KR102394380B1 - Novel electroluminescent compound and organic electroluminescent device comprising same - Google Patents

Abstract

The organic light emitting compound of the present invention has excellent hole and electron transport characteristics, excellent blue light emission maintenance and luminous efficiency, and has high color purity, high efficiency and long lifespan, so that when applied to an organic light emitting device, excellent device characteristics can be exhibited.

Description

Novel light-emitting compound and organic light-emitting device comprising the same

The present invention relates to a novel light emitting compound and an organic light emitting device comprising the same.

Recently, organic light emitting diodes that are self-luminous and capable of low voltage driving have superior viewing angles and contrast ratios compared to liquid crystal displays (LCDs), which are the mainstay of flat panel display devices. It is also advantageous in terms of power consumption and has a wide color reproduction range, attracting attention as a next-generation display device.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to a function. The light emitting material can be classified into high molecular weight and low molecular weight according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to a light emitting mechanism. can be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary to realize better natural colors according to the emission color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant and host used.

To date, various compounds are known as materials used in such organic light emitting devices, but in the case of organic light emitting devices using known materials, there have been many difficulties in practical application due to high driving voltage, low efficiency, and short lifespan. Accordingly, efforts have been made to develop an organic light emitting diode having low voltage driving, high luminance, and long lifespan using a material having excellent properties.

In order to solve the above problems, the present invention is to provide a novel light emitting compound that is excellent in hole and electron transport properties, has excellent blue light emission maintenance and luminous efficiency, and can have high color purity, high efficiency and long lifespan. The purpose.

Another object of the present invention is to provide an organic light emitting device that includes the above compound, which is excellent in low driving voltage, blue light emission maintenance and luminous efficiency, and capable of realizing high color purity, high efficiency and long lifespan.

In order to achieve the above object, the present invention provides a light emitting compound represented by the following formula (1):

[Formula 1]

In the above formula,

each X is independently O, S, Se or Te;

Ar is deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _{6-30 A} C _6-50 aryl group unsubstituted or substituted with an aryloxy group, a C _{6-30 aryl} group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _{2-30 alkenyl} group, _{C 2-30 alkynyl} group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,

*- is a binding site,

n is 1 or 2, and when n is 2, Ar is absent.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1).

The light emitting compound of the present invention has excellent hole and electron transport properties, excellent blue light emission retention and luminous efficiency, and has high color purity, high efficiency and long lifespan, so that it can exhibit excellent device characteristics when applied to an organic light emitting device.

1 schematically shows a cross-section of an OLED according to an embodiment of the present invention.
drawing sign
10: substrate
11: positive electrode
12: hole injection layer
13: hole transport layer
14: light emitting layer
15: electron transport layer
16: cathode

The compound of the present invention is characterized in that it is represented by the following formula (1).

[Formula 1]

In the above formula,

each X is independently O, S, Se or Te;

Ar is deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _{6-30 A} C _6-50 aryl group unsubstituted or substituted with an aryloxy group, a C _{6-30 aryl} group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _{2-30 alkenyl} group, _{C 2-30 alkynyl} group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,

*- is a binding site,

n is 1 or 2, and when n is 2, Ar is absent.

In the present invention, the compound represented by Formula 1 may be one of those represented by Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, X, Ar, R ₁ , R ₂ , R ₃ and R ₄ are as defined in Formula 1.

In the present invention, preferred examples of the compound represented by Formula 1 are as follows:

The compound of Formula 1 according to the present invention has excellent hole and electron transport properties, excellent blue light emission maintenance and luminous efficiency, and has high color purity, high efficiency and long lifespan. .

In addition, the compound of the present invention can be prepared through the following Scheme 1:

[Scheme 1]

In Scheme 1, in the Schemes, X, Ar, R ₁ , R ₂ , R ₃ , and R ₄ are as defined in Formula 1, and R are each independently R 1 of Formula ₁ to R ₂ is the same.

More specifically, the compounds of Formulas 2 to 5 of the present invention may be prepared through the following Reaction Schemes 2 to 5, respectively.

[Scheme 2]

[Scheme 3]

[Scheme 4]

[Scheme 5]

In the above schemes, X, Ar, R ₁ , R ₂ , R ₃ , and R ₄ are as defined in Formula 1, and R are each independently R ₁ to R ₂ of Formula 1 and same.

