KR20150058082A - Novel electroluminescent compound and organic electroluminescent device comprising same - Google Patents

Abstract

An organic electroluminescent compound of the present invention has excellent charge transfer properties, and high triplet energy and Tg, thereby having low driving voltage, high efficiency, low power consumption, and long life when applied to an organic electroluminescent device.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel luminescent compound, and an organic luminescent device including the luminescent compound.

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

In recent years, an organic light emitting device capable of being driven by a low voltage in a self-luminous mode has a better viewing angle and contrast ratio than a liquid crystal display (LCD), which is a mainstream of a flat panel display device, It has been attracting attention as a next generation display device because it is advantageous in terms of power consumption and has a wide color reproduction range.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending largely on functions. The light emitting material may be classified into a polymer and a low molecular weight depending on the molecular weight, and may be classified into a fluorescent material derived from singlet excitation state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism, Can be classified into blue, green and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color depending on the emission color. Further, in order to increase the color purity and to increase the luminous efficiency through energy transfer, a host / dopant system can be used as a luminescent material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, the light of the desired wavelength can be obtained according to the type of the dopant and the host.

Various compounds have been known as materials used in such organic light emitting devices. However, organic light emitting devices using known materials have been difficult to put to practical use due to high driving voltage, low efficiency, and short lifetime. Accordingly, efforts have been made to develop an organic light emitting device having low voltage driving, high luminance, and long life using a material having excellent characteristics.

In order to solve the above-mentioned problems, the present invention has an excellent charge-transporting property, a high triplet energy and a high Tg, and can provide low driving voltage, high efficiency, low power consumption and long life And to provide a novel luminescent compound having such a structure.

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

In order to accomplish the above object, the present invention provides a luminescent compound represented by the following Formula 1:

[Chemical Formula 1]

In this formula,

X are each independently CR ₀ or N, wherein is at least one of X is N, R ₀ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, an amino group, a nitrile group, a nitro group,

Y is S, O, Se, Te or -NAr ₁ , where Ar ₁ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile, nitro,

R ₁ is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl group, a C _2-30 alkynyl group, C _1-30, C _6-30 A C _6-30 aryl group, or a C _6-50 aryl group unsubstituted or substituted with a C _2-30 heteroaryl group; Or a deuterium, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl group, an alkoxy group an alkynyl group, a C _1-30 of C _2-30, aryl of C _6-30 An aryl group of C _6-30 , or a C _2-50 heteroaryl group which is unsubstituted or substituted with a C _2-30 heteroaryl group,

R ₂ and R ₃ are each independently hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile or nitro.

Also, the present invention provides an organic light emitting device including the compound represented by Formula 1 as an organic material layer as a light emitting material.

The luminescent compound of the present invention is excellent in charge transfer characteristics, has high triplet energy and high Tg, and 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.
The sign
10: substrate
11: anode
12: Hole injection layer
13: hole transport layer
14:
15: electron transport layer
16: cathode

The compound of the present invention is characterized by being represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

X are each independently CR ₀ or N, wherein is at least one of X is N, R ₀ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, an amino group, a nitrile group, a nitro group,

Y is S, O, Se, Te or -NAr ₁ , where Ar ₁ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile, nitro,

R ₁ is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl group, a C _2-30 alkynyl group, C _1-30, C _6-30 A C _6-30 aryl group, or a C _6-50 aryl group unsubstituted or substituted with a C _2-30 heteroaryl group; Or a deuterium, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl group, an alkoxy group an alkynyl group, a C _1-30 of C _2-30, aryl of C _6-30 An aryl group of C _6-30 , or a C _2-50 heteroaryl group which is unsubstituted or substituted with a C _2-30 heteroaryl group,

R ₂ and R ₃ are each independently hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by 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 the above formula (1)

Z is CR ₆ or N, R ₆ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile, nitro,

Ar is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl group, a C _2-30 alkynyl group, C _1-30, C _6-30 of An aryloxy group, a C _6-30 aryl group, or a C _6-38 aryl group unsubstituted or substituted with a C _2-30 heteroaryl group; Or a deuterium, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl group, an alkoxy group an alkynyl group, a C _1-30 of C _2-30, aryl of C _6-30 An aryl group of C _6-30 , or a C _6-38 heteroaryl group which 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 halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-30 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-30 heteroaryl group which is unsubstituted or substituted with a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a nitrile group,

R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; A halogen, an amino group, a nitrile group, a nitro group, a substituted or unsubstituted C _1-30 alkyl group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen atom, a halogen atom, an amino group, a nitrile group, a nitro group; A C _1-30 alkoxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-30 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-30 heteroaryl group which is unsubstituted or substituted with a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a nitrile group,

n is an integer of 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 the formula (1) are as follows:

The compound of formula (I) according to the present invention has excellent charge transfer characteristics, and has high triplet energy and high Tg. Thus, when applied to an organic light emitting device, it can have low driving voltage, high efficiency, low power consumption and long life.

