KR101356941B1 - New compounds and organic electronic device using the same - Google Patents

Abstract

The present invention relates to a novel compound having a substituted pyrene structure and an organic electronic device using the same. The compound according to the present invention is an organic electronic device containing at least one layer of the compound according to the present invention alone or as a component of a mixture in an organic electronic device including an organic light emitting device. Excellent properties in terms of voltage and lifetime.

Compounds, organic electronic devices, organic light emitting devices, organic light emitting device materials

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic electronic device using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a novel compound and an organic electronic device using the same.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires the exchange of holes and / or electrons between the electrode and the organic semiconductor material. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Is an electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with the electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. These devices include an electron / hole injecting material, an electron / hole extracting material, Materials or luminescent materials. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently achieved, and therefore, the development of new materials has been continuously required.

The present inventors have found a compound having a novel structure. In addition, when the organic compound layer of the organic electronic device is formed using the novel compound, it has been found that the organic compound layer can exhibit the effects of increasing the efficiency of the device, lowering the driving voltage, and increasing the stability.

Accordingly, an object of the present invention is to provide a novel compound and an organic electronic device using the same.

The present invention provides a compound represented by the following formula (1).

In Formula 1,

R 'and R "are the same as or different from each other, and each independently, a deuterium atom; a C ₁ to C ₆ alkyl group; a cyano group; a fluorine atom; a C ₆ to C ₂₀ aryl group; a C ₅ to C ₁₂ cycloalkyl group C ₁ to C ₂₀ alkoxy group C ₆ to C ₃₀ arylamine group C ₃ to C ₃₀ heteroaryl group including N, O or S; or -Si (Z 1) (Z 2) (Z 3) ego,

R1 and R2 are the same as or different from each other, and each independently hydrogen atom; Deuterium atoms; An alkyl group having ₁ to ₆ carbon atoms; Cyano; A fluorine group; A C ₆ to C ₂₀ aryl group; A cycloalkyl group of C ₅ ~ C _12; C ₃ ~ C ₃₀ Heteroaryl group containing N, O or S; Or an arylamino group of C ₆ ~ C ₂₀ ,

Ar1 and Ar2 are the same as or different from each other, and each independently a C ₆ to C ₂₀ aryl group substituted with a deuterium atom, a fluorine atom, or -Si (Z ₁ ) (Z ₂ ) (Z ₃ ); Or a C ₃ to C ₃₀ heteroaryl group which is substituted with a deuterium atom, a fluorine atom or —Si (Z 1) (Z 2) (Z 3) and includes N, O or S,

Z1, Z2 and Z3 are the same as or different from each other, and each independently a hydrogen atom, an alkyl group of C ₁ to C ₆ or an aryl group of C ₆ to C ₂₀ ,

n and m are the same as or different from each other, and each independently an integer of 0 to 5, when n or m is an integer of 2 or more, the two or more R1 or R2 may be the same or different from each other.

In addition,

1) Lithiated to 1,6-dibromopyrene and then reacted with R'X or R "X or by introducing R 'or R" into a 1,6-dibromopyrene under a palladium catalyst Preparing compound B,

2) reacting Compound B with bromine or NBS (N-bromo succinimide) to produce Compound C, and

3) introducing the amine compound represented by the following Formula 2 to the compound C under a palladium catalyst

Wherein R < 1 > and R < 2 >

[Compound B]

[Compound C]

(2)

In the compound B, compound C and formula 2,

R 'and R "are the same as the definition of R' and R" of Formula 1, R is the same as the definition of R1 and R2 of Formula 1, and Ar is the same as the definition of Ar1 and Ar2 of Formula 1 And p is the same as the definition of n and m in Chemical Formula 1,

X is each independently a halogen group.

The present invention also provides an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the novel compound Wherein the organic electronic device is an organic electronic device.

The novel compounds according to the invention can be used as organic layer materials such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials and the like, in particular as light emitting materials. When the compound according to the present invention is used in an organic electronic device including an organic light emitting device using the material of the organic material layer, the driving voltage of the device is lowered, the efficiency is improved, and the life characteristics are excellent.

