KR102388406B1 - Novel electroluminescent compound and organic electroluminescent device comprising same - Google Patents

Abstract

The organic light emitting compound of the present invention has excellent charge transfer characteristics, and at the same time has high triplet energy and high Tg, so that it can have low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.

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, the organic light emitting device capable of low voltage driving as a self-emitting type has excellent viewing angle and contrast ratio, and does not require a backlight, compared to a liquid crystal display (LCD), which is the mainstream 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 a small amount in the light emitting layer, 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 has excellent charge transfer characteristics and at the same time has high triplet energy and high Tg, so that when applied to an organic light emitting device, it can have low driving voltage, high efficiency, low power consumption, and long life. An object of the present invention is to provide a novel light emitting compound.

Another object of the present invention is to provide an organic light emitting device capable of realizing a low driving voltage, high efficiency, low power consumption, and long life including the above compound.

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

[Formula 1]

A-L-B

In the above formula,

A is one of the structures represented by the following A1 to A30, wherein each hydrogen contained in A may be independently substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group,

L 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,

B is one of the structures represented by the following B1 to B10, wherein each hydrogen included in B may be independently substituted with or unsubstituted with deuterium, halogen, amino, nitrile, or nitro group.

In the above structures, -* is a bonding site, Ar ₁ and Ar ₂ 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group.

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 as a light emitting material in an organic material layer.

The light emitting compound of the present invention has excellent charge transfer characteristics, and at the same time has high triplet energy and high Tg, so that it can have low driving voltage, high efficiency, low power consumption, and long life 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]

A-L-B

In the above formula,

A is one of the structures represented by the following A1 to A30, wherein each hydrogen contained in A may be independently substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group,

L 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 _2-30 heteroaryl group substituted or unsubstituted with a C _2-50 heteroaryl group, preferably L is one of the following structures,

B is one of the structures represented by the following B1 to B10, wherein each hydrogen included in B may be independently substituted with or unsubstituted with deuterium, halogen, amino, nitrile, or nitro group.

In the above structures, -* is a binding site,

Ar ₁ and Ar ₂ 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group. Preferably, Ar ₁ and Ar ₂ are each independently one of the following structures.

In the present invention, the compound represented by Formula 1 is preferably one of the structures shown below.

In the above, X ₁ and X ₂ are each independently S, O, Se, Te or N-Ar ₃ , wherein Ar ₃ is 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,

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 _6-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group.

In the present invention, the compound represented by Formula 1 is more preferably one of the structures shown below.

In the above, X ₁ and X ₂ are each independently S, O, Se, Te or N-Ar ₄ , wherein Ar ₄ is 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,

Y is CR ₁ or N, wherein R ₁ is 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group.

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 charge transfer characteristics, and at the same time has high triplet energy and high Tg, so that it can have low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.

In addition, the compound of the present invention can be prepared in the same manner as in Scheme 1 below.

[Scheme 1]

As a specific example, Scheme 1-1 may be applied.

[Scheme 1-1]

In Scheme 1 and Scheme 1-1, A, L, B, X ₁ , and X ₂ are as defined in Formula 1 above.

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 or starburst-type amine derivatives disclosed in US Patent No. 4,356,429. 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 the hole transport layer within the same range of conditions as that of the hole injection layer.

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.

Thereafter, 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 the light emitting layer 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 the fluorescent dopant, IDE102 or IDE105, or BD142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N ¹² -dimethylchrysene- 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-hydra) 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, in which case the electron transport layer is formed by a method such as a vacuum deposition method, a spin coating method, a casting method, etc. of a conventional electron injection layer material, especially in a 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 charge transfer characteristics, and at the same time includes the compound represented by Formula 1 having high triplet energy and high Tg, and can realize low driving voltage, high efficiency, low power consumption, and long life.

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 A1]

[Synthesis of A1-1]

In a round-bottom flask, 102.2 g of dibenzo[b,d]furan-4-ylboronic acid and 100 g of 1-iodo-2-nitrobenzene are dissolved in 1500 ml of toluene, 600 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) ₄ After adding 13.9 g, the mixture was 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 98.7 g of Intermediate A1-1 (yield 85%).

[Synthesis of A1]

98 g of A1-1 was dissolved in 500 ml of 1,2-dichlorobenzene, 330 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 52.3 g of Intermediate A1 (yield 60%).

[Synthesis of Intermediate A2]

[Synthesis of A2-1]

In a round-bottom flask, 109.9 g of dibenzo[b,d]thiophen-4-ylboronic acid and 100 g of 1-iodo-2-nitrobenzene are dissolved in 1500 ml of toluene, 600 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) ₄ After adding 13.9 g, the mixture was 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 99.3 g of Intermediate A2-1 (yield 81%).