The present invention can also be prepared by the following reaction scheme 1:

[Reaction Scheme 1]

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

[Reaction Scheme 1-1]

The moieties which are not defined in the above reaction formulas are as defined in formula (1).

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

In addition, the organic light emitting device of the present invention includes one or more organic layers including the compound represented by Formula 1, and the method of manufacturing the organic light emitting device will now be described.

The organic light emitting device includes an organic 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 One or more can be included.

First, an anode electrode material having a high work function is deposited on the substrate to form an anode. At this time, the substrate can be a substrate used in conventional organic light emitting devices, and it is particularly preferable to use a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity can be used. The anode electrode material can be deposited by a conventional anode formation method, and specifically, it can be deposited by a deposition method or a sputtering method.

Next, a hole injection layer material may be formed on the anode electrode by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB (Langmuir-Blodgett) method, but it is easy to obtain a uniform film quality, It is preferable to form it by a vacuum evaporation method. When the hole injection layer is formed 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 properties of the desired hole injection layer, and the like. In general, the deposition temperature is 50-500 [ A vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 Å / sec, and a layer thickness range of 10 Å to 5 탆.

The hole injection layer material is not particularly limited and may be a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or a star burst type amine derivative TCTA (4,4 ', 4 "-tri (N-carbazolyl) tri (4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine), m-MTDAPB ^{), HI-406 (N 1} , N 1 '- ( biphenyl-4,4'-diyl) bis (N ¹ - (naphthalen-1-yl) -N ^4, N ⁴ - benzene-1,4-diphenyl -Diamine) can be used as a hole injection layer material.

Next, a hole transporting layer material may be formed on the hole injecting layer by a method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, etc. However, since a uniform film quality can be easily obtained, It is preferably formed by a vapor deposition method. When the hole transporting layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the conditions within the substantially same range as the formation of the hole injection layer.

In addition, the hole transport layer material is not particularly limited, and may be selected from any conventionally known materials used in the hole transport layer. Specifically, the hole transport layer material may be a carbazole derivative such as N-phenylcarbazole or polyvinylcarbazole, a carbazole derivative such as N, N'-bis (3-methylphenyl) -N, N'- Phenyl) -4,4'-diamine (TPD), and N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine Derivatives and the like can be used.

Then, the light emitting layer material may be formed on the hole transporting layer by a method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, etc. However, from the viewpoint of obtaining a uniform film quality and difficulty in producing pin holes, As shown in Fig. When the light emitting layer is formed by the vacuum vapor deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the conditions within the substantially same range as the formation of the hole injection layer. The light emitting layer material may use the compound represented by the formula (1) of the present invention 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 a light emitting layer. At this time, the fluorescent dopant to the possible purchase from Idemitsu Co. (Idemitsu Corporation) IDE102 or IDE105, or BD142 (N ^6, N ^12-bis (3,4-dimethylphenyl) -N ^6, N ¹² - D-mesityl chrysene - as may be used to 6,12- diamine), the phosphorescent dopant is a green phosphorescent dopant Ir (ppy) ₃ (tris (2-phenylpyridine) iridium), a blue phosphorescent dopant F2Irpic (iridium (ⅲ) bis [4,6- Pyridino-N, C2 '] picolinate), UDC's red phosphorescent dopant RD61, and the like can be vacuum vacuum deposited (doped). The doping concentration of the dopant is not particularly limited, but is preferably doped with 0.01 to 15 parts by weight of the dopant relative to 100 parts by weight of the host. If the content of the dopant is less than 0.01 part by weight, the amount of the dopant is not sufficient and color development is not properly performed. If the amount is more than 15 parts by weight, the efficiency is drastically reduced due to the concentration quenching phenomenon.

