistor materials with good electrical properties.

The present invention is to provide an organic semiconductor compound having solubility and excellent electrical properties.

In another aspect, the present invention is to provide an organic electronic device comprising an organic semiconductor compound of the present invention.

The present invention relates to a naphthalene diimide derivative or a derivative compound in which an electron donor substituent is introduced between two naphthalene diimide compounds. The present invention relates to an organic electronic device including the same. .

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₂ are each independently selected from (C1-C50) alkyl, (C1-C50) hydroxyalkyl, (C1-C50) alkoxy and (C6-C30) aryl;

A ₁ to A _4, L ₁ to L ₄ are independently hydrogen, halogen, (C1-C50) alkyl, cyano, and To is selected from the structures from one another;

V ₁ and V ₂ are

or

Is;

Z ₁ to Z ₁₈ are independently of each other S, Se, O, N, NH or NR ′;

A ₁₁ and A ₁₂ are independently of each other hydrogen, cyano, (C 1 -C 50) alkyl, (C 1 -C 50) alkoxy or —COOR ”;

R 'and R "independently of one another are (C1-C50) alkyl or (C6-C50) aryl;

R ₃ to R ₅₉ independently of one another are hydrogen, hydroxy group, amino, (C 1 -C 50) alkyl, (C 6 -C 50) aryl, (C 3 -C 50) heteroaryl, (C 1 -C 50) alkoxy, mono or di ( C1-C50) alkylamino, (C1-50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy, said aryl and heteroaryl being further substituted with (C1-C50) alkyl or (C1-C50) alkoxy Can be;

l, m, n, o and p are each independently an integer from 0 to 3.]

The present invention relates to organic semiconductor compounds for organic electronic devices such as organic thin film transistors (OTFTs) and their use. More specifically, the present invention relates to a novel n-type organic semiconductor compound, a naphthalene diimide derivative compound and an organic electronic device using the same as an organic semiconductor layer by introducing an electron donor substituent between two naphthalene diimide compounds.

Introduced between two naphthalene diimide compounds of Formula 1 according to an embodiment of the present invention

The phosphorus electron donor substituent may be an organic semiconductor compound selected from the following structures.

In the above structural formula,

Z ₁ to Z ₄ are independently S, Se, O, N, NH or NR ', and each other;

A ₁₁ and A ₁₂ are independently hydrogen, cyano, (C1-C50) alkyl, (C1-C50) alkoxy or -COOR "of each other;

R 'and R "independently of one another are (C1-C50) alkyl or (C6-C50) aryl;

R ₃ to R ₈ independently of one another are hydrogen, hydroxy group, amino, (C1-C50) alkyl, (C6-C50) aryl, (C3-C50) heteroaryl, (C1-C50) alkoxy, mono or di ( C1-C50) alkylamino, (C1-50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy, said aryl and heteroaryl being further substituted with (C1-C50) alkyl or (C1-C50) alkoxy Can be.

The organic semiconductor compound of the present invention can improve the electron density of the naphthalene diimide by substitution with a derivative such as the above structural formula to increase the intermolecular interaction and exhibit high mobility.

More specifically, it is introduced between the two naphthalene diimide compounds of Formula 1

The phosphorus electron donor substituent may be an organic semiconductor compound selected from the following structures.

More specifically, R ₁ and R ₂ of Formula 1 may be an organic semiconductor compound that is independently (C ₁ -C 30) alkyl. In more detail, the organic semiconductor compound of the present invention was able to improve solubility and improve electronic properties by substituting an alkyl group rather than an aryl group for an imide group.

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

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 was able to prepare a novel naphthalene diimide derivative compound through the reaction of the naphthalene diimide derivative and the electron donor or electron drag compound.

In addition, the organic semiconductor compound of the present invention is a compound prepared by synthesizing with an unsubstituted or substituted thiophene containing a naphthalene diimide derivative and sulfur (S) has a low band gap, the organic electronic device comprising the Has efficiency.

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

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

Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include all linear or pulverized forms. In addition, "aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms, as appropriate. It includes a ring system, a form in which a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. The "heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si, and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. It means an aryl group which is a 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond.

