KR101294620B1 - Electroluminescent device Green using the electroluminescent compounds - Google Patents

Abstract

리간드 L¹ 및 L² 는 서로 독립적으로 하기 구조로부터 선택되고;

M은 2가 또는 3가 금속이며;
M이 2가 금속인 경우 y는 0이고, M이 3가 금속인 경우 y는 1이고;
Q는 (C₆-C₆₀)아릴옥시 또는 트리(C₆-C₃₀)아릴실릴이고, 상기 Q의 아릴옥시 및 트리아릴실릴은 (C₁-C₆₀)알킬 또는 (C₆-C₆₀)아릴이 더 치환될 수 있다.
본 발명에 따른 전기 발광 소자는 색순도 및 발광효율이 우수하다.The present invention relates to an electroluminescent device, and more particularly, the electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one organic light emitting compound of Formula 1 as a host material.
[Formula 1]

Ligands L ¹ and L ² are independently selected from the following structures;

M is a divalent or trivalent metal;
Y is 0 when M is a divalent metal and y is 1 when M is a trivalent metal;
Q is (C ₆ -C ₆₀ ) aryloxy or tri (C ₆ -C ₃₀ ) arylsilyl, wherein aryloxy and triarylsilyl of Q are (C ₁ -C ₆₀ ) alkyl or (C ₆ -C ₆₀ ) Aryl may be further substituted.
The electroluminescent device according to the present invention is excellent in color purity and luminous efficiency.

Description

Electroluminescent device employing organic light emitting compound as light emitting material {Electroluminescent device Green using the electroluminescent compounds}

The present invention relates to an electroluminescent device comprising at least one host compound represented by the following formula (1).

[Formula 1]

Ligands L ¹ and L ² are independently selected from the following structures;

M is a divalent or trivalent metal;

Y is 0 when M is a divalent metal and y is 1 when M is a trivalent metal;

Q is (C ₆ -C ₆₀ ) aryloxy or tri (C ₆ -C ₃₀ ) arylsilyl, wherein aryloxy and triarylsilyl of Q are (C ₁ -C ₆₀ ) alkyl or (C ₆ -C ₆₀ ) Aryl may be further substituted.

Among electroluminescence devices, electroluminescence device (EL device) is a self-emissive type display device which has a wide viewing angle and excellent contrast as well as a high response speed.

EL elements are classified into inorganic EL elements and organic EL elements according to materials for emitting layer formation and light emitting mechanisms. Among them, the organic EL device has a very advantageous advantage in terms of luminous efficiency, color purity, and driving voltage compared to the inorganic EL device has the advantage that it is easy to implement a full-color display.

Meanwhile, in 1987, Eastman Kodak Co., Ltd. developed for the first time an organic EL device using an aromatic complex of diamine and an aluminum complex as a light emitting layer forming material [Appl. Phys. Lett. 51, 913, 1987].

The luminescent material can be divided into a host material and a dopant material in terms of function. Generally, it is known that an EL material has the best EL structure to form a light emitting layer by doping a host with a dopant. In recent years, development of high-efficiency, long-life organic EL devices has become an urgent task. In particular, considering the level of EL characteristics required for middle- or large-sized OLED panels, it is urgent to develop materials superior to conventional light-emitting materials. For this purpose, the desirable characteristics of the host material acting as a solid state solvent and energy transfer agent should be high purity and have a proper molecular weight to enable vacuum deposition. In addition, the glass transition temperature and thermal decomposition temperature must be high to ensure thermal stability, high electrochemical stability is required for longevity improvement, amorphous thin film must be easy to form, and adhesion to other adjacent layers is good, You should not.

Fluorescent materials have been widely used as a luminescent material that plays an important role in determining the luminescence efficiency in OLEDs, but the development of phosphorescent materials is theoretically the best to improve the luminescence efficiency by four times. Known by the method. Until now, materials such as (acac) Ir (btp) ₂ , Ir (ppy) ₃ and Firpic have been known for each RGB as an iridium (III) complex-based phosphorescent light emitting material. Recently, many phosphorescent materials in Korea, Japan and Gumi are known. Are being studied, it is expected that more advanced phosphorescent materials will be released.

4,4'-N, N'-dicarbazole-biphenyl (CBP) is the most widely known host material for phosphorescent light emitting materials, and highly efficient OLEDs using hole blocking layers such as BCP and BAlq have been developed. In addition, Northeast Pioneer, Japan, has developed a high-performance OLED using Bis (2-methyl-8-quinolinato) (p-phenylphenolato) aluminum (III) (BAlq) and its derivatives as hosts for phosphorescent materials. .

However, existing materials have advantages in terms of luminescent properties, but they have disadvantages such as low glass transition temperature and very poor thermal stability, which can cause material changes when subjected to a high temperature deposition process under vacuum. Since the power efficiency in OLED = (π / voltage) × current efficiency, the power efficiency is inversely proportional to the voltage, and the power efficiency of the OLED should be high if the power consumption is low. OLEDs using real phosphorescent materials have significantly higher current efficiency (cd / A) than OLEDs using fluorescent materials. However, when conventional materials such as BAlq and CBP are used as hosts for phosphorescent materials, OLEDs using fluorescent materials (Lm / w) because the driving voltage is higher than that of the conventional device.

A general organic light emitting element is based on a stacked type of an anode / organic light emitting layer / cathode structure, and a hole injection transport layer and an electron injection layer are appropriately provided therein, for example, an anode / hole injection layer / hole transport layer / organic light emitting layer / cathode. ; Anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode; And anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / electron injection layer / cathode; Such structures are known. Various organic compounds may be used as the electron injection layer, the electron transport layer, or the like of the stacked element. Light metal complexes represented by tris (8-quinolinorate) aluminum (Alq ₃ ), oxadiazole, triazole, benzimidazole, benzoxazole, benzothiazole (benzothiazole) and the like, but compounds sufficiently satisfactory in terms of luminescence brightness and durability have not been obtained. Among them, Alq ₃ having excellent stability and high electron affinity has been reported to be the best. However, when used in a blue light emitting device, color purity is lowered due to emission due to exciton diffusion. As such, recent advances for the practical use of electroluminescent devices are remarkable, and their characteristics are low voltage, high brightness, wide variety of light emission wavelengths, high-speed response, and thin light emitting devices. This is essential.

