KR102447718B1 - 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

A novel light-emitting compound and an 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-luminous type has excellent viewing angle and contrast ratio, and does not require a backlight, compared to liquid crystal display (LCD), which is the mainstream of flat panel display devices. It is advantageous in terms of power consumption and has a wide color reproduction range, attracting attention as a next-generation display device.

Materials used as organic layers in organic light emitting devices may be classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, according to their functions. 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 for realizing 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 excellent 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 the dopant and the 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]

In the above formula,

each X is independently CR ₀ or N, wherein at least one of X is N and R ₀ is hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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 substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

Y is S, O, Se, Te or -NAr ₁ , wherein Ar ₁ is hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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 substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

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

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]

In the above formula,

each X is independently CR ₀ or N, wherein at least one of X is N and R ₀ is hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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,

Y is S, O, Se, Te or -NAr ₁ , wherein Ar ₁ is hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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 substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

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

In the present invention, the compound represented by Formula 1 may have the following structure.

In the above structures, X and Y are as defined in Formula 1,

Z is CR ₆ or N, R ₆ is hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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 substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, 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 C _6-38 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 _6-38 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,

Y ₁ is S, O, Se, Te or -NAr ₂ , wherein Ar ₂ is hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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,

R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; Deuterium, halogen, amino group, nitrile group, nitro group substituted or unsubstituted C _1-30 alkyl group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, or unsubstituted C _2-30 alkynyl group; a C _1-30 alkoxy group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; 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,

n is an integer from 1 to 6, and when n is 1, at least one of X is N.

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 present invention can be prepared by including the steps shown in Scheme 1:

[Scheme 1]

Scheme 1 may be the following Scheme 1-1 as a specific example.

[Scheme 1-1]

Parts not defined in the above Schemes are as defined in Formula 1.

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. 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 of 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 water resistance. In addition, as the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used. 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 the 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 may 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 formation 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 Ordinary amines having an aromatic condensed ring, such as phenyl]-4,4'-diamine (TPD), N.N'-di(naphthalen-1-yl)-N,N'-diphenyl benzidine (α-NPD), etc. 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 it 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.

In addition, when used together with a phosphorescent dopant in the light emitting layer, in order to prevent a phenomenon in which triplet excitons or holes are diffused 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 known hole-blocking materials used as a 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 the 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 within 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 vacuum deposition, spin coating, casting, etc., of a conventional electron injection layer material, particularly 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 a vacuum deposition method or a sputtering method 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 may have an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device having a cathode structure, as well as a structure of an organic light emitting device of various structures is possible, if necessary, 1 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 the present invention, the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent morphological stability because the thickness of the organic material layer can be adjusted in molecular units.

The organic light emitting diode 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, thereby implementing 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.

intermediate synthesis

The intermediate is synthesized by cyclization after the Suzuki reaction according to the following synthesis method.

[Synthesis of Intermediate 01]

[Synthesis of Intermediate 1-1]

Dissolve 95.7 g of benzofuran-3-ylboronic acid and 100 g of 2-bromo-3-nitropyridine in 1000 ml of toluene in a round-bottom flask, add 730 ml of K ₂ CO ₃ (2M) and 17.1 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 93.4 g of Intermediate 1-1 (yield 79%).

[Synthesis of Intermediate 01]

93 g of Intermediate 1-1 was dissolved in 460 ml of 1,2-dichlorobenzene, 380 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 28.2 g of Intermediate 01 (yield 35%).

[Synthesis of other intermediates]

In the same way as in the synthesis of Intermediate 01, instead of benzofuran-3-ylboronic acid, benzo[b]thiophen-3-ylboronic acid, (1-phenyl-1H-indol-3-yl)boronic acid, 3-bromofuro[3,2- b]pyridine, 3-bromofuro[2,3-b]pyridine, 3-bromofuro[2,3-c]pyridine, 3-bromofuro[3,2-c]pyridine, 7-bromofuro[3,2-d] pyrimidine, 5-bromofuro[2,3-d]pyrimidine, 7-bromofuro[2,3-b]pyrazine, 3-bromothieno[3,2-b]pyridine, 3-bromothieno[2,3-b]pyridine, 3-bromothieno[2,3-c]pyridine, 3-bromothieno[3,2-c]pyridine, 7-bromothieno[3,2-d]pyrimidine, 5-bromothieno[2,3-d]pyrimidine, 7- Use bromothieno[2,3-b]pyrazine, 3-bromo-2-nitropyridine, 4-bromo-3-nitropyridine, 3-bromo-4-nitropyridine, 4-bromo-5 instead of 2-bromo-3-nitropyridine The following intermediates 02 to 135 were synthesized using -nitropyrimidine, 5-bromo-4-nitropyrimidine, and 2-bromo-3-nitropyrazine.