[Synthesis of A2]

After dissolving 99 g of A2-1 in 490 ml of 1,2-dichlorobenzene, 320 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 54.0 g of Intermediate A2 (yield 61%).

[Synthesis of Intermediate A3]

[Synthesis of A3-1]

In a round-bottom flask, 124.53 g of (9-phenyl-9H-carbazol-1-yl)boronic acid and 90 g of 1-iodo-2-nitrobenzene are dissolved in 1500 ml of toluene, and 540 ml of K ₂ CO ₃ (2M) and Pd(PPh) are dissolved in it. ₃ ) After adding 12.5 g of ₄ , the mixture was 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 105.4 g of Intermediate A3-1 (yield 80%).

[Synthesis of A3]

105 g of A3-1 was dissolved in 530 ml of 1,2-dichlorobenzene, 290 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 39.2 g of Intermediate A3 (yield 41%).

[Synthesis of Intermediate B1]

[Synthesis of B1-1]

Dissolve 78.5 g of benzofuran-3-ylboronic acid and 100 g of 1-iodo-2-nitrobenzene in 1000 ml of toluene in a round-bottom flask, add 600 ml of K ₂ CO ₃ (2M) and 13.9 g of Pd(PPh ₃ ) ₄ , and reflux stirred. 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 78.7 g of Intermediate B1-1 (yield 82%).

[Synthesis of B1]

After dissolving 78 g of B1-1 in 400 ml of 1,2-dichlorobenzene, 260 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 36.4 g of Intermediate B1 (yield 54%).

[Synthesis of Intermediate B2]

[Synthesis of B2-1]

Dissolve 87.7 g of benzo[b]thiophen-3-ylboronic acid and 100 g of 1-iodo-2-nitrobenzene in 1000 ml of toluene in a round-bottom flask, 600 ml of K ₂ CO ₃ (2M) and 13.9 g of Pd(PPh ₃ ) ₄ After adding, the mixture was 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 82 g of Intermediate B2-1 (yield 80%).

[Synthesis of B2]

80 g of B2-1 was dissolved in 400 ml of 1,2-dichlorobenzene, 310 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 39.8 g of Intermediate B2 (yield 57%).

[Synthesis of Intermediate B3]

[Synthesis of B3-1]

In a round-bottom flask, 102.8 g of (1-phenyl-1H-indol-3-yl)boronic acid and 90 g of 1-iodo-2-nitrobenzene are dissolved in 1000 ml of toluene, and 540 ml of K ₂ CO ₃ (2M) and Pd(PPh) are dissolved in it. ₃ ) After adding 12.5 g of ₄ , the mixture was 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 93.1 g of Intermediate B3-1 (yield 82%).

[Synthesis of B3]

93 g of B3-1 was dissolved in 460 ml of 1,2-dichlorobenzene, 290 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 40.9 g of intermediate B3 (yield 49%).

[Synthesis of Intermediate B6]

[Synthesis of B6-1]

Dissolve 78.5 g of benzofuran-2-ylboronic acid and 100 g of 1-iodo-2-nitrobenzene in 1000 ml of toluene in a round-bottom flask, add 600 ml of K ₂ CO ₃ (2M) and 13.9 g of Pd(PPh ₃ ) ₄ , and reflux stirred. 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 81.6 g (yield: 85%) of Intermediate B6-1.

[Synthesis of B6]

78 g of B6-1 was dissolved in 410 ml of 1,2-dichlorobenzene, 330 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 42.1 g of an intermediate (yield 60%).

[Synthesis of Intermediate B7]

[Synthesis of B7-1]

In a round-bottom flask, 85.7 g of benzo[b]thiophen-2-ylboronic acid and 100 g of 1-iodo-2-nitrobenzene are dissolved in 1000 ml of toluene, 600 ml of K ₂ CO ₃ (2M) and 13.9 g of Pd(PPh ₃ ) ₄ After adding, the mixture was 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 80.9 g of Intermediate B7-1 (yield 79%).

[Synthesis of B7]

80 g of B7-1 was dissolved in 400 ml of 1,2-dichlorobenzene, 310 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 38.5 g of intermediate B7 (yield 55%).

[Synthesis of Intermediate B8]

[Synthesis of B8-1]

In a round-bottom flask, 102.8 g of (1-phenyl-1H-indol-2-yl)boronic acid and 90 g of 1-iodo-2-nitrobenzene are dissolved in 1000 ml of toluene, and 540 ml of K ₂ CO ₃ (2M) and Pd(PPh) are dissolved in it. ₃ ) After adding 12.5 g of ₄ , the mixture was 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 87.5 g of Intermediate B8-1 (yield 77%).