An object of the present invention is a first electrode; A second electrode; And an electroluminescent device comprising at least one organic layer interposed between the first electrode and the second electrode, the electroluminescent device comprising various light emitting dopants using a divalent or trivalent metal complex as the host material on the organic material layer. To provide.

Another object of the present invention is to provide an electroluminescent device having excellent luminous efficiency, excellent color purity, low driving voltage and good driving life.

The present invention relates to an electroluminescent device, and more particularly, the electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one organic light emitting compound of Formula 1 as a host material.

[Formula 1]

Ligands L ¹ and L ² are independently selected from the following structures;

M is a divalent or trivalent metal;

Y is 0 when M is a divalent metal and y is 1 when M is a trivalent metal;

Q is (C ₆ -C ₆₀ ) aryloxy or tri (C ₆ -C ₃₀ ) arylsilyl, wherein aryloxy and triarylsilyl of Q are (C ₁ -C ₆₀ ) alkyl or (C ₆ -C ₆₀ ) Aryl may be further substituted.

X is O, S or Se;

Ring A and Ring B are each independently a 5- to 6-membered heteroaromatic ring or a 5- to 6-membered heteroaromatic ring fused with a (C6-C60) aromatic ring, and the ring A is chemically bonded to R ₁ . Ring A and ring B are (C1-C60) alkyl, halogen, halogen-substituted (C1-C60) alkyl, (C6-C60) aryl, (C4-C60) heteroaryl , Tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino and di (C6-C30) aryl One or more selected from amino may be further substituted;

R ₁ to R ₇ are independently of each other hydrogen, (C 1 -C 60) alkyl, halogen, halogen substituted (C 1 -C 60) alkyl, tri (C 1 -C 30) alkylsilyl, di (C 1 -C 30) alkyl Or (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C60) aryl, (C4-C60) heteroaryl, di (C1-C30) alkylamino or di (C6-C30) arylamino , May combine with adjacent substituents with alkylene or alkenylene to form a fused ring;

The fused ring formed by combining aryl or heteroaryl substituted with ring A and ring B and aryl, heteroaryl or adjacent substituents of R ₁ to R ₇ with alkylene or alkenylene is (C 1 -C 60) alkyl, halogen, cyan Furnace, halogen-substituted (C1-C60) alkyl, (C3-C60) cycloalkyl, (C1-C30) alkoxy, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkyl One selected from the group consisting of silyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino and di (C6-C30) arylamino The above may be further substituted.]

* "Alkyl" or "alkoxy" of the present invention includes both straight and branched chain alkyl or alkoxy groups.

The heteroaromatic ring is a 5- or 6-membered aromatic ring containing one or more N, O or S atoms, for example pyrrole, pyrazole, oxazole, isoxazole, thiazole, isoazole, imidazole , Oxadiazole, thiadiazole, pyridine, pyrazine, pyrimidine or pyridazine. In addition, specific examples of the 5- to 6-membered heteroaromatic ring in which the (C6-C30) aromatic ring is fused include indazole, benzoxazole, benzothiazole, benzoimidazole, phthalazine, quinoxaline, quinazoline, Cinnoline, carbazole, phenanthridine, acridine, quinoline or isoquinoline. The A ring is preferably selected from oxazole, thiazole, imidazole, oxadiazole, thiadiazole, benzoxazole, benzothiazole, benzoimidazole, pyridine or quinoline.

The ligands L ¹ and L ² are independently selected from the following structures.

[X, R ₁ , R ₂ , R ₃ and R ₄ are the same as defined in Formula 1 above;

Y is O, S or NR ₂₄ ;

R ₁₁ to R ₂₃ are each independently hydrogen, (C1-C60) alkyl, halogen, (C1-C60) alkyl substituted by halogen, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1- C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino or di (C6-C30) arylamino, R ₁₃ To R ₁₆ and R ₁₇ to R ₂₀ may be bonded to a substituent adjacent to each other and alkylene or alkenylene to form a fused ring, and the fused ring may be substituted with (C 1 -C 60) alkyl, halogen, cyano, halogen (C1-C60) alkyl, (C3-C60) cycloalkyl, (C1-C30) alkoxy, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkylsilyl, di (C1- One or more selected from the group consisting of C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino and di (C6-C30) arylamino can be further substituted There is;

R ₂₄ is (C 1 -C ₆₀ ) alkyl or (C 6 -C ₆₀ ) aryl;

The aryl or heteroaryl of R ₁₁ to R ₂₄ may be selected from (C1-C60) alkyl, halogen, cyano, halogen-substituted (C1-C60) alkyl, (C3-C60) cycloalkyl, (C1-C30) alkoxy, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di ( One or more selected from the group consisting of C1-C30) alkylamino and di (C6-C30) arylamino may be further substituted.]

The ligands L ¹ and L ² may be independently selected from the following structures.

[X is the same as defined in Formula 1 above;

R ₁ to R ₇ are each independently hydrogen, (C1-C60) alkyl, halogen, halogen-substituted (C1-C60) alkyl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6- C60) arylsilyl, tri (C6-C30) arylsilyl, (C6-C60) aryl, (C4-C60) heteroaryl, di (C1-C30) alkylamino or di (C6-C30) arylamino;

R ₁₁ to R ₂₃ are each independently hydrogen, (C1-C60) alkyl, halogen, (C1-C60) alkyl substituted by halogen, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1- C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino or di (C6-C30) arylamino;

R ₂₄ is (C1-C60) alkyl or (C6-C60) aryl, (C4-C60) heteroaryl;

R ₂₅ to R ₃₂ are each independently hydrogen, (C 1 -C 60) alkyl, halogen, cyano, halogen substituted (C 1 -C 60) alkyl, (C 3 -C 60) cycloalkyl, (C 1 -C 30) alkoxy, ( C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1 -C30) alkylamino or di (C6-C30) arylamino;

The (C6-C60) aryl or (C4-C60) heteroaryl of R ₁ to R ₇ , R ₁₁ to R ₂₃ , R ₂₄ and R ₂₅ to R ₃₂ is (C 1 -C 60) alkyl, halogen, cyano, halogen Substituted (C1-C60) alkyl, (C3-C60) cycloalkyl, (C1-C30) alkoxy, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkylsilyl, di One or more selected from the group consisting of (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino and di (C6-C30) arylamino May be substituted;

The alkyl includes straight chain or branched alkyl.]