Hereinafter, the present invention will be described in more detail.

The compound according to the present invention is characterized by being represented by the above formula (1).

In the compound according to the present invention, the substituents of the above formula (1) will be described in more detail as follows.

Examples of the C ₁ to C ₆ alkyl group include a methyl group, an ethyl group, a tert-butyl group, and the like, but are not limited thereto.

Examples of the C ₆ to C ₂₀ aryl group include a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, and a fluorenyl group, but are not limited thereto.

Examples of the C ₅ to C ₁₂ cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.

Examples of the C ₃ to C ₃₀ heteroaryl group containing N, O or S include carbazolyl group, pyridyl group, quinoline group, isoquinoline group, thiophenyl group, furanyl group, imidazole group, oxazolyl group and thiazolyl group , Triazine groups, and the like, but are not limited thereto.

Examples of the C ₁ -C ₂₀ alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.

The C ₆ ~ C ₃₀ arylamine group may include a deuterium atom; An alkyl group having ₁ to ₆ carbon atoms; Cyano; A fluorine group; A C ₆ to C ₂₀ aryl group; A cycloalkyl group of C ₅ ~ C _12; Or an arylamine group unsubstituted or substituted with a C ₃ to C ₃₀ heteroaryl group including N, O or S, but is not limited thereto.

Specific examples of the compound represented by the formula (1) include, but are not limited to, the following compounds.

In addition, the preparation method of the compound represented by Formula 1 according to the present invention is 1) lithiated in 1,6-dibromopyrene and reacted with R'X or R''X, or 1,6-di Preparing compound B by introducing R 'or R "into bromopyrene under a palladium catalyst, 2) preparing compound C by reacting compound B with bromine or N-bromo succinimide (NBS), And 3) introducing the amine compound represented by Chemical Formula 2 into the compound C under a palladium catalyst.

In the method for preparing a compound represented by Formula 1 according to the present invention, the introduction of R 'or R "into 1,6-dibromopyrene under the palladium catalyst of step 1) includes R' or R" It may be carried out using an arylboronic acid compound or a heteroarylboronic acid compound, but is not limited thereto.

Compound represented by the formula (1) according to the present invention enables fine adjustment of the energy bandgap by introducing a suitable substituent as described above, while improving the properties at the interface between the organic material and the use of the material Can be varied.

On the other hand, the compound represented by the formula (1) has a high glass transition temperature (Tg) and is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

Further, the organic electronic device according to the present invention is an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers And a compound represented by the above formula (1).

The organic electronic device of the present invention can be produced by a conventional method and materials for producing an organic electronic device, except that one or more organic compound layers are formed using the above-described compounds.

The compound represented by Chemical Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method in the manufacture of an organic electronic device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic electronic device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic electronic device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and the like as an organic material layer. However, the structure of the organic electronic device is not limited to this, and may include a smaller number of organic layers.

Therefore, in the organic electronic device of the present invention, the organic material layer may include a hole injection layer and a hole transport layer, the hole injection layer or hole transport layer may include a compound represented by the formula (1).

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include a compound represented by the general formula (1).

In the organic compound layer having such a multi-layer structure, the compound represented by Formula 1 may be included in a light emitting layer, a layer that simultaneously transports and injects holes, a layer that simultaneously transports light and emits light, or a layer that simultaneously transports electrons and emits light have.

In particular, the organic electronic device according to the present invention includes a light emitting layer, it is more preferable that the compound represented by the formula (1) is included in the light emitting layer.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in Figs. 1 to 4, but is not limited thereto.

FIG. 1 illustrates a structure of an organic light emitting device in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound represented by Chemical Formula 1 may be included in the emission layer 105.

2 illustrates a structure of an organic light emitting device in which an anode 102, a hole injection / hole transporting and light emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound represented by Chemical Formula 1 may be included in the hole injection / hole transport or light emitting layer 105.