When the phosphorescent dopant is used together with the phosphorescent dopant, it is preferable to further laminate the hole blocking material (HBL) by a vacuum evaporation method or a spin coating method in order to prevent the triplet exciton or hole from diffusing into the electron transporting layer. The hole blocking material that can be used at this time is not particularly limited, but any known hole blocking material may be used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole blocking material described in Japanese Patent Laid-Open Publication No. 11-329734 (A1) can be exemplified. Typically, Balq (bis Phenanthrolines based compounds such as UDC company BCP (bassocouroin), and the like can be used.

An electron transport layer is formed on the light emitting layer formed as described above. The electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is preferably formed by a vacuum deposition method.

The electron transport layer material serves to stably transport electrons injected from the electron injection electrode. The material is not particularly limited, and examples thereof include quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq ₃ ), Or ET4 (6,6 '- (3,4-dimemethyl-1,1-dimethyl-1H-silanol-2,5-diyl) di-2,2'-bipyridine). 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 laminated on the electron transport layer. Examples of the electron injection layer material include LiF, NaCl, CsF, Li ₂ O, BaO Can be used.

The deposition conditions of the electron transporting layer depend on the compound used, but it is generally preferable to select the conditions within the same range as the formation of the hole injection layer.

Thereafter, an electron injection layer material may be formed on the electron transport layer, and the electron transport layer may be formed by a vacuum deposition method, a spin coating method, a casting method, or the like, .

Finally, a metal for forming a cathode is formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like, and used as a cathode. As the metal for cathode formation, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof can be used. Specific examples thereof include Li, Mg, Al, Al-Li, Ca, Mg-In, Mg-Ag, . Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

The organic light emitting device of the present invention can have an organic light emitting device having various structures as well as an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode structure, Layer or an intermediate layer of two layers may be further formed.

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

In addition, since the organic material layer containing the compound represented by the formula (1) can control the thickness of the organic material layer in the molecular unit, the present invention has advantages of uniform surface and excellent shape stability.

The organic light emitting device of the present invention can realize a low driving voltage, high efficiency, low power consumption and long life by including a compound represented by Chemical Formula 1 having excellent charge transfer characteristics and high triplet energy and high Tg.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Intermediate synthesis

The intermediate is synthesized by ring-opening after the Suzuki reaction according to the following synthesis method.

[Synthesis of Intermediate 01]

[Synthesis of intermediate 1-1]

95.7 g of benzofuran-3-ylboronic acid and 100 g of 2-bromo-3-nitropyridine were dissolved in 1000 ml of toluene, 730 ml of K ₂ CO ₃ (2M) and 17.1 g of Pd (PPh ₃ ) ₄ were added to a round bottom flask, Lt; / RTI > After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 93.4 g (yield 79%) of Intermediate 1-1.

[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, and the mixture was stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification to obtain 28.2 g (yield: 35%) of Intermediate 01.

[Synthesis of other intermediates]

Benzo [b] thiophen-3-ylboronic acid, (1-phenyl-1H-indol-3- yl) boronic acid, 3-bromofuro [3,2- 2,3-c] pyridine, 3-bromofuro [3,2-c] pyridine, 7-bromofuro [3,2- d] pyridine, pyrimidine, 5-bromofuro [2,3-d] pyrimidine, 7-bromofuro [2,3-b] pyrazine, 3-bromothieno [ 3-bromothieno [3,2-c] pyridine, 7-bromothieno [3,2-d] pyrimidine, bromothieno [2,3-b] pyrazine was used instead of 2-bromo-3-nitropyridine and 3-bromo-2-nitropyridine, 4-bromo-3-nitropyridine, -nitropyrimidine, 5-bromo-4-nitropyrimidine and 2-bromo-3-nitropyrazine, the following intermediates 02 to 135 were synthesized.

Example 1: Synthesis of Compound 1

Intermediate 01 2.0 g, 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, ( was dissolved t-Bu) ₃ P 0.5 ml in 30 ml of toluene was stirred under reflux. After the completion of the reaction was confirmed by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification to obtain 1.77 g (yield 35%) of Compound 1.