In Formula 1, M is a divalent metal selected from the group consisting of Be, Zn, Mg, Cu, and Ni, or a trivalent metal selected from the group consisting of Al, Ga, In, and B, and Q is selected from the following structures: do.

The compound of Formula 1 may be specifically exemplified by the following compounds, but is not limited thereto.

[X is O, S or Se; M is Be, Zn, Mg, Cu or Ni;

R ₁ to R ₇ are independently of each other hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, trimethylsilyl, tri Ethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, dimethylamino, diethylamino or diphenylamino;

R ₁₁ to R ₂₃ independently of one another are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, trimethylsilyl, tri Ethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, dimethylamino, diethylamino or diphenylamino;

R ₂₄ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl Hexyl, n-nonyl, decyl, dodecyl, hexadecyl, phenyl, biphenyl, naphthyl, anthryl or fluorenyl;

R ₂₅ to R ₃₂ independently of one another are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, cyano, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, cyclo Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methoxy, ethoxy, butoxy, hexyloxy, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl , Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t- Butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, dimethylamino, diethylamino or diphenylamino ;

Phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furanyl, thiophenyl, R ₁ to R ₇ , R ₁₁ to R ₂₃ , R ₂₄ and R ₂₅ to R ₃₂ Thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl and benzooxazolyl are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl , n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, cyano, trifluoromethyl, per Fluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methoxy, ethoxy, butoxy, hexyloxy, phenyl, biphenyl , Naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimimi Dazolyl, benzoxazolyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, dimethylamino, diethylamino or diphenylamino One or more selected from may be further substituted.]

In addition, the compound of Formula 1 may be specifically exemplified by the following compounds, but is not limited thereto.

[X is O, S or Se; M is Al, Ga, In or B; Q is (C ₆ -C ₆₀ ) aryloxy or tri (C ₆ -C ₃₀ ) arylsilyl, wherein aryloxy and triarylsilyl of Q are (C ₁ -C ₆₀ ) alkyl or (C ₆ -C ₆₀ ) Aryl may be further substituted;

R ₁ to R ₇ are independently of each other hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, trimethylsilyl, tri Ethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, dimethylamino, diethylamino or diphenylamino;

R ₁₁ to R ₂₃ independently of one another are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, trimethylsilyl, tri Ethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, dimethylamino, diethylamino or diphenylamino;

R ₂₄ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl Hexyl, n-nonyl, decyl, dodecyl, hexadecyl, phenyl, biphenyl, naphthyl, anthryl or fluorenyl;

R ₂₅ to R ₃₂ independently of one another are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, cyano, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, cyclo Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methoxy, ethoxy, butoxy, hexyloxy, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl , Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t- Butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, dimethylamino, diethylamino or diphenylamino ;

Phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furanyl, thiophenyl, R ₁ to R ₇ , R ₁₁ to R ₂₃ , R ₂₄ and R ₂₅ to R ₃₂ Thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl and benzooxazolyl are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl , n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, cyano, trifluoromethyl, per Fluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methoxy, ethoxy, butoxy, hexyloxy, phenyl, biphenyl , Naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimimi Dazolyl, benzoxazolyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, dimethylamino, diethylamino or diphenylamino One or more selected from may be further substituted.]

Compounds of Formula 1 are preferably selected from the following compounds, but are not limited thereto.

In the electroluminescent device according to the present invention, the organic material layer includes a light emitting region, and the light emitting region includes at least one light emitting dopant using 2 to 30% by weight of at least one organic light emitting compound of Formula 1 as a light emitting host. Characterized in that, the light emitting dopant applied to the electroluminescent device of the present invention is not particularly limited, it may be exemplified by a compound represented by the following formula (2).

The organic layer includes a light emitting region, and the light emitting region includes at least one host compound represented by Formula 1 and at least one light emitting dopant represented by Formula 2.

[Formula 2]

Wherein M ¹ is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, and the ligands L ³ , L ⁴ and L ⁵ Are independently selected from the following structures.

[R ₆₁ to R ₆₃ are independently are hydrogen, a halogen substituted or unsubstituted with each other (C ₁ -C ₆₀₎ alkyl, (C ₁ -C ₆₀₎ alkyl is optionally substituted (C ₆ -C ₆₀₎ aryl Or halogen;

R ₆₄ to R ₇₉ are each independently hydrogen, (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₃ -C ₆₀ ) cycloalkyl, (C ₂ -C ₃₀ ) alkenyl, ( C ₆ -C ₆₀ ) aryl, mono or di (C ₁ -C ₃₀ ) alkylamino, mono or di (C ₆ -C ₃₀ ) arylamino, SF ₅ , tri (C ₁ -C ₃₀ ) alkylsilyl, di ( C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) arylsilyl, tri (C ₆ -C ₃₀ ) arylsilyl, cyano or halogen, R ₇₀ and R ₇₆ are adjacent to each other a substituent and (C ₂ -C ₁₂ ) May be combined with an alkylene or (C ₂ -C ₁₂ ) alkenylene to form a fused or multifused ring, wherein the alkyl, cycloalkyl, alkenyl, aryl of R ₆₄ to R ₇₉ or R ₇₀ and R ₇₆ The fused or multifused ring formed by linking with this alkylene or alkenylene may be further substituted with one or more substituents selected from (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl or halogen;

R ₈₀ to R ₈₃ are independently hydrogen, halogen is optionally substituted (C ₁ -C ₆₀₎ alkyl or (C ₁ -C ₆₀₎ alkyl is optionally substituted (C ₆ -C ₆₀₎ aryl each other ;

R ₈₄ and R ₈₅ are independently of each other hydrogen, straight chain or branched (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl or halogen, or R ₈₄ and R ₈₅ may or may not contain a fused ring Linked with (C ₃ -C ₁₂ ) alkylene or (C ₃ -C ₁₂ ) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, wherein the alkyl, aryl or fused ring of R ₈₄ and R ₈₅ with or without a (C ₃ -C ₁₂₎ alkylene or (C ₃ -C ₁₂₎ cycloaliphatic ring, or a monocyclic or polycyclic aromatic ring formed alkenylene or is a halogen-substituted or unsubstituted, linear Crushed (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, halogen, tri (C ₁ -C ₃₀ ) alkylsilyl, tri (C ₆ -C ₃₀ ) arylsilyl and (C ₆ -C ₆₀ May be further substituted with one or more substituents selected from aryl;