3 shows a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting and emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked. . In such a structure, the compound represented by Chemical Formula 1 may be included in the hole injection / hole transport or light emitting layer 105.

4 shows a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially laminated. . In such a structure, the compound represented by Chemical Formula 1 may be included in the electron transport or light emitting layer 105.

For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymeric materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

Accordingly, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic phosphor device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

Hereinafter, the method for preparing the compound represented by the formula (1) of the present invention, the method for producing the organic electronic device using the same, and the performance will be described in detail. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited by the following examples.

The evaluation method in the examples is as follows.

1. Driving voltage: measured using Kethley 236 (source measure unit)

2. Current efficiency: measured using SpectraScan Pr-650

3. Color Coordinates: Measured using SpectraScan Pr-650

The compound represented by formula (1) according to the present invention can be generally prepared by a multistage chemical reaction. That is, some of the intermediate compounds are first prepared, and the compounds of formula (1) are prepared from the intermediate compounds. Exemplary intermediate compounds are the compounds shown in the table below.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

< Synthetic example >

< Synthetic example  1-1> Preparation of Compound B-1

1,6-dibromopyrene (1,6-dibromopyrene, 7.2 g, 20.0 mmol) was put in anhydrous THF (100 mL) under nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 9.6 mL, 24 mmol) was added dropwise to the reaction solution, stirred for about 40 minutes, and then chlorotrimethylsilane (3.3 g, 30 mmol) was added to the reaction mixture and stirred. After about 1 hour to warm to room temperature and stirred for 3 hours at room temperature. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. After drying the organic layer with anhydrous magnesium sulfate, ethyl ether was added and stirred to prepare a solid compound B-1 (4.2 g, 61%).

MS: [M + H] ⁺ = 347

< Synthetic example  1-2> Preparation of Compound B-2

In the preparation of Compound B-1 of Synthesis Example 1-1, Compound B-2 was prepared by the same method except that compound methyliodide was used instead of compound chlorotrimethylsilane. .

MS: [M + H] ⁺ = 231

< Synthetic example  1-3> Preparation of Compound B-3

1,6-dibromopyrene (10.8-dibromopyrene, 10.8 g, 31.2 mmol) and phenyl boronic acid (9.5 g, 78.0 mmol) were dissolved in anhydrous THF (300 mL), followed by Pd (PPh ₃ ) ₄ ( 0.52 g, 0.45 mmol) and 120 mL of a 2M K ₂ CO ₃ / H ₂ O aqueous solution were added and refluxed for 3 hours. Distilled water was added to the reaction solution, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with CH ₂ Cl ₂ / EtOH to prepare compound B-3 (6.4 g, yield 58%).

MS: [M + H] ⁺ = 355

< Synthetic example  1-4> Preparation of Compound B-4

1,6-dibromopyrene (1,6-dibromopyrene, 4 g, 11.1 mmol) was dissolved in 5-phenylthiophene-2-boronic acid (5.7 g, 27.8 mmol) in anhydrous THF (150 mL), and then Pd (PPh ₃ ) ₄ (0.26 g, 0.23 mmol) and 120 mL of 2M K ₂ CO ₃ / H ₂ O aqueous solution were added and refluxed for 3 hours. Distilled water was added to the reaction solution, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with CH ₂ Cl ₂ / EtOH to prepare compound B-4 (4.1 g, 72% yield).

MS: [M + H] ⁺ = 519

< Synthetic example  1-5> Preparation of Compound B-5

In the preparation of Compound B-4 of Synthesis Example 1-4, except that compound 5-methylthiophene-2-boronic acid was used instead of compound 5-phenylthiophene-2-boronic acid, Compound B-5 (7.9 g, yield 67%) was prepared.

MS: [M + H] &lt; ⁺ &gt; = 395

< Synthetic example  1-6> Preparation of Compound B-6

In the preparation of Compound B-4 of Synthesis Example 1-4, except that Compound 1-cycloboronic acid was used instead of Compound 5-phenylthiophene-2-boronic acid, Compound B-6 ( 5.3 g, yield 89%) was prepared.