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 as a light emitting material in an organic material layer. In this case, the compound of the present invention may be used alone or in combination with a known organic light emitting compound.

In addition, since the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Formula 1, a method for manufacturing the organic light emitting device will be described as follows.

The organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) between an anode and a cathode. It may contain more than one.

First, an anode is formed by depositing a material for an anode electrode having a high work function on a substrate. In this case, as the substrate, a substrate used in a conventional organic light emitting device may be used, and in particular, it is preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. In addition, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc. may be used as the material for the anode electrode. The material for the anode electrode may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.

Then, the hole injection layer material on the anode electrode can be formed by a method such as vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett) method, etc., but it is easy to obtain a uniform film quality, and also It is preferable to form by a vacuum evaporation method from the point of being difficult to generate|occur|produce. In the case of forming the hole injection layer by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal characteristics of the desired hole injection layer, etc., but in general, a deposition temperature of 50-500 ℃, It is preferable to appropriately select a vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 Å/sec, and a layer thickness of 10 Å to 5 μm.

The hole injection layer material is not particularly limited, and TCTA (4,4',4"-tri(N-carbazolyl)tri, which is a phthalocyanine compound such as copper phthalocyanine disclosed in US Patent No. 4,356,429 or starburst-type amine derivatives) Phenylamine), m-MTDATA (4,4',4"-tris(3-methylphenylamino)triphenylamine), m-MTDAPB(4,4',4"-tris(3-methylphenylamino)phenoxybenzene ), HI-406(N ¹ ,N ¹ '-(biphenyl-4,4'-diyl)bis(N ¹ -(naphthalen-1-yl)-N ⁴ ,N ⁴ -diphenylbenzene-1,4 -diamine) and the like can be used as the hole injection layer material.

Next, the hole transport layer material on the hole injection layer can be formed by a method such as vacuum deposition, spin coating, casting, LB method, etc., but it is easy to obtain a uniform film quality, It is preferable to form by vapor deposition. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same range of conditions as those for the hole injection layer formation.

In addition, the hole transport layer material is not particularly limited, and may be arbitrarily selected from commonly known materials used for the hole transport layer. Specifically, the hole transport layer material is a carbazole derivative such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-bi Phenyl]-4,4'-diamine (TPD), N.N'-di(naphthalen-1-yl)-N,N'-diphenyl benzidine (α-NPD), such as common amines having an aromatic condensed ring derivatives and the like can be used.

After that, the light emitting layer material on the hole transport layer can be formed by methods such as vacuum deposition, spin coating, casting, LB, etc., but it is easy to obtain a uniform film quality and it is difficult to generate pin holes. It is preferable to form by In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same range of conditions as those for the formation of the hole injection layer. In addition, as the light emitting layer material, the compound represented by Formula 1 of the present invention may be used as a host or a dopant.

When the compound represented by Formula 1 is used as a light emitting host, a phosphorescent or fluorescent dopant may be used together to form the light emitting layer. In this case, as a fluorescent dopant, IDE102 or IDE105, or BD142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N ¹² -dimethylchrysene-, available from Idemitsu) 6,12-diamine) can be used, and the phosphorescent dopant is a green phosphorescent dopant Ir(ppy) ₃ (tris(2-phenylpyridine) iridium), and a blue phosphorescent dopant F2Irpic (iridium (III) bis[4,6- Difluorophenyl)-pyridinato-N,C2'] picolinic acid salt), UDC's red phosphorescent dopant RD61, etc. may be co-evacuated (doped). The doping concentration of the dopant is not particularly limited, but it is preferable that the dopant be doped in an amount of 0.01 to 15 parts by weight relative to 100 parts by weight of the host. If the dopant content is less than 0.01 parts by weight, there is a problem that the color development is not performed properly because the dopant amount is insufficient, and when it exceeds 15 parts by weight, there is a problem that the efficiency is rapidly reduced due to the concentration quenching phenomenon.