Hereinafter, the present invention will be described in detail by way of examples. However, the following Preparation Examples and Examples are only for illustrating the present invention, and the content of the present invention is not limited by the following Examples.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

(Manufacture example 1) 4,9-dibromoisochromeno [6,5,4-def] isochromen- 1,3, 6,8-tet Rawon  synthesis

In a 500 mL three neck round bottom flask, add isochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone (17.60 g, 65.64 mmol) and dissolve in 100 mL of oleum. In another 500 mL three-neck round bottom flask, add 1,3-dibromo-1,3,5-triazinane-2,4,6-trione (18.83 g, 65.64 mmol) and dissolve in oleum (50 mL). After stirring for 1 hour at room temperature, 1,3-dibromo-1,3,5-triazinane-2,4,6-trione dissolved in oleum 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 1000mL beaker, pour the reaction and stir for at least 1 hour. After washing with water several times, washed with methanol, filtered and dried to obtain 4,9-dibromoisochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone as a light green solid (26 g, 94%). The prepared compound could be analyzed by ¹ H NMR and IR.

¹ H NMR (300 MHz, CDCl ₃ , δ): 8.71 (s, 2H); IR (KBr, cm ⁻¹ ): 1786,1746.

Preparation Example 2 4,9-Dibromo-2,7-dioctylbenzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H Tetraone Synthesis

4,9-dibromoisochromeno [6,5,4-def] isochromene-1,3,6,8-tetraone (9.50 g, 22.30 mmol) was added to a 500 mL three-neck round bottom flask, and dissolved in 200 mL of acetic acid, glacial. Octylamine (14.78 mL, 89.21 mmol) was added thereto. After reacting at 130 ° C. for 1 hour, water was added to the reaction vessel, stirred, washed with water, and filtered. Column chromatography (eluent: dichloromethane / hexane = 1/1) gave an ivory solid, 4,9-dibromo-2,7-dioctylbenzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H ) -tetraone was obtained (2.9 g, 20%). The prepared compound could be analyzed by ¹ H NMR.

¹ H NMR (300 MHz, CDCl ₃ , δ): 9.02 (s, 2H), 4.23-4.18 (t, 4H), 1.78-1.73 (m, 4H), 1.44-1.30 (m, 20H), 0.92-0.88 ( t, 6H)

Preparation Example 3 9-Bromo-2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8 ] Synthesis of phenantronin-4-carbonitrile

4,9-dibromo-2,7-dioctybenzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H ) -tetraone (10.54 g, 16.37 in a 250 mL three-neck round bottom flask mmol), add 160 mL of DMF, and heat at 100 ° C. for 1 hour. Put cyanocopper (0.8 g, 9.01 mmol) in a 100 mL three neck round bottom flask and add 20 mL of DMF to dissolve at room temperature. Take the dissolved cyanocopper with a syringe and slowly add it to the reaction vessel containing 4,9-dibromo-2,7-dioctylbenzo [lmn] [3,8] phenanthroline-1,3,6,8 (2 H , 7 H ) -tetraone. Inject and react for 1 hour. Extraction with dichloromethane followed by column chromatography (eluent: dichloromethane / hexane = 5/1) gave the ivory solid 9-bromo-2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6, 7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4-carbonitrile was obtained (2.8 g, 29%).

¹ HNMR (300MHz, CD ₂ Cl ₂ ,): 9.06 (s, 1H), 9.02 (s, 1H), 4.25-4.19 (t, 4H), 1.81-1.71 (m, 4H), 1.42-1.30 (m, 20H), 0.92-0.90 (t, 6H)

(Manufacture example 4) ( E Synthesis of) -1,2-bis (thiophen-2-yl) ethene

Add thiophen-2-carbaldehyde (5.6 g, 50 mmol) to the flask, dissolve in tetrahydrofuran (THF) (100 mL), lower the temperature to -18 ° C, and titanium (IV) chloride (6.5 mL) for 30 minutes. While slowly dropping. After stirring for 30 minutes, zinc powder (7.8 g) is added over 30 minutes. After stirring at −18 ° C. for 30 minutes, the temperature was raised to room temperature and refluxed for 3 hours 30 minutes. Then pour iced water to terminate the reaction, filter the inorganics with water, wash with methylene chloride, extract, remove the water and recrystallize with hexane to give yellow solid ( E ) -1,2-bis (thiophen-2-yl) ethene. Was obtained (4.7 g, 98%).