Example 1: Synthesis of compound 1

2.0 g of intermediate 01, 9-(3'-bromo-[1,1'-biphenyl]-3-yl)-9H-carbazole 4.6 g, t-BuONa 1.4 g, Pd ₂ (dba) ₃ 0.35 g, ( t-Bu) ₃ P 0.5 ml was 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 1.77 g of Compound 1 (yield 35%).

m/z: 525.18 (100.0%), 526.19 (40.3%), 527.19 (8.1%), 528.19 (1.2%), 526.18 (1.1%)

Example 2: Synthesis of compound 2

Compound 2 was synthesized in the same manner as in Compound 1, except that Intermediate 05 was used.

m/z: 526.18 (100.0%), 527.18 (40.5%), 528.19 (7.5%), 529.19 (1.0%)

Example 3: Synthesis of compound 3

Compound 3 was synthesized in the same manner as in Compound 1, except that Intermediate 33 was used.

m/z: 542.16 (100.0%), 543.16 (40.0%), 544.16 (8.3%), 544.15 (4.5%), 545.16 (1.9%), 543.15 (1.5%)

Example 4: Synthesis of compound 4

Compound 4 was synthesized in the same manner as in Compound 1, except that Intermediate 86 was used.

m/z: 542.16 (100.0%), 543.16 (40.0%), 544.16 (8.3%), 544.15 (4.5%), 545.16 (1.9%), 543.15 (1.5%)

Example 5: Synthesis of compound 5

Intermediate 29 3.0 g, 3,3'-dibromo-1,1'-biphenyl 4.3 g, t-BuONa 2.1 g, Pd ₂ (dba) ₃ 0.53 g, (t-Bu) ₃ P 0.3 ml 45 ml toluene After dissolving in the reflux was stirred. 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 2.69 g of Compound 5 (yield 33%).

m/z: 598.13 (100.0%), 599.13 (44.4%), 600.12 (9.0%), 600.14 (8.3%), 601.13 (4.0%), 600.13 (1.3%), 601.14 (1.1%)

Example 6: Synthesis of compound 6

Compound 6 was synthesized in the same manner as in Compound 5, except that Intermediate 18 was used.

m/z: 716.27 (100.0%), 717.27 (56.3%), 718.28 (14.5%), 719.28 (2.5%), 718.27 (1.2%)

Example 7: Synthesis of compound 7

3.0 g of Intermediate 01, 3.8 g of 2-bromodibenzo[b,d]thiophene, 1.7 g of t-BuONa, 0.44 g of Pd ₂ (dba) ₃ , and 0.6 ml of (t-Bu) ₃ P were dissolved in 40 ml of toluene and refluxed. stirred. 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 1.78 g of Compound 7 (yield 38%).

m/z: 390.08 (100.0%), 391.09 (27.2%), 392.08 (4.7%), 392.09 (4.0%), 391.08 (1.5%), 393.08 (1.3%)

Example 8: Synthesis of compound 8

Compound 8 was synthesized in the same manner as in Compound 7 using Intermediate 30 and 2-bromodibenzo[b,d]furan.

m/z: 390.08 (100.0%), 391.09 (27.2%), 392.08 (4.7%), 392.09 (4.0%), 391.08 (1.5%), 393.08 (1.3%)

Example 9: Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Compound 7 using Intermediate 26 and 2,8-dibromodibenzo[b,d]thiophene.

m/z: 598.12 (100.0%), 599.12 (42.0%), 600.13 (7.9%), 600.12 (5.7%), 601.12 (2.0%), 601.13 (1.1%)

Example 10: Synthesis of compound 10

Compound 10 was synthesized in the same manner as in Compound 7 using Intermediate 04 and 3-bromo-9-phenyl-9H-carbazole.

m/z: 449.15 (100.0%), 450.16 (33.8%), 451.16 (5.7%), 450.15 (1.1%)

Example 11: Synthesis of compound 11

Compound 11 was synthesized in the same manner as in Compound 7 using the intermediate 11 and 3-bromo-9-phenyl-9H-carbazole.

m/z: 465.13 (100.0%), 466.13 (35.4%), 467.14 (5.5%), 467.13 (5.2%), 468.13 (1.6%)