MS: [M + H] ⁺ = 367

< Synthetic example  2-1> Preparation of Compound C-1

Compound B-1 (4.2 g, 12.2 mmol) was dissolved in chloroform (120 mL), and N-bromo succinimide (4.3 g, 24.4 mmol) was added, followed by stirring at room temperature for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with toluene to obtain compound C-1 (4.1 g, yield 67%).

MS: [M] ⁺ = 504

< Synthetic example  2-2> Preparation of Compound C-2

Compound B-2 (4.6 g, 20.0 mmol) was dissolved in chloroform (120 mL), and N-bromo succinimide (7.8 g, 44 mmol) was added, followed by stirring at room temperature for 7 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. The reaction solution was concentrated and recrystallized twice with toluene to obtain compound C-2 (4.3 g, yield 56%).

MS: [M] ⁺ = 388

< Synthetic example  2-3> Preparation of Compound C-3

Compound B-3 (5.3 g, 10.3 mmol) was dissolved in chloroform (150 mL), and N-bromo succinimide (3.6 g, 24.4 mmol) was added, followed by stirring at 40 ° C. for 6 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with toluene to obtain compound C-3 (2.5 g, 47% yield).

MS: [M] ⁺ = 512

< Synthetic example  2-4> Preparation of Compound C-4

Compound B-4 (5.2 g, 10.0 mmol) was dissolved in chloroform (120 mL), and N-bromo succinimide (3.2 g, 22.0 mmol) was added, followed by stirring at room temperature for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with toluene to give compound C-4 (5.1 g, yield 75%).

MS: [M] ⁺ = 676

< Synthetic example  2-5> Preparation of Compound C-5

Compound B-5 (7.9 g, 20.0 mmol) was dissolved in chloroform (120 mL), and N-bromo succinimide (7.8 g, 44 mmol) was added, followed by stirring at room temperature for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. The reaction solution was concentrated and recrystallized twice with toluene to obtain compound C-5 (4.8 g, yield 43%).

MS: [M] ⁺ = 552

< Synthetic example  2-6> Preparation of Compound C-6

Compound B-6 (5.3 g, 14.5 mmol) was dissolved in chloroform (120 mL), and N-bromo succinimide (5.4 g, 30.4 mmol) was added, followed by stirring at room temperature for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. The reaction solution was concentrated and recrystallized twice with toluene to obtain compound C-6 (4.5 g, 59% yield).

MS: [M] ⁺ = 524

< Manufacturing example  1> Preparation of Compound 1-1-1

Compound C-1 (4.5 g, 8.8 mmol), N- (4-fluorophenyl) benzeneamine (N- (4-fluorophenyl) benzenamine (3.6 g, 19.4 mmol) was dissolved in 200 ml of xylene, tert-butoxide (2.5g, 26.5mmol), Pd [ P (t-Bu) 3] 2 0.09g after the addition of (0.17mmol), and reflux was conducted in a nitrogen atmosphere for 5 hours, distilled water was added to the reaction solution, the reaction Normal-hexane / ethyl acetate = 10/1, column separation was carried out, and the mixture was stirred in petroleum ether and dried in vacuo to give compound 1-1-1 (4.2 g, yield 66%). It was.

MS: [M + H] &lt; ⁺ &gt; = 717

< Manufacturing example  2> Preparation of Compound 1-1-3

In Chemical Formula 1-1-1 of Preparation Example 1, Compound C-1 (5.0 g, 9.9 mmol), Compound N- (4-fluorophenyl) benzeneamine (N- (4-fluorophenyl) benzenamine) Except for using N- (3-fluorophenyl) benzeneamine (N- (3-fluorophenyl) benzenamine) (4.0 g, 21.7 mmol) was prepared in the same manner to give the compound 1-1-3 (3.8 g, yield 53%) was prepared.