In addition, when used with a phosphorescent dopant in the light emitting layer, in order to prevent the phenomenon of triplet excitons or holes from diffusing into the electron transport layer, it is preferable to further laminate a hole blocking material (HBL) by vacuum deposition or spin coating. At this time, the hole-blocking material that can be used is not particularly limited, and any one of the known hole-blocking materials used as the hole-blocking material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole-inhibiting material described in Japanese Patent Application Laid-Open No. Hei 11-329734 (A1), etc. are mentioned. Representatively, Balq (bis(8-hyde) Roxy-2-methylquinolinol nato)-aluminum biphenoxide), phenanthrolines-based compounds (eg, UDC's BCP (vasocuproin)), etc. may be used.

An electron transport layer is formed on the light emitting layer formed as described above. In this case, the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, etc., and is particularly preferably formed by a vacuum deposition method.

The electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited. For example, a quinoline derivative, particularly tris(8-quinolinolato)aluminum (Alq ₃ ) ), or ET4 (6,6'-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl)di-2,2'-bipyridine) can be used. In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and as the electron injection layer material, LiF, NaCl, CsF, Li ₂ O, BaO, etc. material can be used.

In addition, although the deposition conditions of the electron transport layer vary depending on the compound used, in general, it is preferable to select the electron transport layer in the same range of conditions as those for the formation of the hole injection layer.

Thereafter, an electron injection layer material may be formed on the electron transport layer, and in this case, the electron transport layer is formed using a conventional electron injection layer material by vacuum deposition, spin coating, casting, etc., especially in the vacuum deposition method. It is preferable to form by

Finally, a metal for forming a cathode on the electron injection layer is formed by a method such as vacuum deposition or sputtering and used as a cathode. Here, as the metal for forming the cathode, a metal having a low work function, an alloy, an electrically conductive compound, and a mixture thereof may be used. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. There is this. In addition, in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

The organic light emitting device of the present invention can have an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an organic light emitting device having a cathode structure, as well as a structure of an organic light emitting device having a variety of structures. It is also possible to further form a layer or an intermediate layer of two layers.

As described above, the thickness of each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.

In addition, in the present invention, the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.

The organic light emitting device of the present invention has excellent device characteristics such as low driving voltage, blue light emitting maintenance and luminous efficiency, and high color purity, high efficiency, and long lifespan.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples.

Synthesis of Intermediate A

[Synthesis of A-1]

In a round-bottom flask, 28.5 g of benzofuran-2-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate are dissolved in 600 ml of toluene, and 220 ml of K ₂ CO ₃ (2M) and 5.1 g of Pd(PPh ₃ ) ₄ are added. It was stirred at reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 35.8 g of Intermediate A-1 (yield 72%).

[Synthesis of A-2]

After dissolving 35 g of the A-1 in 800 ml of THF, the temperature was lowered to 0 °C. 105 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 25.2 g of Intermediate A-2 (yield 70%).

[Synthesis of A]

After adding 250 ml of acetic acid and 1 ml of hydrochloric acid to 25 g of A-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 14.2 g of Intermediate A (yield: 60%).

Synthesis of Intermediate B

[Synthesis of B-1]

In a round-bottom flask, 28.5 g of benzofuran-2-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate are dissolved in 600 ml of toluene, and 220 ml of K ₂ CO ₃ (2M) and 5.1 g of Pd(PPh ₃ ) ₄ are added. It was stirred at reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 35.8 g of Intermediate B-1 (yield 72%).

[Synthesis of B-2]

After dissolving 35 g of the B-1 in 850 ml of THF, the temperature was lowered to 0 °C. 105 ml of PhMgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 33.7 g of Intermediate B-2 (yield 70%).

[Synthesis of B]

After adding 330 ml of acetic acid and 1.3 ml of hydrochloric acid to 33 g of B-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 20.6 g of Intermediate B (yield 65%).

Synthesis of Intermediate C

[Synthesis of C-1]

In a round-bottom flask, 31.3 g of benzo[b]thiophen-2-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate are dissolved in 600 ml of toluene, and 220 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) ₄ 5.1 g, and then stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 38.2 g of Intermediate C-1 (yield 75%).

[Synthesis of C-2]

After dissolving 38 g of C-1 in 900 ml of THF, the temperature was lowered to 0 °C. 110 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 26.6 g of Intermediate C-2 (yield 70%).

[Synthesis of C]

After adding 260 ml of acetic acid and 1 ml of hydrochloric acid to 26 g of C-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 14.8 g of Intermediate C (yield: 60%).