Example 12: Synthesis of compound 12

Compound 12 was synthesized in the same manner as in Compound 7 using Intermediate 01 and 3,6-dibromo-9-phenyl-9H-carbazole.

m/z: 655.20 (100.0%), 656.20 (49.4%), 657.21 (11.7%), 658.21 (1.9%)

Example 13: Synthesis of compound 13

3.0 g of Intermediate 01 and 0.41 g of NaH were added to 30 ml of DMF and stirred. Here, 4.7 g of 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 45 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 3.36 g of compound 13 (yield 53%).

m/z: 439.14 (100.0%), 440.15 (30.5%), 441.15 (4.7%), 440.14 (1.8%)

Example 14: Synthesis of compound 14

Compound 14 was synthesized in the same manner as in Compound 13, except that Intermediate 02 was used.

m/z: 439.14 (100.0%), 440.15 (30.5%), 441.15 (4.7%), 440.14 (1.8%)

Example 15: Synthesis of compound 15

Compound 15 was synthesized in the same manner as in Compound 13, except that Intermediate 08 was used.

m/z: 455.12 (100.0%), 456.12 (32.9%), 457.12 (5.3%), 457.13 (4.5%), 458.12 (1.5%)

Example 16: Synthesis of compound 16

Compound 16 was synthesized in the same manner as in Compound 13, except that Intermediate 19 was used.

m/z: 514.19 (100.0%), 515.19 (39.0%), 516.20 (6.7%)

Example 17: Synthesis of compound 17

Compound 17 was synthesized in the same manner as in Compound 13 using Intermediate 01 and 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole.

m/z: 528.17 (100.0%), 529.17 (39.0%), 530.18 (6.7%), 530.17 (1.0%)

Example 18: Synthesis of compound 18

Intermediate 01 2.5 g, 4-(3-bromophenyl)-2,6-diphenylpyrimidine 5.6 g, t-BuONa 1.7 g, Pd ₂ (dba) ₃ 0.45 g, (t-Bu) ₃ P 0.6 ml 40 ml toluene After dissolving in the reflux was stirred. 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 2.47 g of Compound 18 (yield 40%).

m/z: 514.18 (100.0%), 515.18 (39.4%), 516.19 (7.1%)

Example 19: Synthesis of compound 19

Compound 19 was synthesized in the same manner as in Compound 18 using Intermediate 01 and 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine.

m/z: 515.17 (100.0%), 516.18 (37.1%), 517.18 (7.6%), 516.17 (1.8%)

Example 20: Synthesis of compound 20

Compound 20 was synthesized in the same manner as in Compound 18 using Intermediate 29 and 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine.

m/z: 531.15 (100.0%), 532.16 (37.0%), 533.16 (6.7%), 533.15 (5.5%), 532.15 (2.6%), 534.15 (1.7%)

Example 21: Synthesis of compound 21

2.0 g of Intermediate 05, 4.4 g of 2-(3-bromophenyl)triphenylene, 4.4 g of t-BuONa, 0.35 g of Pd ₂ (dba) ₃ , and 0.5 ml of (t-Bu) ₃ P were dissolved in 30 ml of toluene and stirred under reflux. did. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and recrystallized after silica filter to obtain 2.1 g of compound 21 (yield 43%).

m/z: 511.17 (100.0%), 512.17 (40.3%), 513.18 (7.5%), 514.18 (1.0%)

Example 22: Synthesis of compound 22

Compound 22 was synthesized in the same manner as in Compound 21, except that Intermediate 12 was used.

m/z: 527.15 (100.0%), 528.15 (40.0%), 529.15 (8.1%), 529.14 (4.5%), 530.14 (1.8%), 528.14 (1.1%)

Example 23: Synthesis of compound 23

Compound 23 was synthesized in the same manner as in Compound 21, except that Intermediate 26 was used.

m/z: 511.17 (100.0%), 512.17 (40.3%), 513.18 (7.5%), 514.18 (1.0%)

Example 24: Synthesis of compound 24

Compound 24 was synthesized in the same manner as in Compound 21, except that Intermediate 33 was used.

m/z: 527.15 (100.0%), 528.15 (40.0%), 529.15 (8.1%), 529.14 (4.5%), 530.14 (1.8%), 528.14 (1.1%)

Example 25: Synthesis of compound 25

Compound 25 was synthesized in the same manner as in Compound 21, except that Intermediate 115 was used.