¹ HNMR (300 MHz, CDCl ₃ , δ): 7.18 (d, 2H), 7.05 (s, 2H), 7.04 (d, 2H), 6.99 (m, 2H).

(Manufacture example 5) ( E Synthesis of) -1,2-bis (5- (trimethylstannyl) thiophen-2-yl) ethene

A flask (E) -1,2- bis (thiophen-2-yl) ethene (1.78 g, 9.6 mmol) was dissolved in a mixture of tetra hydro furan / hexane (volume ratio of 2/1, 50 mL), 2 mol Of cyclohexane with n-butyllithium (11 ml, 22 mmol) was slowly added at -78 ° C and stirred for 30 minutes. After raising to room temperature and reacting for 1 hour, the reaction temperature is lowered to -78 ° C. At the same temperature, tetrahydrofuran (22 mL, 22 mmol) in which 1 mol of trimethyltin chloride is dissolved is slowly added dropwise to the reaction, followed by stirring at room temperature for 2 hours. Extract with ether, remove moisture with anhydrous magnesium sulfate, concentrate the solvent and recrystallize with ethanol to give white needle-like ( E ) -1,2-bis (5- (trimethylstannyl) thiophen-2- I) ethene was obtained (3.88 g, 80%).

¹ H NMR (300 MHz, CDCl ₃ , δ): 7.11 (d, 2H), 7.08 (s, 2H), 7.07 (d, 2H), 0.36 (s, 18H).

Example 1 9,9 '-([2,2'-bithiophene] -5,5'-diyl) bis (2,7-dioctyl-1,3,6,8-tetraoxo- 1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenantronin-4-carbonitrile)

9-bromo-2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline in a 100 mL two-neck round bottom flask 4-carbonitrile (1.02 g, 1.72 mmol) and 5,5'-bis (trimethylstannyl) -2,2'-bithiophene (0.34 g, 0.69 mmol), Pd (PPh ₃ ) ₄ (0.02 g, 0.02 mmol), 20mLtoluene was added and then reacted at 85 ° C. for 24 hours under a stream of nitrogen. Extracted with chloroform, and then purified by column chromatography (eluent: dichloromethane / hexane = 5/1) to give a dark solid 9,9 '-([2,2'-bithiophene] -5,5'-diyl) bis (2,7- dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4-carbonitrile) (0.71 g, 86%).

¹ H NMR (300MHz, CD ₂ Cl ₂ ,): 9.01 (s, 2H), 8.89 (s, 2H), 7.45 (s, 4H), 4.25-4.17 (m, 8H), 1.80-1.75 (m, 8H ), 1.33-1.31 (m, 40H), 0.92-0.90 (t, 12H).

(Example 2) ( E ) -9,9 '-(5,5'-(ethene-1,2-diyl) bis (thiophen-5,2-diyl)) bis (2,7-dioctyl-1,3,6 , 8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenantronin-4-carbonitrile)

9-bromo-2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline in a 100 mL two-neck round bottom flask 4-carbonitrile (0.2 g, 0.34 mmol) and ( E ) -1,2-bis (5- (trimethylstannyl) thiophen-2-yl) ethene (0.07g, 0.13mmol), Pd (PPh ₃ ) ₄ (0.005 g, 0.004 mmol) and 10 mL toluene were added and then reacted at 85 ° C. for 24 hours under a nitrogen stream. Extracted with chloroform, and then purified by column chromatography (eluent: dichloromethane) to give ( E ) -9,9 '-(5,5'-(ethene-1,2-diyl) bis (thiophene-5,2-diyl) ) bis (2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4-carbonitrile) was obtained. g, 63%).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ): 8.99 (s, 2H), 8.86 (s, 2H), 7.40-7.39 (d, 2H), 7.21-7.16 (d, 2H), 4.26-4.13 (m, 8H), 1.84-1.68 (m, 8H), 1.44-1.30 (m, 40H), 0.91-0.88 (m, 12H).