R ₈₆ is (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl, (C ₅ -C ₆₀ ) heteroaryl or halogen;

R ₈₇ to R ₉₀ are independently of each other hydrogen, (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl or halogen, wherein the alkyl and aryl of R ₈₆ to R ₈₈ are halogen or (C ₁ -C ₆₀ ) may be further substituted with alkyl;

,

또는

이며, R₁₀₁ 내지 R₁₁₂는 서로 독립적으로 수소, 할로겐이 치환되거나 치환되지 않은 (C₁-C₆₀)알킬, (C₁-C₃₀)알콕시, 할로겐, (C₆-C₆₀)아릴, 시아노, (C₅-C₆₀)시클로알킬이거나, R₁₀₁ 내지 R₁₁₂는 서로 인접한 치환체와 알킬렌 또는 알케닐렌으로 연결되어 (C₅-C₇)스피로고리 또는 (C₅-C₉)융합고리를 형성하거나 R₆₇ 또는 R₆₈과 알킬렌 또는 알케닐렌으로 연결되어 (C₅-C₇)융합고리를 형성할 수 있다.]
Z is

,

or

R ₁₀₁ to R ₁₁₂ independently of one another are hydrogen, a substituted or unsubstituted (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, halogen, (C ₆ -C ₆₀ ) aryl, cyan Or a (C ₅ -C ₆₀ ) cycloalkyl, or R ₁₀₁ to R ₁₁₂ are linked to a substituent adjacent to each other with alkylene or alkenylene to form a (C ₅ -C ₇ ) spirocycle or (C ₅ -C ₉ ) fused ring Or R ₆₇ or R ₆₈ and alkylene or alkenylene to form a (C ₅ -C ₇ ) fused ring.]

M ¹ is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag, ligand L ³ of the compound of Formula 2, L ⁴ and L ⁵ Are independently selected from the following structures, but are not limited thereto.

[R ₆₄ to R ₇₉ are independently of each other hydrogen, (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₃ -C ₆₀ ) cycloalkyl, (C ₂ -C ₁₂ ) alkenyl, (C ₆ -C ₆₀ ) aryl, mono or di (C ₁ -C ₃₀ ) alkylamino, mono or di (C ₆ -C ₃₀ ) arylamino, SF ₅ , tri (C ₁ -C ₃₀ ) alkylsilyl, di (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) arylsilyl, tri (C ₆ -C ₃₀ ) arylsilyl, cyano or halogen;

The alkyl, cycloalkyl, alkenyl or aryl of R ₆₄ to R ₇₉ may be further substituted with one or more substituents selected from (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl or halogen;

R ₈₀ to R ₈₁ independently represent hydrogen, halogen-substituted or unsubstituted (C ₁ -C ₆₀₎ alkyl or (C ₁ -C ₆₀₎ alkyl is optionally substituted (C ₆ -C ₆₀₎ aryl, ;

R ₈₅ is independently of each other hydrogen, straight chain or branched (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl or halogen, wherein alkyl or aryl of R ₈₅ is straight or unsubstituted or substituted with halogen; Crushed (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, halogen, tri (C ₁ -C ₃₀ ) alkylsilyl, tri (C ₆ -C ₃₀ ) arylsilyl and (C ₆ -C ₆₀ May be further substituted with one or more substituents selected from aryl;

R ₈₆ is (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl or halogen, wherein the alkyl and aryl of R ₈₆ may be further substituted with halogen or (C ₁ -C ₆₀ ) alkyl;

R ₉₁ to R ₉₈ are each independently hydrogen, halogen substituted or unsubstituted, straight chain or branched (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, halogen, tri (C ₁ -C ₃₀ ) Alkylsilyl, tri (C ₆ -C ₃₀ ) arylsilyl or (C ₆ -C ₆₀ ) aryl;

R ₁₀₁ to R ₁₀₈ , R ₁₁₁ and R ₁₁₂ independently of one another are hydrogen, halogen substituted or unsubstituted (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, halogen, (C ₆ -C ₆₀ ) Aryl, cyano, (C ₅ -C ₆₀ ) cycloalkyl.]

The dopant compound of Formula 2 may be specifically exemplified as a compound having the following structure, but is not limited thereto.

The electroluminescent device of the present invention has excellent luminous efficiency, good color purity, and low driving voltage, and has a very good driving life.

Figure 1-Cross-sectional view of OLED device

Hereinafter, the light emitting characteristics of the novel electroluminescent device according to the present invention will be described based on the preparation examples and examples, but the following examples are provided to help the understanding of the present invention. It is not limited to the embodiment of.

[Manufacturing Example]

Preparation Example 1 to Preparation Example 18 are described in Korean Patent Registration No. 0684109.

Preparation Example 1 Preparation of Compound 101

1.0 g (5.84 mmol) of 2-pyridin-2-yl-phenol was dissolved in 50 mL of methanol, followed by addition of 10 mL of 1 M aqueous sodium hydroxide solution. To the mixed solution was added dropwise 10 mL of methanol solution (methanol 7 mL: 3 mL of water) in which 1.05 g (5.93 mmol) of beryllium sulfate tetrahydrate was added dropwise, followed by stirring at room temperature for 2 hours. After stirring was complete, 1.54 g (7.30 mmol) of 2-hydroxy-phenyl benzoxazole dissolved in 50 mL of methanol was slowly added. The reaction solution was stirred at room temperature for 2 hours and then heated to 50 ° C. and stirred for 10 hours. After stirring was complete, the resulting precipitate was filtered, washed with 50 mL of water and 50 mL of acetone, and dried to give 0.80 g (2.04 mmol, 34% yield) of the title compound ( 101 ).

MS / FAB: 391 (found), 391.43 (calculated)

EA: C 73.55%, H 4.59%, N 7.05%, O 12.41%

Preparation Example 2 Preparation of Compound 102

1.0 g (5.84 mmol) of 2-pyridin-2-yl-phenol was dissolved in 50 mL of methanol, followed by addition of 10 mL of 1 M aqueous sodium hydroxide solution. 10 mL of a methanol solution of 0.95 g (5.18 mmol) of zinc acetate was added dropwise to the mixed solution, followed by stirring at room temperature for 2 hours. After stirring was completed, 1.50 g (7.10 mmol) of 2-hydroxy-phenyl benzoxazole dissolved in 50 mL of methanol was slowly added thereto, followed by stirring at room temperature for 10 hours. After stirring was complete, the resulting precipitate was filtered, washed with 50 mL of water and 50 mL of acetone, and dried to give 0.72 g (1.61 mmol, 27% yield) of the title compound 102 .