MS: [M + H] ⁺ = 717

< Manufacturing example  3> Preparation of Compound 1-1-9

In Chemical Formula 1-1-1 of Preparation Example 1, Compound C-1 (4.8 g, 9.5 mmol) and Compound N- (4-fluorophenyl) benzeneamine (N- (4-fluorophenyl) benzenamine) instead of N -(4-fluorophenyl) -4- (trimethylsilyl) benzeneamine (N- (4-fluorophenyl) -4- (trimethylsilyl) benzenamine) (5.5 g, 22.8 mmol) was prepared in the same manner except Compound 1-1-9 (5.2 g, yield 66%) was prepared.

MS: [M + H] ⁺ = 825

< Manufacturing example  4> Preparation of Compound 1-2-9

In Chemical Formula 1-1-9 of Preparation Example 3, Compound C-2 (3.7 g, 9.5 mmol) was used instead of Compound C-1, and N- (4-fluorophenyl) -4- (trimethylsilyl) Compound 1-2-9 (3.7 g, 52% yield) was prepared by the same method using benzeneamine (N- (4-fluorophenyl) -4- (trimethylsilyl) benzenamine) (5.5 g, 22.8 mmol). .

MS: [M + H] ⁺ = 709

< Manufacturing example  5> Preparation of Compound 1-2-10

In Chemical Formula 1-2-9 of Preparation Example 4, Compound C-2 (4.9 g, 12.5 mmol) was used and N- (4-fluorophenyl) -4- (trimethylsilyl) benzeneamine (N- Using 4- (4- (trimethylsilyl) phenylamino) benzonitrile (4- (4- (trimethylsilyl) phenylamino) benzonitrile, 7.2 g, 30.0 mmol) instead of (4-fluorophenyl) -4- (trimethylsilyl) benzenamine) Compound 1-2-10 (5.8 g, yield 63%) was prepared in the same manner.

MS: [M + H] ⁺ = 759

< Manufacturing example  6> Preparation of Compound 1-2-25

In Chemical Formula 1-1-1 of Preparation Example 1, Compound C-3 (5.1 g, 10.0 mmol) was substituted for Compound C-1, and Compound N- (4-fluorophenyl) benzeneamine (N- (4- except that compound N- (4-fluorophenyl) -4- (trimethylsilyl) benzeneamine (N- (4-fluorophenyl) -4- (trimethylsilyl) benzenamine, 6.2 g, 24.0 mmol) was used instead of fluorophenyl) benzenamine). Compound 1-2-25 was prepared by the same method.

MS: [M + H] ⁺ = 869

< Manufacturing example  7> Preparation of Compound 1-2-17

In Chemical Formula 1-1-1 of Preparation Example 1, Compound C-4 (5.1 g, 10.0 mmol) was substituted for Compound C-1, and Compound N- (4-fluorophenyl) benzeneamine (N- (4- Compound 1-2- was prepared by the same method except that 4- (4-fluorophenylamino) benzonitrile (6.2 g, 24.0 mmol) was used instead of fluorophenyl) benzenamine). 17 (6.2 g, 24.0 mmol) was prepared.

MS: [M + H] ⁺ = 939

< Manufacturing example  8> Preparation of Compound 1-2-29

In Chemical Formula 1-1-1 of Preparation Example 1, except that Compound C-5 (5.1 g, 10.0 mmol) was used instead of Compound C-1, Compound 1-2-29 (6.2 g, 24.0 mmol) was prepared.

MS: [M + H] ⁺ = 917

< Manufacturing example  9> Preparation of Compound 1-2-22

In Chemical Formula 1-2-17 of Preparation Example 7, except that Compound C-6 (1.5 g, 2.86 mmol) was used instead of Compound C-4, Compound 1-2-22 (0.97 g, Yield 43%) was prepared.

MS: [M + H] ⁺ = 787

< Comparative Example  1-1>

The glass substrate coated with ITO (indium tin oxide) film with a thickness of 1,500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used. Distilled water, which was filtered by a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. NPB (400 kPa), which is a material for transporting holes, was vacuum-deposited thereon, and then a dopant D1 (4 wt%) was deposited together with the following Compound H1 (300 kPa) to form a light emitting layer.