Synthesis of Intermediate D

[Synthesis of D-1]

In a round-bottom flask, 31.3 g of benzo[b]thiophen-2-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate are dissolved in 600 ml of toluene, and 220 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) ₄ 5.1 g, and then stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and purified by column to obtain 38.2 g of Intermediate D-1 (yield 75%).

[Synthesis of D-2]

After dissolving 38 g of D-1 in 900 ml of THF, the temperature was lowered to 0 °C. 110 ml of PhMgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 36.6 g (yield 71%) of Intermediate D-2.

[Synthesis of D]

After adding 360 ml of acetic acid and 1.5 ml of hydrochloric acid to 36 g of D-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 23.2 g of Intermediate D (yield 67%).

Example 1: Synthesis of compound 1

In a round-bottom flask, 3.0 g of Intermediate A and 3.4 g of (10-phenylanthracen-9-yl)boronic acid were dissolved in 100 ml of toluene, 15 ml of K ₂ CO ₃ (2M) and 0.33 g of Pd(PPh ₃ ) ₄ were added and refluxed. stirred. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.0 g of Compound 1 (yield 43%).

Example 2: Synthesis of compound 2

In a round-bottom flask, dissolve 3.0 g of Intermediate A and 4.0 g of (10-(naphthalen-2-yl)anthracen-9-yl)boronic acid in 105 ml of toluene, 15 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) After adding 0.33 g of ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.1 g of Compound 2 (yield 40%).

Example 3: Synthesis of compound 3

In a round-bottom flask, dissolve 3.0 g of Intermediate A and 4.0 g of (10-(naphthalen-1-yl)anthracen-9-yl)boronic acid in 105 ml of toluene, 15 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) After adding 0.33 g of ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.3 g of compound 3 (yield: 44%).

Example 4: Synthesis of compound 4

In a round-bottom flask, dissolve 3.0 g of Intermediate A and 4.3 g of (10-([1,1'-biphenyl]-4-yl)anthracen-9-yl)boronic acid in 110 ml of toluene, K ₂ CO ₃ (2M) 15 ml and 0.33 g of Pd(PPh ₃ ) ₄ were added and stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.0 g of compound 4 (yield 38%).

Example 5: Synthesis of compound 5

In a round-bottom flask, dissolve 3.0 g of Intermediate A and 4.3 g of (10-([1,1'-biphenyl]-3-yl)anthracen-9-yl)boronic acid in 110 ml of toluene, K ₂ CO ₃ (2M) 15 ml and 0.33 g of Pd(PPh ₃ ) ₄ were added and stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.4 g of Compound 5 (yield 45%).

Example 6: Synthesis of compound 6

In a round-bottom flask, dissolve 3.0 g of Intermediate A and 4.3 g of (10-([1,1'-biphenyl]-2-yl)anthracen-9-yl)boronic acid in 110 ml of toluene, K ₂ CO ₃ (2M) 15 ml and 0.33 g of Pd(PPh ₃ ) ₄ were added and stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.2 g of compound 6 (yield 40%).

Example 7: Synthesis of compound 7

Dissolve 2.5 g of Intermediate A and 4.0 g of (10-(4-(naphthalen-1-yl)phenyl)anthracen-9-yl)boronic acid in 100 ml of toluene in a round-bottom flask, and then dissolve in 100 ml of K ₂ CO ₃ (2M) and 12 ml of K 2 CO 3 (2M). After adding 0.3 g of Pd(PPh ₃ ) ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.2 g of Compound 7 (yield 45%).

Example 8: Synthesis of compound 8

Dissolve 2.5 g of Intermediate A and 4.0 g of (10-(4-(naphthalen-2-yl)phenyl)anthracen-9-yl)boronic acid in 100 ml of toluene in a round-bottom flask, and dissolve in 100 ml of K ₂ CO ₃ (2M) and 12 ml of K 2 CO 3 (2M). After adding 0.3 g of Pd(PPh ₃ ) ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.3 g of compound 8 (yield 47%).