MS / FAB: 447 (found), 447.79 (calculated)

EA: C 64.22%, H 4.01%, N 6.05%, O 10.95%

Preparation Example 3 Preparation of Compound 103

1.23 g (5.82 mmol) of 2-hydroxy-phenyl benzoxazole, 1.48 g (7.58 mmol) of 10-hydroxybenzo [h] quinoline and beryllium sulfate 0.35 g (0.84 mmol, 14% yield) of the title compound 103 was obtained in the same manner as in Preparation Example 1, using 1.05 g (5.93 mmol) of (beryllium sulfate) tetrahydrate.

MS / FAB: 415 (found), 415.46 (calculated)

EA: C 75.02%, H 4.27%, N 6.64%, O 11.65%

Preparation Example 4 Preparation of Compound 104

1.23 g (5.82 mmol) of 2-hydroxy-phenyl benzoxazole, 1.48 g (7.58 mmol) of zinc acetate and 10-hydroxybenzo [h] quinoline (Zinc acetate) 0.95 g (5.18 mmol) was used in the same manner as in Preparation Example 2, to obtain 0.52 g (1.10 mmol, 19%) of the title compound 104.

MS / FAB: 471 (found), 471.81 (calculated)

EA: C 66.08%, H 3.79%, N 5.84%, O 10.30%

Preparation Example 5 Preparation of Compound 105

1.23 g (5.82 mmol) of 2-hydroxy-phenyl benzoxazole, 1.72 g (7.57 mmol) of 2-hydroxy-phenyl benzothiazole and beryllium sulfate 0.95 g (2.15 mmol, 37% yield) of the title compound 105 was obtained in the same manner as in Preparation Example 1, using 1.05 g (5.93 mmol) of beryllium sulfate) tetrahydrate.

MS / FAB: 447 (found), 447.52 (calculated)

EA: C 69.68%, H 4.01%, N 6.16%, O 10.85% S 7.05%

Preparation Example 6 Preparation of Compound 106

1.23 g (5.82 mmol) of 2-hydroxy-phenyl benzoxazole, 1.72 g (7.57 mmol) of 2-hydroxy-phenyl benzothiazole and zinc acetate ( 1.36 g (2.70 mmol, yield 46%) of the title compound 106 was obtained by the same method as Preparation Example 2, using 0.95 g (5.18 mmol) of zinc acetate).

MS / FAB: 503 (found), 503.88 (calculated)

EA: C 61.88%, H 3.54%, N 5.46%, O 9.73%, S 6.26%

Preparation Example 7 Preparation of Compound 107

1.32 g (5.80 mmol) of 2-hydroxy-phenyl benzothiazole, 1.30 g (7.59 mmol) of 2-pyridin-2yl-phenol and 1.05 g of beryllium sulfate tetrahydrate 5.93 mmol) was obtained in the same manner as in Preparation Example 1 to obtain 0.59 g (1.45 mmol, yield 25%) of the title compound 107.

MS / FAB: 407 (found), 407.50 (calculated)

EA: C 70.64%, H 4.35%, N 6.76%, O 7.96%, S 7.75%

Preparation Example 8 Preparation of Compound 108

1.32 g (5.80 mmol) of 2-hydroxy-phenyl benzothiazole, 1.30 g (7.59 mmol) of 2-pyridin-2yl-phenol and 0.95 g (5.18 mmol) of zinc acetate ), 0.83 g (1.79 mmol, yield 31%) of the title compound 108 was obtained in the same manner as in Preparation Example 2).

MS / FAB: 463 (found), 463.86 (calculated)

EA: C 62.04%, H 3.82%, N 5.98%, O 7.02%, S 6.83%

Preparation Example 9 Preparation of Compound 109

1.32 g (5.80 mmol) of 2-hydroxy-phenyl benzothiazole, 10-hydroxybenzo [h] quinoline (10-hydroxybenzo [h] instead of 2-hydroxy-phenyl benzoxazole 0.98 g (2.27 mmol, yield 39%) of the title compound (109) was obtained by the same method as Preparation Example 1, using 1.48 g (7.58 mmol) of quinoline and 1.05 g (5.93 mmol) of beryllium sulfate (4). It was.

MS / FAB: 431 (found), 431.52 (calculated)

EA: C 72.22%, H 4.10%, N 6.40%, O 7.62%, S 7.33%

Preparation Example 10 Preparation of Compound 110

1.32 g (5.80 mmol) 2-hydroxy-phenyl benzothiazole, 1.48 g (7.58 mmol) and zinc 10-hydroxybenzo [h] quinoline 0.95 g (5.18 mmol) of acetate was used to obtain 1.22 g (2.50 mmol, 43%) of the title compound 110 in the same manner as in Preparation Example 4.

MS / FAB: 487 (found), 487.88 (calculated)

EA: C 63.93%, H 3.65%, N 5.64%, O 6.70%, S 6.44%

Preparation Example 11 Preparation of Compound 111

1.23 g (5.82 mmol) of 2-hydroxy-phenyl benzoxazole, 2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl- 1 H-bezoimidazol-2-yl) -phenol) 2.17 g (7.58 mmol) and beryllium sulfate tetrahydrate 1.05 g (5.93 mmol) were used in the same manner as in Preparation Example 1, 0.56 g of the compound 111. (1.11 mmol, yield 19%) was obtained.

MS / FAB: 506 (found), 506.57 (calculated)

EA: C 75.67%, H 4.50%, N 8.20%, O 9.68%

Preparation Example 12 Preparation of Compound 112

1.23 g (5.82 mmol) of 2-hydroxy-phenyl benzoxazole, 2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl- 1H-bezoimidazol-2-yl) -phenol) 2.17 g (7.58 mmol) 2.17 g (7.58 mmol) and 0.95 g (5.18 mmol) zinc acetate were used for the title compound in the same manner as in Preparation Example 2. 0.72 g (1.28 mmol, yield 22%) of compound 112 were obtained.