Compound E1 was vacuum deposited to a thickness of 200 kPa on the light emitting layer to form an electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 의 and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

As a result of applying a forward electric field of 7.6V to the organic light emitting device manufactured above, blue light emission of 3.1 cd / A corresponding to x = 0.154 and y = 0.192 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

< Comparative Example  1-2>

The same experiment was conducted except that Compound D2 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 7.3V to the organic light emitting device manufactured above, blue emission of 3.8 cd / A corresponding to x = 0.153 and y = 0.189 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. It became.

< Experimental Example  1-1>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-1-1 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.7V to the organic light emitting device manufactured above, blue light emission of 4.2 cd / A corresponding to x = 0.143 and y = 0.158 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

< Experimental Example  1-2>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-1-3 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.9V to the organic light emitting device manufactured above, blue light emission of 4.1 cd / A corresponding to x = 0.144 and y = 0.177 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. It became.

< Experimental Example  1-3>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-1-9 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6V to the organic light emitting device manufactured above, blue light emission of 3.3 cd / A corresponding to x = 0.154 and y = 0.157 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

< Experimental Example  1-4>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-2-9 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6V to the organic light emitting device manufactured above, blue emission of 3.9 cd / A corresponding to x = 0.156 and y = 0.177 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. It became.

< Experimental Example  1-5>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-2-10 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6 V to the organic light emitting device manufactured above, blue light emission of 5.1 cd / A corresponding to x = 0.151 and y = 0.232 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. It became.

< Experimental Example  1-6>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-2-25 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6 V to the organic light emitting device manufactured above, blue light emission of 4.8 cd / A corresponding to x = 0.151 and y = 0.241 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

< Experimental Example  1-7>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-2-17 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6V to the organic light emitting device manufactured above, blue light emission of 5.3 cd / A corresponding to x = 0.206 and y = 0.337 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

< Experimental Example  1-8>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-2-29 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6V to the organic light emitting device manufactured above, blue light emission of 5.6 cd / A corresponding to x = 0.203 and y = 0.324 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

< Experimental Example  1-9>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that Compound 1-2-22 was used instead of Compound D1 in Comparative Example 1-1.

As a result of applying a forward electric field of 6.6V to the organic light emitting device manufactured above, blue light emission of 5.1 cd / A corresponding to x = 0.197 and y = 0.214 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

As shown in the experimental results, in the compound according to the present invention and the organic electroluminescent device using the same, the compounds according to the present invention exhibit various color coordinates by silyl group, fluorine group, nitrile group, heteroaryl group, aryl group, etc. In the electroluminescent device, low voltage and high efficiency are shown. Therefore, the present compounds may be utilized as light emitting materials having various color coordinates and the like that can respond to industrial products using light.

1 is an example of an organic light emitting device structure in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101.

2 is an example of an organic light emitting device structure in which an anode 102, a hole injection / hole transporting and light emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially laminated on a substrate 101.

3 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting and emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked .

4 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially stacked .

Claims (10)

A compound represented by the following formula (1): [Formula 1]