Example 9: Synthesis of compound 9

Dissolve 2.5 g of Intermediate A and 4.0 g of (10-(3-(naphthalen-1-yl)phenyl)anthracen-9-yl)boronic acid in 100 ml of toluene in a round-bottom flask, and mix with 12 ml of K ₂ CO ₃ (2M) After adding 0.3 g of Pd(PPh ₃ ) ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.3 g of compound 9 (yield: 47%).

Example 10: Synthesis of compound 10

Dissolve 2.5 g of Intermediate A and 4.0 g of (10-(3-(naphthalen-2-yl)phenyl)anthracen-9-yl)boronic acid in 100 ml of toluene in a round-bottom flask, and dissolve in 100 ml of K ₂ CO ₃ (2M) and 12 ml of K 2 CO 3 (2M). After adding 0.3 g of Pd(PPh ₃ ) ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and when the reaction was completed, water was added and the organic layer was extracted with MC. After filtration under reduced pressure, column purification was performed to obtain 2.1 g of Compound 10 (yield 43%).

Example 11: Synthesis of compound 11

Compound 11 was synthesized in the same manner as in Compound 1, except that it was reacted with Intermediate B instead of Intermediate A.

Example 12: Synthesis of compound 12

Compound 12 was synthesized in the same manner as in Compound 2, except that it was reacted with Intermediate B instead of Intermediate A.

Example 13: Synthesis of compound 13

Compound 13 was synthesized in the same manner as in Compound 3, except that intermediate B was used instead of intermediate A.

Example 14: Synthesis of compound 14

Compound 14 was synthesized in the same manner as in Compound 4, except that it was reacted with Intermediate B instead of Intermediate A.

Example 15: Synthesis of compound 15

Compound 15 was synthesized in the same manner as in Compound 5, except that it was reacted with Intermediate B instead of Intermediate A.

Example 16: Synthesis of compound 16

Compound 16 was synthesized in the same manner as in Compound 6, except that it was reacted with Intermediate B instead of Intermediate A.

Example 17: Synthesis of compound 17

Compound 17 was synthesized in the same manner as in Compound 7, except that it was reacted with Intermediate B instead of Intermediate A.

Example 18: Synthesis of compound 18

Compound 18 was synthesized in the same manner as in Compound 8, except for reacting with Intermediate B instead of Intermediate A.

Example 19: Synthesis of compound 19

Compound 19 was synthesized in the same manner as in Compound 9, except that it was reacted with Intermediate B instead of Intermediate A.

Example 20: Synthesis of compound 20

Compound 20 was synthesized in the same manner as in Compound 10, except that it was reacted with Intermediate B instead of Intermediate A.

Example 21: Synthesis of compound 21

Compound 21 was synthesized in the same manner as in Compound 1, except that Intermediate C was used instead of Intermediate A.

Example 22: Synthesis of compound 22

Compound 22 was synthesized in the same manner as in Compound 2, except that Intermediate C was used instead of Intermediate A.

Example 23: Synthesis of compound 23

Compound 23 was synthesized in the same manner as in Compound 3, except for reacting with Intermediate C instead of Intermediate A.

Example 24: Synthesis of compound 24

Compound 24 was synthesized in the same manner as in Compound 4, except that the reaction was performed as Intermediate C instead of Intermediate A.

Example 25: Synthesis of compound 25

Compound 25 was synthesized in the same manner as in Compound 5, except that Intermediate C was used instead of Intermediate A.

Example 26: Synthesis of compound 26

Compound 26 was synthesized in the same manner as in Compound 6, except for reacting with Intermediate C instead of Intermediate A.

Example 27: Synthesis of compound 27

Compound 27 was synthesized in the same manner as in Compound 7, except that the reaction was performed as Intermediate C instead of Intermediate A.

Example 28: Synthesis of compound 28

Compound 28 was synthesized in the same manner as in Compound 8, except for reacting with Intermediate C instead of Intermediate A.

Example 29: Synthesis of compound 29

Compound 29 was synthesized in the same manner as in Compound 9, except that the reaction was performed as Intermediate C instead of Intermediate A.

Example 30: Synthesis of compound 30

Compound 30 was synthesized in the same manner as in Compound 10, except for reacting with Intermediate C instead of Intermediate A.

Example 31: Synthesis of compound 31

Compound 31 was synthesized in the same manner as in Compound 1, except that the reaction was performed as Intermediate D instead of Intermediate A.