m/z: 528.14 (100.0%), 529.14 (40.1%), 530.15 (7.0%), 530.14 (5.4%), 531.14 (1.8%)

Manufacture 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 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,

mCP

HI01,

NPB,

mCP

CBP,

비교화합물1,

CBP,

Comparative compound 1,

비교화합물2,

Firpic,

Comparative compound 2,

Firpic,

Ir(ppy)^3,

ET01,

Liq

Ir(ppy) ^3,

ET01,

Liq

Example 26

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 the substrate is cleaned using oxygen plasma for 5 minutes. An 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 the compound 1:Firpic 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 into a film, and the device was encapsulated in a glove box to manufacture a blue organic light emitting device. .

Examples 27-37

In the same manner as in Example 26, blue organic light emitting diodes were fabricated using compounds 2 to 12 as light emitting layer hosts, respectively.

Example 38

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After washing 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 the substrate is 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 10% of the compound 13: Ir(ppy) ₃ 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 a green organic light emitting device was manufactured by encapsulating the device in a glove box. .

Examples 39 to 50

In the same manner as in Example 38, green organic light emitting diodes were fabricated using compounds 14 to 25 as light emitting layer hosts, respectively.

Comparative Example 1

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

Comparative Example 2

A blue 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 device was manufactured in the same manner as in Example 13, except that CBP was used instead of Compound 13 as the host of the light emitting layer.

Comparative Example 4

A green organic light emitting diode was manufactured in the same manner as in Example 13, except that Comparative Compound 1 was used instead of Compound 13 as a host for the light emitting layer of Example 13.

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 26 7.241 12.92 20.09 8.89 0.173 0.293 21 Example 27 7.052 13.10 21.25 8.81 0.171 0.297 20 Example 28 7.003 12.80 22.98 8.96 0.172 0.292 23 Example 29 7.021 13.19 20.95 8.94 0.173 0.291 30 Example 30 7.112 12.79 21.10 8.92 0.175 0.296 29 Example 31 7.103 13.21 20.94 8.94 0.170 0.293 27 Example 32 7.195 13.13 20.17 8.99 0.170 0.297 28 Example 33 7.317 12.88 20.10 8.69 0.170 0.296 29 Example 34 7.018 13.10 21.13 8.64 0.172 0.290 26 Example 35 7.159 12.98 22.89 8.84 0.171 0.295 31 Example 36 7.303 13.10 21.99 8.77 0.175 0.296 30 Example 37 7.207 13.13 23.10 8.79 0.171 0.298 31 Example 38 7.142 13.76 20.23 8.85 0.172 0.292 28 Comparative Example 1 8.032 10.12 13.97 7.26 0.179 0.134 12 Comparative Example 2 7.596 3.32 3.98 2.71 0.179 0.234 - Example 39 6.931 17.33 45.98 19.81 0.301 0.621 42 Example 40 6.987 17.10 47.13 21.03 0.299 0.619 38 Example 41 7.023 16.98 50.20 20.04 0.298 0.620 39 Example 42 6.940 17.54 47.22 19.98 0.300 0.623 37 Example 43 7.085 16.85 48.39 21.23 0.298 0.614 42 Example 44 7.121 17.26 46.83 18.72 0.298 0.609 51 Example 45 7.343 17.01 49.17 22.46 0.297 0.618 49 Example 46 6.920 17.07 45.55 21.98 0.302 0.609 53 Example 47 7.010 16.93 43.62 20.76 0.300 0.620 48 Example 48 7.193 17.36 47.45 18.99 0.299 0.622 40 Example 49 7.110 17.28 51.11 19.54 0.299 0.619 52 Example 50 6.998 17.49 50.29 20.67 0.297 0.620 49 Comparative Example 3 7.824 12.43 38.12 15.74 0.301 0.623 25 Comparative Example 4 7.328 14.56 39.98 17.60 0.300 0.613 36

As shown in Table 1, it can be confirmed that the Examples of the present invention have superior physical properties in all aspects of the organic light emitting device compared to Comparative Examples 1 to 4. In particular, in the case of Comparative Compounds 2 and 4, when applied to a blue phosphorescent device, it was confirmed that the luminous efficiency was low with a triplet energy lower than that of the blue dopant. It can be seen that the luminous efficiency due to the energy is improved.

Claims (3)

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

. 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. 3. The method of claim 2,
The organic light emitting device, characterized in that the organic layer contains the compound of claim 1 as a light emitting host or dopant.

Images