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

Example 2: Synthesis of Compound 2

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

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

Example 3: Synthesis of Compound 3

Compound 3 was synthesized in the same manner as 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 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

4.3 g of 3,3'-dibromo-1,1'-biphenyl, 2.1 g of t-BuONa, 0.53 g of Pd ₂ (dba) _{3 and} 0.3 ml of (t-Bu) ₃ P were added to 45 ml And the mixture was stirred under reflux. After confirming the termination of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification to obtain 2.69 g (yield 33%) of Compound 5.

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 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

Example 7: Synthesis of Compound 7

3.0 g of the 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, Lt; / RTI > After the completion of the reaction was confirmed by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification to obtain 1.78 g (yield: 38%) of Compound 7.

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 by the same method as Compound 7 using the 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 by the same method as Compound 7 using the above 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

Example 10: Synthesis of Compound 10

Compound 10 was synthesized by the same method as 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

Example 11: Synthesis of Compound 11

Compound 11 was synthesized by the same method as Compound 7 using 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

Example 12: Synthesis of Compound 12

Compound 12 was synthesized by the same method as 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

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. 4.7 g of 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 45 ml of DMF, followed by dropwise addition. After stirring at room temperature, the reaction was terminated by TLC, followed by silica filtration and recrystallization to obtain 3.36 g (yield: 53%) of Compound 13.

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

Example 14: Synthesis of Compound 14

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

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

Example 15: Synthesis of compound 15

Compound 15 was synthesized in the same manner as 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%

Example 16: Synthesis of Compound 16

Compound 16 was synthesized in the same manner as 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 Compound 13 by 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

Example 18: Synthesis of Compound 18

5.6 g of 4- (3-bromophenyl) -2,6-diphenylpyrimidine, 1.7 g of t-BuONa, 0.45 g of Pd ₂ (dba) _{3 and} 0.6 ml of (t-Bu) ₃ P were added to 40 ml And the mixture was stirred under reflux. After completion of the reaction was confirmed by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification to obtain 2.47 g (yield 40%) of Compound 18.

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 Compound 18 by 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

Example 20: Synthesis of Compound 20

Compound 20 was synthesized by the same method as 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%

Example 21: Synthesis of Compound 21

2.0 g of the intermediate 05, 4.4 g of 2- (3-bromophenyl) triphenylene, 1.4 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, Respectively. After confirming the termination of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, filtered through silica, and recrystallized to obtain 2.1 g (yield: 43%) of Compound 21.

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

Example 22: Synthesis of Compound 22

Compound 22 was synthesized in the same manner as 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%

Example 23: Synthesis of Compound 23

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

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

Example 24: Synthesis of Compound 24

Compound 24 was synthesized in the same manner as 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%

Example 25: Synthesis of Compound 25

Compound 25 was synthesized in the same manner as 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

Manufacture of organic light emitting device

An organic light emitting device was prepared according to the structure shown in FIG. The organic light emitting device includes an anode (hole injecting electrode 11) / a hole injecting layer 12 / a hole transporting layer 13 / a light emitting layer 14 / an electron transporting layer 15 / a cathode (electron injecting electrode 16) Respectively.

The following materials were used for the hole injecting layer 12, the hole transporting layer 13, the light emitting layer 14, and the electron transporting 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

The glass substrate coated with thin film of indium tin oxide (ITO) 1500 Å in thickness was washed with distilled water ultrasonic waves. After the distilled water was cleaned, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 5 minutes, and then a thermal vacuum evaporator evaporator) to form a hole injection layer HT01 600 Å and a hole transport layer NPB 250 Å. Next, the light emitting layer was doped with Compound 1: Firpic 10% to form a 250 Å film. Next, ET01: Liq (1: 1) 300 Å was formed as an electron transport layer, LiF 10 Å and aluminum (Al) 1000 Å were formed, and the device was encapsulated in a glove box to fabricate a blue organic light emitting device .

Examples 27 to 37

A blue organic light emitting device formed by using the compounds 2 to 12 as a light emitting layer host was prepared.

Example 38

The glass substrate coated with thin film of indium tin oxide (ITO) 1500 Å in thickness was washed with distilled water ultrasonic waves. After the distilled water was cleaned, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 5 minutes, and then a thermal vacuum evaporator evaporator) to form a hole injection layer HT01 600 Å and a hole transport layer NPB 250 Å. Next, the light emitting layer was doped with 10% of the compound 13: Ir (ppy) ₃ to form a 250 Å film. Next, an ET01: Liq (1: 1) 300 Å film was formed as an electron transport layer, LiF 10 Å and aluminum (Al) 1000 Å were formed, and the device was encapsulated in a glove box to produce a green organic light emitting device .