MS / FAB: 562 (found), 562.93 (calculated)

EA: C 68.16%, H 4.05%, N 7.36%, O 8.68%

Preparation Example 13 Preparation of Compound 113

2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl-1H-bezoimidazol-2-yl) -phenol) 1.67 g (5.83 mmol), 2-pyridine-2 0.84 g (1.80 mmol, 31% yield) of the title compound 113 in the same manner as in Preparation Example 1, using 1.30 g (7.59 mmol) of mono-phenol and 1.05 g (5.93 mmol) of beryllium sulfate tetrahydrate. Obtained.

MS / FAB: 466 (found), 466.55 (calculated)

EA: C 77.08%, H 4.87%, N 8.90%, O 6.98%

Preparation Example 14 Preparation of Compound 114

2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl-1H-bezoimidazol-2-yl) -phenol) 1.67 g (5.83 mmol), 2-pyridine-2 0.88 g (1.68 mmol, yield 29%) of the title compound 114 was obtained by the same method as Preparation Example 2, using 1.30 g (7.59 mmol) of mono-phenol and 0.95 g (5.18 mmol) of zinc acetate. It was.

MS / FAB: 522 (found), 522.91 (calculated)

EA: C 68.81%, H 4.33%, N 7.92%, O 6.32%

Preparation Example 15 Preparation of Compound 115

2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl-1H-bezoimidazol-2-yl) -phenol) 1.67 g (5.83 mmol), 10-hydroxybenzo Compound 115, the title compound, in the same manner as in Preparation Example 1, using 1.50 g (7.68 mmol) of [h] quinoline (10-hydroxybenzo [h] quinoline) and 1.05 g (5.93 mmol) of beryllium sulfate tetrahydrate. 0.26 g (0.53 mmol, 9% yield) were obtained.

MS / FAB: 490 (found), 490.57 (calculated)

EA: C 78.20%, H 4.68%, N 8.42%, O 6.70%

Preparation Example 16 Preparation of Compound 116

2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl-1H-bezoimidazol-2-yl) -phenol) 1.67 g (5.83 mmol), 10-hydroxybenzo 0.42 g of Compound 116, the title compound, in the same manner as in Preparation Example 2, using 1.50 g (7.68 mmol) of [h] quinoline (10-hydroxybenzo [h] quinoline) and 0.95 g (5.18 mmol) of zinc acetate. (0.77 mmol, 13% yield) was obtained.

MS / FAB: 546 (found), 546.93 (calculated)

EA: C 70.13%, H 4.16%, N 7.58%, O 5.98%

Preparation Example 17 Preparation of Compound 117

1.32 g (5.80 mmol) 2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl) 2-hydroxy-phenyl benzothiazole -1H-bezoimidazol-2-yl) -phenol) 2.17 g (7.58 mmol) and 1.05 g (5.93 mmol) of beryllium sulfate tetrahydrate were used as the title compound in the same manner as in Preparation Example 1, 0.64 g of the compound 117. (1.22 mmol, 21% yield) was obtained.

MS / FAB: 522 (found), 522.64 (calculated)

EA: C 73.42%, H 4.34%, N 7.97%, O 6.25%, S 6.04%

Preparation Example 18 Preparation of Compound 118

1.32 g (5.80 mmol) 2- (1-phenyl-1H-benzoimidazol-2-yl) -phenol (2- (1-phenyl) 2-hydroxy-phenyl benzothiazole -1H-bezoimidazol-2-yl) -phenol) using 2.17 g (7.58 mmol) and 0.95 g (5.18 mmol) of zinc acetate in the same manner as in Preparation Example 2 0.94 g (1. 1.62 mmol, yield 28%) was obtained.

MS / FAB: 578 (found), 578.99 (calculated)

EA: C 66.22%, H 3.94%, N 7.16%, O 5.70%, S 5.49%

Preparation Example 19 Preparation of Compound 119

compound A Manufacturing

5-bromo-2-hydroxybenzaldehyde (20.0 g, 99.5 mmol), phenyl boronic acid (13.4 g, 109.5 mmol), tetrakis palladium (0) triphenylphosphine ( Pd (PPh ₃ ) ₄ ) (5.8 g, 5.0 mmol) was dissolved in dimethylethylene glycol (200 mL) and ethanol (100 mL), then 2M aqueous potassium carbonate solution (132 mL) was added thereto, and the mixture was stirred under reflux for 4 hours at 90 ° C. . When the reaction was completed, the mixture was quenched with water (100 mL), extracted with ethyl acetate (200 mL), and dried under reduced pressure. This was separated by silica gel column chromatography (n-Hexane: MC = 1: 5) to give a compound A (12.0 g, 61.0 mmol).

compound B Manufacturing

2-aminobenzenethiol (3.8 g, 30.2 mmol) and Compound A (5.0 g, 25.2 mmol) were dissolved in 1,4-dioxane (12 mL) and stirred under pressure at 100 ° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane (100 mL) and water (100 mL), and dried under reduced pressure. This was separated by silica gel column chromatography (n-Hexane: MC = 3: 1) to give a compound B (4.5 g, 4.8 mmol).

compound 119 Manufacturing

Compound B (4.5 g, 14.8 mmol) and sodium hydroxide (0.6 g, 14.8 mmol) were added thereto, dissolved in ethanol (100 mL), and stirred for 30 minutes. Zn (CH ₃ COO) ₂ .2H ₂ O (1.8 g, 8.2 mmol) was added slowly. Then stirred at room temperature for 12 hours. After the reaction was completed, the mixture was washed with water (200 mL), ethanol (200 mL) and hexane (200 mL), and dried under reduced pressure to obtain the title compound 119 (4.5 g, 6.7 mmol, 45%).