Example 32: Synthesis of compound 32

Compound 32 was synthesized in the same manner as in Compound 2, except that the reaction was performed as Intermediate D instead of Intermediate A.

Example 33: Synthesis of compound 33

Compound 33 was synthesized in the same manner as in Compound 3, except for the reaction as Intermediate D instead of Intermediate A.

Example 34: Synthesis of compound 34

Compound 34 was synthesized in the same manner as in Compound 4, except that the reaction was performed as Intermediate D instead of Intermediate A.

Example 35: Synthesis of compound 35

Compound 35 was synthesized in the same manner as in Compound 5, except for reacting with Intermediate D instead of Intermediate A.

Example 36: Synthesis of compound 36

Compound 36 was synthesized in the same manner as in Compound 6, except for reacting with Intermediate D instead of Intermediate A.

Example 37: Synthesis of compound 37

Compound 37 was synthesized in the same manner as in Compound 7, except that the reaction was performed with Intermediate D instead of Intermediate A.

Example 38: Synthesis of compound 38

Compound 38 was synthesized in the same manner as in Compound 8, except for reacting with Intermediate D instead of Intermediate A.

Example 39: Synthesis of compound 39

Compound 39 was synthesized in the same manner as in Compound 9, except that the reaction was performed as Intermediate D instead of Intermediate A.

Example 40: Synthesis of compound 40

Compound 40 was synthesized in the same manner as in Compound 10, except that the reaction was performed as Intermediate D instead of Intermediate A.

Manufacturing of organic light emitting device

An organic light emitting diode was manufactured according to the structure shown in FIG. 1 . The organic light emitting device is from the bottom anode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transport layer 15 / cathode (electron injection electrode 16) stacked in order.

The following materials were used for the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples.

HI01,

NPB,

AND,

비교화합물 1,

HI01,

NPB,

AND,

Comparative compound 1,

BD01,

ET01,

Liq

BD01,

ET01,

Liq

Example 41

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a plasma cleaner, and then cleaned using oxygen plasma for 5 minutes. An evaporator) was used to form a hole injection layer HT01 600 Å and Compound 1 250 Å as a hole transport layer. Next, the light emitting layer was doped with Compound 1:BD01 5% to form a film of 250 Å. Next, ET01:Liq (1:1) 300 Å was formed as an electron transport layer, LiF 10 Å, and aluminum (Al) 1000 Å were formed into a film, and an organic light emitting device was manufactured by encapsulating the device in a glove box.

Examples 42-80

In the same manner as in Example 41, an organic light emitting device in which a hole injection layer and a hole transport layer were respectively formed using Compounds 2 to 40 instead of Compound 1 was fabricated.

Comparative Example 1

A device was manufactured in the same manner as in Example 41, except that an AND was used instead of Compound 1 as the light emitting layer.

Comparative Example 2

A device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used instead of Compound 1 as the emission layer of Example 1.

Performance evaluation of organic light emitting devices

Electrons and holes are injected by applying voltage with a Kiethley 2400 source measurement unit, and the luminance when light is emitted is measured using a Konica Minolta spectroradiometer (CS-2000). By doing so, the performances of the organic light emitting devices of Examples and Comparative Examples were evaluated by measuring current density and luminance with respect to applied voltage under atmospheric pressure conditions, and the results are shown in Table 1.