Examples 39 to 50

A green organic light-emitting device was fabricated in the same manner as in Example 38, using the compounds 14 to 25 as the light-emitting layer host, respectively.

Comparative Example 1

A blue organic light emitting device was fabricated 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 device was fabricated in the same manner as in Example 1 except that Compound 1 was used instead of Compound 1 as the light emitting layer host.

Comparative Example 3

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

Comparative Example 4

A green organic light emitting device was fabricated in the same manner as in Example 13, except that Compound 13 was used instead of Compound 13 as the light emitting layer host.

Evaluation of performance of organic light emitting device

A voltage was applied to the Keithley 2400 source measurement unit to inject electrons and holes and the luminance was measured using a Konica Minolta spectroscope (CS-2000). The performance of the organic light emitting devices of the examples and comparative examples was evaluated by measuring the current density and the luminance with respect to the applied voltage under the atmospheric pressure condition, and the results are shown in Table 1.

Op. V QE (%) Cd / A lm / w CIEx CIEy life span@
1000nit 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 seen that the embodiments of the present invention are superior in physical properties to all aspects of the organic light emitting device in comparison with Comparative Examples 1 to 4. In particular, in the case of Comparative Compounds 2 and 4, it was confirmed that the luminous efficiency was low due to lower triplet energy than the blue dopant when applied to a blue phosphorescent device, The luminous efficiency due to the energy is improved.

Claims (6)

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

In this formula,
X are each independently CR ₀ or N, wherein is at least one of X is N, R ₀ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, an amino group, a nitrile group, a nitro group,
Y is S, O, Se, Te or -NAr ₁ , where Ar ₁ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile, nitro,
R ₁ is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl group, a C _2-30 alkynyl group, C _1-30, C _6-30 A C _6-30 aryl group, or a C _6-50 aryl group unsubstituted or substituted with a C _2-30 heteroaryl group; Or a deuterium, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl group, an alkoxy group an alkynyl group, a C _1-30 of C _2-30, aryl of C _6-30 An aryl group of C _6-30 , or a C _2-50 heteroaryl group which is unsubstituted or substituted with a C _2-30 heteroaryl group,
R ₂ and R ₃ are each independently hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile or nitro. The method according to claim 1,
A luminescent compound, characterized in that it is represented by any one of the following structures:

In the above structures, X and Y are as defined in the above formula (1)
Z is CR ₆ or N, R ₆ is hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-50 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group which is unsubstituted or substituted by deuterium, halogen, amino, nitrile, nitro,
Ar is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl group, a C _2-30 alkynyl group, C _1-30, C _6-30 of An aryloxy group, a C _6-30 aryl group, or a C _6-38 aryl group unsubstituted or substituted with a C _2-30 heteroaryl group; Or a deuterium, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl group, an alkoxy group an alkynyl group, a C _1-30 of C _2-30, aryl of C _6-30 An aryl group of C _6-30 , or a C _6-38 heteroaryl group which 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 halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-30 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-30 heteroaryl group which is unsubstituted or substituted with a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a nitrile group,
R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; A halogen atom, an amino group, a nitrile group, a C _1-30 alkyl group unsubstituted or substituted with a nitro group; A C _2-30 alkenyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _2-30 alkynyl group which is unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; A C _1-30 alkoxy group which is unsubstituted or substituted with a nitro group, a halogen, an amino group, a nitrile group, a nitro group; A C _6-30 aryloxy group _optionally substituted by deuterium, halogen, an amino group, a nitrile group, or a nitro group; A C _6-30 aryl group unsubstituted or substituted with a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-30 heteroaryl group which is unsubstituted or substituted with a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a nitrile group,
n is an integer of 1 to 6, and when n is 1, at least one of X is N. The method according to claim 1,
A luminescent compound represented by any one of the following formulas:

1. A process for preparing a compound represented by the formula (1), which comprises the steps of:
[Reaction Scheme 1]

In the above Reaction Scheme 1, Ar is as defined in Formula 1 above. An organic light emitting device comprising at least one layer of an organic material containing an anode, a cathode, and a compound according to claim 1 between two electrodes. 6. The method of claim 5,
Wherein the organic material layer contains the compound of claim 1 as a light emitting host or a dopant.

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