Preparation Example 20 Preparation of Compound 179

compound C Manufacturing

Dissolve 5-iodoindoline-2,3-dione (10.0 g, 36.6 mmol) and phenylboronic acid (5.4 g, 43.9 mmol) in dimethylene glycol (600 mL) Tetrakis palladium (0) triphenylphosphine (Pd (PPh ₃ ) ₄ ) (2.1 g, 1.8 mmol) and 2M aqueous sodium carbonate solution (120 mL) were added. The mixture was stirred under reflux for 12 hours, and when the reaction was completed, the solvent was removed, and 120 mL of 5% aqueous sodium hydroxide solution was added to the remaining filtrate, followed by stirring at room temperature. The aqueous solution was extracted with dichloromethane, the water layer was collected, 120 mL of 30% hydrogen peroxide solution was added, and the temperature was raised to 50 ° C and stirred for 30 minutes. After cooling to room temperature, 1N aqueous hydrochloric acid solution was slowly added to the aqueous solution to adjust the pH to 4. At this time, a solid was produced, which was filtered under reduced pressure to obtain compound C (5.5 g, 26.0 mmol).

compound D Manufacturing

Compound C (7.1 g, 33.3 mmol) was dissolved in water (18 mL) and concentrated hydrochloric acid (7 mL) and stirred at room temperature. After 10 minutes, the temperature was lowered to 0 ° C. and sodium nitrate (NaNO ₃ ) (2.3 g, 33.3 mmol) dissolved in water (10 mL) was added slowly. Then stirred while maintaining 0 ℃. In another reaction vessel, dissolve sodium sulfide nonahydrate (Na ₂ S9H ₂ O) (9.6 g, 39.9 mmol) and sulfur (1.3 g, 39.9 mmol) in water (10 mL), and then add 4 mL of 10M aqueous sodium hydroxide solution. Added. It was added to the reaction mixture at 0 ° C. and then stirred at room temperature until no gas was generated. After the reaction was completed, concentrated hydrochloric acid was added until a solid was formed, which was then filtered under reduced pressure. The obtained solid was poured into aqueous sodium hydrocarbonate (NaHCO ₃ ) solution (85 mL), stirred at reflux for 20 minutes, cooled to room temperature, and then the solid product (purity) was removed. Then, concentrated hydrochloric acid was added to the aqueous solution to form a solid. The solid obtained by filtration under reduced pressure was added to ethanol (30 mL) again and stirred under reflux for 20 minutes. Undissolved solids (impurities) were removed and the filtrate was concentrated. Zinc (2.2 g, 33.3 mmol) and glacial acetic acid (30 mL) were added thereto, and the mixture was stirred under reflux for 48 hours. After the reaction was completed, the mixture was cooled to room temperature, and the resulting solids were collected and poured into 5M aqueous sodium hydroxide solution (63 mL), followed by stirring under reflux for 30 minutes. The undissolved solids were removed (impurity) and acidified by adding a little hydrochloric acid to the aqueous solution. At this time, a solid was formed, which was collected and added to ethanol (20 mL) and stirred under reflux for 30 minutes. The undissolved solid (impurity) was removed and the filtrate was concentrated to give compound D (1.8 g, 7.6 mmol).

compound E Manufacturing

Compound D (5.0 g, 21.7 mmol), 2-aminobenzenethiol (2.1 mL, 19.5 mmol) and polyphosphoric acid (20 g) were added thereto, and the mixture was stirred under reflux at 140 ° C. for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, and then saturated sodium hydroxide aqueous solution was slowly added to adjust pH to neutrality. At this time, a solid was produced, which was filtered under reduced pressure to obtain a solid. The obtained solid was washed with ethanol and dried to give compound E (5.4 g, 17.1 mmol).

compound 179 Manufacturing

Compound E (50 g, 15.6 mmol) and sodium hydroxide (0.6 g, 15.6 mmol) were dissolved in ethanol (100 mL) and stirred for 30 minutes, followed by Zn (CH ₃ COO) ₂ .2H ₂ O (1.9 g, 8.7 mmol) was added slowly and stirred at rt for 12 h. After stirring was complete, washed with water (200 mL), ethanol (200 mL) and hexane (200 mL) and dried under reduced pressure to give the title compound 179 (7.1 g, 10.1 mmol, 65%).

Compounds 19 to 336 of Table 1 were prepared in the same manner as in Preparation Examples 19 and 20. Table 1 shows ¹ H NMR and MS / FAB. Table 1 below is a compound in which M is a divalent metal.

[Table 1]

Preparation Example 21 Preparation of Compound 337

Compound B (4.5 g, 14.8 mmol) and aluminum isopropoxide (3.0 g, 14.8 mmol) were dissolved in chloroform (50 mL) / isopropyl alcohol (150 mL) and stirred at 60 ° C. for 3 hours. When it became transparent, 4-phenylphenol (3.0 g, 17.8 mmol) was added thereto, and the mixture was stirred under reflux at 80 ° C. for 3 hours. Compound B (4.5 g, 14.8 mmol) was further added, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the resulting solid was filtered off under reduced pressure, which was then washed with isopropyl alcohol (500 mL), methanol (300 mL) and ethyl ether (250 mL), respectively, to obtain the title compound 337 (3.8 g, 7.6). mmol, 51%).

Compounds 337 to 426 of Table 3 were prepared by the same method as Preparation Example 21, and ¹ H NMR and MS / FAB are shown in Table 4 below. The compounds in Table 3 below are compounds wherein M is a trivalent metal.

[Table 3]

[Table 4]

Example 1 Fabrication of OLED Device

OLED devices were fabricated using the red phosphorescent compounds according to the invention.

First, the transparent electrode ITO thin film (15 Ω / □, 2) obtained from the OLED glass (manufactured by Samsung Corning Co., Ltd.) (1) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol, and distilled water sequentially, and then isopropanol It was used after storing in.

Next, the ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (2-TNATA) is installed in the cell in the vacuum deposition apparatus. After the evacuation and evacuation until the vacuum in the chamber reached 10 ⁻⁶ torr, a current was applied to the cell to evaporate 2-TNATA to deposit a hole injection layer 3 having a thickness of 60 nm on the ITO substrate.

Then, to another cell of the vacuum vapor-deposit device N, N '-bis (α- naphthyl) - N, N' into the -diphenyl-4,4'-diamine (NPB) , and evaporation of the NPB by applying a current to the cell A 20 nm thick hole transport layer 4 was deposited on the hole injection layer.

In addition, H-26, which is a light emitting host material according to the present invention, is placed in another cell in the vacuum deposition apparatus, and Compound D-4, which is a red phosphorescent compound according to the present invention, is placed in another cell, and then the two materials are mixed at different speeds. A 30 nm thick light emitting layer 5 was deposited on the hole transport layer by evaporation and doping. The doping concentration at this time is suitable 4 to 10 mol% based on the host.