Op. V mA/cm2 Cd/A lm/w CIEx CIEy life span
LT95 Example 41 4.147 10 6.55 5.09 0.139 0.118 21 Example 42 4.192 10 6.12 5.21 0.140 0.118 25 Example 43 4.218 10 6.23 5.13 0.140 0.118 23 Example 44 4.119 10 6.19 5.09 0.140 0.121 24 Example 45 4.152 10 5.99 5.11 0.140 0.114 29 Example 46 4.188 10 6.02 5.22 0.141 0.119 21 Example 47 4.208 10 6.17 5.99 0.140 0.119 25 Example 48 4.144 10 6.22 5.76 0.140 0.120 30 Example 49 4.147 10 6.03 5.38 0.140 0.117 29 Example 50 4.219 10 5.98 5.54 0.142 0.123 20 Example 51 4.214 10 6.26 5.96 0.142 0.113 23 Example 52 4.212 10 6.17 5.45 0.141 0.124 22 Example 53 4.159 10 6.09 5.94 0.142 0.118 23 Example 54 4.165 10 5.97 5.44 0.140 0.115 24 Example 55 4.203 10 6.19 5.79 0.140 0.112 27 Example 56 4.186 10 6.23 6.00 0.140 0.123 20 Example 57 4.179 10 6.03 5.86 0.140 0.112 27 Example 58 4.162 10 5.93 5.63 0.143 0.121 23 Example 59 4.198 10 5.96 5.65 0.141 0.121 31 Example 60 4.163 10 6.38 5.77 0.141 0.120 27 Example 61 4.011 10 6.69 5.89 0.141 0.122 21 Example 62 4.052 10 6.75 5.81 0.141 0.118 23 Example 63 4.033 10 6.88 5.96 0.142 0.130 20 Example 64 4.021 10 6.95 5.94 0.139 0.121 25 Example 65 4.012 10 6.12 5.92 0.138 0.120 29 Example 66 4.003 10 5.94 5.94 0.140 0.118 23 Example 67 4.095 10 6.17 5.99 0.140 0.117 28 Example 68 4.012 10 6.20 5.69 0.140 0.117 22 Example 69 4.010 10 6.13 5.64 0.138 0.120 29 Example 70 4.059 10 6.88 5.84 0.141 0.119 27 Example 71 4.009 10 5.93 5.77 0.142 0.116 25 Example 72 4.007 10 6.10 5.79 0.141 0.118 20 Example 73 4.100 10 6.23 5.85 0.142 0.122 24 Example 74 4.041 10 6.01 5.87 0.141 0.116 22 Example 75 4.014 10 5.99 5.80 0.141 0.124 21 Example 76 4.044 10 6.61 5.90 0.141 0.124 22 Example 77 4.053 10 6.73 5.91 0.140 0.113 25 Example 78 4.005 10 6.81 5.87 0.140 0.130 26 Example 79 4.025 10 5.99 5.85 0.140 0.121 27 Example 80 4.110 10 6.28 5.71 0.138 0.120 26 Comparative Example 1 5.032 10 4.97 4.26 0.143 0.130 5 Comparative Example 2 4.243 10 5.88 5.59 0.142 0.123 12

As shown in Table 1, it was confirmed that the Examples of the present invention had superior driving voltage, efficiency, and lifespan compared to Comparative Examples 1 and 2. In particular, it is judged that the 4-ring ring in this proposal is due to the improvement of efficiency and lifespan.

Claims (7)

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

In the above formula,
each X is independently O, S, Se or Te;
Ar is deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _{2-30 alkynyl} group, C _{1-30 alkoxy} group, _{C 6-30 A} C _6-50 aryl group unsubstituted or substituted with an aryloxy group, a C _{6-30 aryl} group, or a _{C 2-30} heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _{2-30 alkenyl} group, _{C 2-30 alkynyl} group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,
*- is a binding site,
n is 1 or 2, and when n is 2, Ar is absent. The method of claim 1,
A light-emitting compound, characterized in that it is represented by one of the following formulas 2 to 5:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, X, Ar, R ₁ , R ₂ , R ₃ and R ₄ are as defined in Formula 1. The method of claim 1,
A luminescent compound, characterized in that it is represented by any one of the following formulas:

The preparation method of Formula 1 represented by the following Reaction Scheme 1:
[Scheme 1]

[Formula 1]

In the above formula,
each X is independently O, S, Se or Te;
Ar is deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 C _6-50 aryl group unsubstituted or substituted with an aryloxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,
*- is a binding site,
n is 1 or 2, and when n is 2, Ar is absent;
R is each independently the same as R ₁ to R ₂ above. 5. The method of claim 4,
A method of preparing Formula 1 represented by any one of the following Reaction Schemes 2 to 5:
[Scheme 2]

[Scheme 3]

[Scheme 4]

[Scheme 5]

In the above schemes, X, Ar, R, R ₁ , R ₂ , R ₃ , and R ₄ are as defined in claim 4. An organic light emitting device comprising an anode, a cathode, and at least one organic material layer containing the compound of claim 1 between the two electrodes. 7. The method of claim 6,
The organic light emitting device, characterized in that the organic material layer contains the compound of claim 1 as a light emitting host or dopant.

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