[Synthesis of B8]

87 g of B8-1 was dissolved in 430 ml of 1,2-dichlorobenzene, 270 ml of P(OEt) ₃ was added thereto, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 25.7 g of intermediate B8 (yield 33%).

Using the intermediate synthesis method, the following intermediates are synthesized by different starting materials.

Example 1: Synthesis of compound 1

The intermediate A3 4.0 g, 1-bromo-3-iodobenzene 4.1 g, t-BuONa 1.7 g, Pd ₂ (dba) ₃ 0.45 g, (t-Bu) ₃ P 0.6 ml was dissolved in 60 ml toluene and stirred under reflux. . After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 2.05 g of Intermediate 1-1 (yield 35%).

2.05 g of Intermediate 1-1, 2.05 g of Intermediate B1, 0.61 g of t-BuONa, 0.15 g of Pd ₂ (dba) ₃ , and 0.2 ml of (t-Bu) ₃ P were dissolved in 30 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 1.34 g of Compound 1 (Yield 52%).

m/z: 613.22 (100.0%), 614.22 (47.9%), 615.22 (11.8%), 616.23 (1.7%), 614.21 (1.1%)

Example 2: Synthesis of compound 2

Compound 2 was synthesized in the same manner as in Compound 1, except that Intermediate A1 was used instead of Intermediate A3.

m/z: 538.17 (100.0%), 539.17 (42.2%), 540.17 (8.9%), 541.18 (1.3%)

Example 3: Synthesis of compound 3

Compound 3 was synthesized in the same manner as in Compound 1, except that Intermediate A2 instead of Intermediate A3 and B2 instead of Intermediate B1 were used.

m/z: 570.12 (100.0%), 571.13 (41.4%), 572.12 (9.4%), 572.13 (9.0%), 573.12 (3.9%), 571.12 (2.3%), 573.13 (1.3%)

Example 4: Synthesis of compound 4

Compound 4 was synthesized in the same manner as in Compound 1, except that B8 was used instead of Intermediate B1.

m/z: 688.26 (100.0%), 689.27 (54.4%), 690.27 (14.5%), 691.27 (2.7%), 689.26 (1.5%)

Example 5: Synthesis of compound 5

Compound 5 was synthesized in the same manner as in Compound 1, except that B6 was used instead of Intermediate B1.

m/z: 613.22 (100.0%), 614.22 (47.9%), 615.22 (11.8%), 616.23 (1.7%), 614.21 (1.1%)

Example 6: Synthesis of compound 6

Compound 6 was synthesized in the same manner as in Compound 1, except that B7 was used instead of Intermediate B1.

m/z: 629.19 (100.0%), 630.20 (47.9%), 631.20 (11.6%), 631.19 (5.1%), 632.19 (2.2%), 630.19 (1.9%), 632.20 (1.9%)

Example 7: Synthesis of compound 7

4.0 g of the intermediate A3 and 0.35 g of NaH were added to 40 ml of DMF and stirred. Here, 3.26 g of 2,4-dichloro-6-phenyl-1,3,5-triazine was dissolved in 35 ml of DMF, and then slowly added dropwise. After stirring at room temperature, the completion of the reaction was confirmed by TLC and recrystallized after silica filter to obtain 2.70 g (yield 43%) of Intermediate 7-1.

0.90 g of the intermediate B1 and 0.13 g of NaH were added to 10 ml of DMF and stirred. After dissolving 2.72 g of Intermediate 7-1 in 30 ml of DMF, it was slowly added dropwise. After stirring at room temperature, the completion of the reaction was confirmed by TLC and recrystallized after silica filter to obtain 1.56 g of compound 7 (yield 52%).

m/z: 692.23 (100.0%), 693.24 (51.2%), 694.24 (13.0%), 695.24 (2.4%), 693.23 (2.2%), 694.23 (1.1%)

Example 8: Synthesis of compound 8

Compound 8 was synthesized in the same manner as in Compound 7, except that B2 was used instead of Intermediate B1.

m/z: 708.21 (100.0%), 709.21 (53.9%), 710.22 (12.8%), 710.21 (6.1%), 711.21 (2.6%), 711.22 (2.2%)

Example 9: Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Compound 7, except that A1 was used instead of Intermediate A3.

m/z: 617.19 (100.0%), 618.19 (44.7%), 619.19 (11.0%), 618.18 (1.8%), 620.20 (1.4%)

Example 10: Synthesis of compound 10

Compound 10 was synthesized in the same manner as in Compound 7, except that Intermediate A2 instead of Intermediate A3 and B2 instead of Intermediate B1 were used.

m/z: 649.14 (100.0%), 650.14 (47.8%), 651.14 (10.6%), 651.15 (9.7%), 652.14 (4.2%), 652.15 (1.5%)

Example 11: Synthesis of compound 11

Compound 11 was synthesized in the same manner as in Compound 7, except that Intermediate A18 was used instead of Intermediate A3.

m/z: 692.23 (100.0%), 693.24 (51.2%), 694.24 (13.0%), 695.24 (2.4%), 693.23 (2.2%), 694.23 (1.1%)

Example 12: Synthesis of compound 12

Compound 12 was synthesized in the same manner as in Compound 7, except that Intermediate A18 instead of Intermediate A3 and B2 instead of Intermediate B1 were used.

m/z: 708.21 (100.0%), 709.21 (53.9%), 710.22 (12.8%), 710.21 (6.1%), 711.21 (2.6%), 711.22 (2.2%)

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.