Subsequently, tris (8-hydroxyquinoline) -aluminum (III) (Alq) was deposited as an electron transport layer 6 to a thickness of 20 nm. Next, after depositing lithium quinolate (Liq) with an electron injection layer 7 to a thickness of 1 to 2 nm, an Al cathode 8 was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED.

Comparative Example 1 Fabrication of Devices Using Existing Phosphorescent Hosts

After the hole injection layer and the hole transport layer were formed in the same manner as in Example 1, the light emitting layer was deposited thereon as follows. 4,4'-N, N ', which is a light emitting host material, was deposited in another cell in the vacuum deposition apparatus. -dicarbazole-biphenyl (CBP) was added, and another cell was added with a red phosphorescent compound (D-4) according to the present invention, followed by evaporation and doping of the two materials at different rates. (5) was deposited. The doping concentration at this time is 4 to 10 mol% is appropriate based on CBP.

Subsequently, Bis (2-methyl-8-quinolinato) ( p- phenylphenolato) aluminum (III) (BAlq) was deposited to a thickness of 10 nm using a hole blocking layer on the light emitting layer in the same manner as in NPB. 6) tris (8-hydroxyquinoline)-aluminum (III) (Alq) was deposited to a thickness of 20 nm. Next, after depositing lithium quinolate (Liq) with an electron injection layer 7 to a thickness of 1 to 2 nm, an Al cathode 8 was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED.

[ Experimental Example  1] OLED  Device Characterization

In order to confirm the performance of the OLED device of Example 1 containing the electroluminescent compound according to the present invention and the OLED device containing the conventional light emitting compound according to the present invention prepared in Comparative Example 1 of the OLED at 10 mA / cm ² The luminous efficiency was measured, and various properties are shown in Table 5 below.

[Table 5]

When the device was manufactured using the host and the dopant according to the present invention, a red phosphorescent light emitting device having a high efficiency of up to 12.6 cd / A was able to be manufactured, and the host of the present invention was used without using a hole blocking layer. It shows an efficiency equal to or higher than that of CBP, a phosphorescent light emitting host, and has an effect of significantly lowering power consumption of OLED devices by lowering a driving voltage of 0.9 to 1.7 V. When applied to mass production of OLED devices, mass production time is also remarkable. It is expected to be of great help in commercialization as it can be reduced.

1-Glass 2-Transparent Electrode
3-Hole injection layer 4-Hole transfer layer
5-Light Emitting Layer 6-Electron Transport Layer
7-electron injection layer 8-Al cathode

Claims (5)

A first electrode;
A second electrode; And
In the electroluminescent device consisting of at least one organic layer interposed between the first electrode and the second electrode,
The organic material layer is an electroluminescent device comprising at least one host compound represented by the formula (1).
[Formula 1]

In Formula 1, the ligands L ¹ and L ² are independently selected from the following structures;

M is a divalent metal selected from the group consisting of Be, Zn, Mg, Cu and Ni;
y is 0;
Q is (C6-C60) aryloxy or tri (C6-C30) arylsilyl, wherein aryloxy and triarylsilyl of Q may be further substituted with (C1-C60) alkyl or (C6-C60) aryl;
X is O, S or Se;
R ₁ to R ₇ are each independently hydrogen, (C1-C60) alkyl, halogen, halogen-substituted (C1-C60) alkyl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6- C60) arylsilyl, tri (C6-C30) arylsilyl, (C6-C60) aryl, (C4-C60) heteroaryl, di (C1-C30) alkylamino or di (C6-C30) arylamino;
R ₁₁ to R ₂₃ are each independently hydrogen, (C1-C60) alkyl, halogen, (C1-C60) alkyl substituted by halogen, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1- C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino or di (C6-C30) arylamino;
R ₂₄ is (C1-C60) alkyl, (C6-C60) aryl or (C4-C60) heteroaryl;
R ₂₅ to R ₃₂ are each independently hydrogen, (C 1 -C 60) alkyl, halogen, cyano, halogen substituted (C 1 -C 60) alkyl, (C 3 -C 60) cycloalkyl, (C 1 -C 30) alkoxy, ( C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1 -C30) alkylamino or di (C6-C30) arylamino;
The (C6-C60) aryl or (C4-C60) heteroaryl of R ₁ to R ₇ , R ₁₁ to R ₂₃ , R ₂₄ and R ₂₅ to R ₃₂ is (C 1 -C 60) alkyl, halogen, cyano, halogen Substituted (C1-C60) alkyl, (C3-C60) cycloalkyl, (C1-C30) alkoxy, (C6-C60) aryl, (C4-C60) heteroaryl, tri (C1-C30) alkylsilyl, di One or more selected from the group consisting of (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkylamino and di (C6-C30) arylamino Can be substituted. The method of claim 1,
The compound of Chemical Formula 1 is selected from the following compounds.

X is O, S or Se; M is Be, Zn, Mg, Cu or Ni;
R ₁ to R ₇ are independently of each other hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, trimethylsilyl, tri Ethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, dimethylamino, diethylamino or diphenylamino;
R ₁₁ to R ₂₃ independently of one another are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, trimethylsilyl, tri Ethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, dimethylamino, diethylamino or diphenylamino;
R ₂₄ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl Hexyl, n-nonyl, decyl, dodecyl, hexadecyl, phenyl, biphenyl, naphthyl, anthryl or fluorenyl;
R ₂₅ to R ₃₂ independently of one another are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, cyano, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, cyclo Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methoxy, ethoxy, butoxy, hexyloxy, phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl , Furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl, benzooxazolyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t- Butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, dimethylamino, diethylamino or diphenylamino ;
Phenyl, biphenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furanyl, thiophenyl, R ₁ to R ₇ , R ₁₁ to R ₂₃ , R ₂₄ and R ₂₅ to R ₃₂ Thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimidazolyl and benzooxazolyl are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl , n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chloro, cyano, trifluoromethyl, per Fluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methoxy, ethoxy, butoxy, hexyloxy, phenyl, biphenyl , Naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furanyl, thiophenyl, thiazolyl, imidazolyl, oxazolyl, benzofuranyl, benzothiazolyl, benzoimimi Dazolyl, benzoxazolyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, dimethylamino, diethylamino or diphenylamino One or more selected from may be further substituted. delete delete delete

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