In Formula 1, R ′ and R ″ are the same as or different from each other, and each independently, an alkyl group of C ₁ to C ₆ ; a cyano group; an aryl group of C ₆ to C ₂₀ ; a cycloalkyl group of C ₅ to C ₁₂ ; C ₁ to C ₂₀ An alkoxy group of C ₃ to C ₃₀ heteroaryl group containing N, O or S, or —Si (Z 1) (Z 2) (Z 3), R1 and R2 are the same as or different from each other, and each independently hydrogen atom; Deuterium atoms; An alkyl group having ₁ to ₆ carbon atoms; Cyano; A fluorine group; A C ₆ to C ₂₀ aryl group; A cycloalkyl group of C ₅ ~ C _12; C ₃ ~ C ₃₀ Heteroaryl group containing N, O or S; C ₁ ~ C ₂₀ Alkoxy group; An ester group; Or a carbonyl group, or adjacent substituents form a condensed ring of aliphatic, a condensed ring of aromatic hetero, or an aromatic condensed ring, Ar1 and Ar2 are the same as or different from each other, and are each independently a C ₆ to C ₂₀ aryl group substituted with a deuterium atom, a fluorine atom, or -Si (Z 1) (Z 2) (Z 3), wherein the aryl group is further C ₁ It may be substituted with an alkyl group of ~ C ₆ , Z1, Z2 and Z3 are the same as or different from each other, and are each independently an alkyl group of C ₁ to C ₆ or an aryl group of C ₆ to C ₂₀ , n and m are the same as or different from each other, and each independently an integer of 0 to 5, when n or m is an integer of 2 or more, the two or more R1 or R2 may be the same or different from each other. The compound of claim 1, wherein the alkyl group of C ₁ to C ₆ of Formula 1 is selected from the group consisting of methyl group, ethyl group and tert-butyl group. The compound of claim 1, wherein the C ₆ to C ₂₀ aryl group of Formula 1 is selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, and a fluorenyl group. The compound according to claim 1, wherein the cycloalkyl group of C ₅ to C ₁₂ in Chemical Formula 1 is a cyclopentyl group or a cyclohexyl group. The heteroaryl group of C ₃ to C ₃₀ including N, O or S of Formula 1 is a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, A compound characterized in that it is selected from the group consisting of an oxazolyl group, thiazolyl group and triazine group. The compound according to claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of the following compounds:

1) Lithiated to 1,6-dibromopyrene and reacted with R'X or R "X, or R 'or R" was introduced to 1,6-dibromopyrene under a palladium catalyst. Preparing compound B, 2) reacting Compound B with bromine or NBS (N-bromo succinimide) to produce Compound C, and 3) introducing the amine compound represented by the following Formula 2 to the compound C under a palladium catalyst Method for preparing a compound represented by the following formula (1) comprising: [Formula 1]

[Compound B]

[Compound C]

(2)

In Chemical Formula 1, Chemical Formula 2, Compound B, and Compound C, R ′ and R ″ are the same as or different from each other, and each independently C ₁ to C ₆ alkyl group; cyano group; C ₆ to C ₂₀ aryl group; C ₅ to C ₁₂ cycloalkyl group; C ₁ to C ₂₀ An alkoxy group; a C ₃ to C ₃₀ heteroaryl group containing N, O or S; or —Si (Z 1) (Z 2) (Z 3), R, R1 and R2 are the same as or different from each other, and each independently a hydrogen atom; Deuterium atoms; An alkyl group having ₁ to ₆ carbon atoms; Cyano; A fluorine group; A C ₆ to C ₂₀ aryl group; A cycloalkyl group of C ₅ ~ C _12; C ₃ ~ C ₃₀ Heteroaryl group containing N, O or S; C ₁ ~ C ₂₀ Alkoxy group; An ester group; Or a carbonyl group, or adjacent substituents form an aliphatic condensed ring, an aromatic heterocondensed ring, or an aromatic condensed ring, Ar, Ar1 and Ar2 are the same as or different from each other, and are each independently a C ₆ to C ₂₀ aryl group substituted with a deuterium atom, a fluorine atom or -Si (Z1) (Z2) (Z3), wherein the aryl group is further C ₁ ~ C ₆ It may be substituted with an alkyl group, Z1, Z2 and Z3 are the same as or different from each other, and are each independently an alkyl group of C ₁ to C ₆ or an aryl group of C ₆ to C ₂₀ , n, m and p are the same as or different from each other, and each independently an integer of 0 to 5, when n, m or p is an integer of 2 or more, the two or more R1, R2 or R may be the same or different from each other , X is each independently a halogen group. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer is represented by Chemical Formula 1 according to any one of claims 1 to 6. An organic electronic device comprising the compound shown. The organic electronic device of claim 8, wherein the organic material layer comprises at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer. The organic electronic device of claim 8, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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