Example 3 9,9 '-(1,5-dimethoxynaphthalene-2,6-dil) bis (2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3 , 6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4-carbonitrile)

9-bromo-2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline in a 100 mL two-neck round bottom flask 4-carbonitrile (0.4 g, 0.67 mmol) and 2,2 '-(1,5-dimethoxynaphthalene-2,6-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (0.14g, 0.32mmol), Pd (PPh ₃ ) ₄ (0.01g, 0.01mmol), 5mL toluene and 2mL THF were added, followed by stirring for 30 minutes under a nitrogen stream, followed by 2M K ₂ CO ₃ , followed by 85 ° C. React for 48 hours. Extracted with chloroform, and then purified by column chromatography (eluent: chloroform) to give 9,9 '-(1,5-dimethoxynaphthalene-2,6-diyl) bis (2,7-dioctyl-1,3,6,8) as a red solid. -tetraoxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline-4-carbonitrile) (0.41 g, 50%).

¹ H NMR (300 MHz, CDCl ₃ ): 9.06 (s, 2H), 8.86 (s, 2H), 8.04 (d, 2H) 7.74 (d, 2H), 4.28-4.10 (m, 8H), 3.80 (s , 6H), 1.81 (m, 8H), 1.61 (m, 40H), 0.87 (t, 12H), FT-IR (KBr, cm ^-1 ): 3100 (aromatic CH str), 2955-2895 (aliphatic CH str ), 2254 (CN), 1719-1652 (C = O)

Claims (6)

1. An organic semiconductor compound represented by the following formula (1).

   [Formula 1]

   

   In Chemical Formula 1,

   R ₁ and R ₂ are each independently selected from (C1-C50) alkyl, (C1-C50) hydroxyalkyl, (C1-C50) alkoxy and (C6-C30) aryl;

   A ₁ to A _4, L ₁ to L ₄ are each independently selected from hydrogen, halogen, (C 1 -C 50) alkyl, cyano and the following structures;

   

   V ₁ and V ₂ are

   

   or

   

   Is;

   Z ₁ to Z ₁₈ are independently of each other S, Se, O, N, NH or NR ′;

   A ₁₁ and A ₁₂ are independently of each other hydrogen, cyano, (C 1 -C 50) alkyl, (C 1 -C 50) alkoxy or —COOR ”;

   R 'and R "independently of one another are (C1-C50) alkyl or (C6-C50) aryl;

   R ₃ to R ₅₉ independently of one another are hydrogen, hydroxy group, amino, (C 1 -C 50) alkyl, (C 6 -C 50) aryl, (C 3 -C 50) heteroaryl, (C 1 -C 50) alkoxy, mono or di ( C1-C50) alkylamino, (C1-50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy, said aryl and heteroaryl being further substituted with (C1-C50) alkyl or (C1-C50) alkoxy Can be;

   l, m, n, o and p are each independently an integer from 0 to 3.]
2. The method of claim 1,

   Of Formula 1

   

   Is an organic semiconductor compound selected from the following structures.

   

   In the above structural formula,

   Z ₁ to Z ₄ are each independently S, Se, O, N, NH or NR ';

   A ₁₁ and A ₁₂ are independently of each other hydrogen, cyano, (C 1 -C 50) alkyl, (C 1 -C 50) alkoxy or —COOR ”;

   R 'and R "independently of one another are (C1-C50) alkyl or (C6-C50) aryl;

   R ₃ to R ₈ are independently from each other hydrogen, hydroxyl, amino, (C1-C50) alkyl, (C6-C50) aryl, (C3-C50) heteroaryl, (C1-C50) alkoxy, mono- or di ( C1-C50) alkylamino, (C1-50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy, said aryl and heteroaryl being further substituted with (C1-C50) alkyl or (C1-C50) alkoxy Can be.
3. The method of claim 1,

   Of Formula 1

   

   Is an organic semiconductor compound selected from the following structures.

   

   

   
4. The method of claim 1,

   In Chemical Formula 1, R ₁ and R ₂ are independently of each other (C1-C30) alkyl.
5. The method of claim 1,

   The organic semiconductor compound selected from the following structures.

   

   

   

   
6. An organic electronic device comprising the organic semiconductor compound according to any one of claims 1 to 5.