,

,

,

,

,

,

비교화합물1,

비교화합물2,

Comparative compound 1,

Comparative compound 2,

,

,

,

,

Example 13

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. evaporator) was used to form a hole injection layer HT01 600 Å and NPB 250 Å as a hole transport layer. Next, the light emitting layer was doped with Compound 1: Ir(ppy) ₃ 10% 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 as a film, and a green organic light emitting device was manufactured by encapsulating the device in a glove box. .

Examples 14 to 24

In the same manner as in Example 13, green organic light emitting diodes were fabricated using compounds 2 to 12 as light emitting layer hosts, respectively.

Comparative Example 1

A green organic light emitting diode was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound 1 as the light emitting layer host.

Comparative Example 2

A green organic light emitting diode was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used instead of Compound 1 as a host for the emission layer of Example 1.

Comparative Example 3

A green organic light emitting diode was manufactured in the same manner as in Example 1, except that Comparative Compound 2 was used instead of Compound 1 as the light emitting layer host.

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 QE (%) Cd/A lm/w CIEx CIEy life span@
1000nits Example 13 6.900 17.21 47.68 20.11 0.301 0.621 40 Example 14 6.921 17.32 50.21 20.03 0.299 0.619 42 Example 15 6.897 17.29 49.90 21.04 0.298 0.620 41 Example 16 6.904 17.33 49.01 20.01 0.300 0.623 40 Example 17 6.945 16.99 50.21 19.39 0.298 0.614 43 Example 18 6.984 16.80 49.92 20.24 0.298 0.609 51 Example 19 6.879 17.01 48.01 21.12 0.297 0.618 55 Example 20 6.889 17.25 48.65 20.23 0.302 0.609 53 Example 21 6.891 16.90 47.28 21.00 0.300 0.620 52 Example 22 6.901 17.42 49.63 19.78 0.299 0.622 50 Example 23 6.889 17.16 49.11 20.14 0.299 0.619 50 Example 24 6.900 16.97 46.52 19.81 0.301 0.631 53 Comparative Example 1 7.824 12.43 38.12 13.72 0.301 0.623 25 Comparative Example 2 7.309 14.50 40.01 17.55 0.302 0.619 30 Comparative Example 3 7.021 16.12 42.98 18.07 0.300 0.622 35

As shown in Table 1, it can be confirmed that the examples of the present invention have superior physical properties of the organic light emitting device in all aspects compared to Comparative Examples 1 to 3.

Claims (8)

A light-emitting compound represented by the following formula (1):
[Formula 1]
ALB
In the above formula,
A is one of the structures represented by the following A1 to A30, wherein each hydrogen contained in A may be independently substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group,
L 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 an aryloxy group, a C _6-30 aryl group, or a C _6-50 arylene group unsubstituted or substituted with 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 heteroarylene group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
B is one of the structures represented by the following B1 to B10, wherein each hydrogen included in B may be independently substituted with or unsubstituted with deuterium, halogen, amino, nitrile, or nitro group.

In the above structures, -* is a bonding site, Ar ₁ and Ar ₂ 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group. According to claim 1,
A luminescent compound, characterized in that it is represented by any one of the following formulas:

In the above, X ₁ and X ₂ are each independently S, O, Se, Te or N-Ar ₃ , wherein Ar ₃ is 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,
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 an aryloxy group, a C _6-30 aryl group, or a C _6-50 arylene group unsubstituted or substituted with 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 It is a C _6-50 heteroarylene group that is unsubstituted or substituted with an oxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group. According to claim 1,
A luminescent compound, characterized in that it is represented by any one of the following formulas:

In the above, X ₁ and X ₂ are each independently S, O, Se, Te or N-Ar ₄ , wherein Ar ₄ is 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,
Y is CR ₁ or N, wherein R ₁ is 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 _6-30 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-30 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group. According to claim 1,
Wherein L is a light-emitting compound, characterized in that represented by any one of the following structures:

According to claim 1,
A luminescent compound, characterized in that it is represented by any one of the following formulas:

delete 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. 8. The method of claim 7,
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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