KR20190027203A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light-emitting compound and an organic electroluminescent device comprising the same. The organic light-emitting compound is represented by chemical formula (I) to chemical formula (III). When the organic light-emitting compound is applied in a light-emitting layer, the organic electroluminescent device having excellent luminescent properties such as luminescent efficiency and quantum efficiency can be implemented.

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescent compound and an electroluminescent device comprising the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent compound, and more particularly, to an organic electroluminescent device employing an organic electroluminescent compound employed in an organic electroluminescent element in the organic electroluminescent device and a light emitting element such as quantum efficiency and luminous efficiency.

The organic electroluminescent device can not only form an element on a transparent substrate but also can operate at a low voltage of 10 V or less as compared with a plasma display panel (Plasma Display Panel) or an inorganic electroluminescence (EL) display, It has the advantage of excellent color and has three colors of green, blue, and red. It has recently become a subject of interest as a next generation display device.

However, in order for such an organic electroluminescent device to exhibit the above characteristics, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, an electron blocking material, The organic material layer for an organic electroluminescence device has not yet been developed sufficiently. Therefore, development of a new material capable of improving luminescence characteristics and development of an organic layer structure in a device are continuously required.

Accordingly, it is an object of the present invention to provide a novel organic light emitting compound and an organic electroluminescent device including the same, which can be used as a light emitting layer compound in an organic electroluminescent device to remarkably improve light emitting properties such as quantum efficiency and luminous efficiency.

The present invention provides an organic electroluminescent compound represented by any one of the following formulas (I) to (III) and an organic electroluminescent device comprising the same.

(I) [Formula II]

[Formula (III)

Specific structures and substituents of the above-mentioned formulas (I) to (III) will be described later.

The organic electroluminescent device employing the organic electroluminescent compound according to the present invention in the light emitting layer has remarkably excellent light emitting properties such as quantum efficiency and luminescent efficiency as compared with the conventional device, and thus can be used for various display devices.

1 is a schematic diagram showing the structure of an organic luminescent compound according to the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention relates to an organic electroluminescent compound represented by any one of the following formulas (I) to (III), wherein the electroluminescent compound is an organic electroluminescent compound having a remarkably improved light emitting property such as quantum efficiency, It is possible to realize a light emitting device.

(I) [Formula II]

[Formula (III)

[Formula (I)] to [Formula (III)] in the above Formulas (I) to (III) are asymmetric structures based on L --- L ', respectively.

X ₁ to X ₃ and Z ₁ to Z ₂ are each independently a single bond or any one selected from O, S and R ₃ -CR ₄ (wherein R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms) have.

R ₁ and R ₂ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms A substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 hetero aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl, A substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C1 to C24 alkylamino group, a C6 to C24 arylamino group and a substituted or unsubstituted C2 to C24 heteroaryl group in which at least one unsubstituted C3 to C30 cycloalkyl is fused, And a heteroarylamino group having 6 to 24 carbon atoms.

According to a preferred embodiment of the present invention, each of X ₁ to X ₃ may independently be O, and each of Z ₁ to Z ₂ is independently R ₃ -CR ₄ (wherein R ₃ and R ₄ are each a carbon number of 1 Lt; / RTI > to 3).

[Formula I] to [Formula III] according to the present invention each have an asymmetric structure based on L --- L ', and accordingly, R ₁ is hydrogen and R ₂ is the following Formula 1 .

[Structural formula 1]

In the above formula 1,

L is a single bond or a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, A substituted or unsubstituted C 6 -C 50 arylene group and a substituted or unsubstituted C 3 -C 30 cycloalkyl wherein at least one of the substituted or unsubstituted C 3 -C 30 cycloalkyl is fused or a substituted or unsubstituted carbon 2 to 50 heteroarylene groups (n is an integer of 1 to 3).

Ar ₁ represents a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted carbon number 3 A substituted or unsubstituted C6 to C50 aryl group and at least one substituted or unsubstituted C3 to C30 cycloalkyl wherein at least one of the substituted or unsubstituted C2 to C30 cycloalkyl is fused, (Wherein m is an integer of 1 to 3).

When the host compound of the present invention is employed as a host compound in the light emitting layer in accordance with the structural features as described above, the present invention can provide a light emitting element having a quantum efficiency and a luminescence efficiency An organic light emitting device having excellent characteristics can be realized.

In the definition of R ₁ to R ₂ , L and Ar ₁ , the substitution or unsubstitution means that R ₁ to R ₂ , L and Ar ₁ are each a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, A heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms An aryloxy group having 1 to 24 carbon atoms, an aryloxy group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms, , Or substituted by the substituent the substituent is two or more substituents attached wherein means do or have any substituent.

Specific examples of the substituted aryl group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group and an anthracenyl group substituted with other substituents do.

The substituted heteroaryl group includes a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group and condensed heterocyclic groups thereof such as a benzquinoline group, An imidazole group, a benzoxazole group, a benzothiazole group, a benzoxazole group, a dibenzothiophenyl group, a dibenzofurane group and the like are substituted with other substituents.

In the present invention, examples of the substituents will be specifically described below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, isobutyl, isobutyl, A tert-butyl group, a tert-butyl group, a 2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, Ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group and the like, but are not limited thereto.

Specific examples of the aryloxy group used in the present invention include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy and the like, and at least one hydrogen atom contained in the aryloxy group Can be further substituted.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylpurylsilyl And the like.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, , A chlorenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluororanthrene group, but the scope of the present invention is not limited to these examples.

More specifically, at least one hydrogen atom of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ') (R "), R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms and in this case an "alkylamino group"), an amidino group, An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroatom having 1 to 24 carbon atoms, An alkyl group having 6 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms,

In the present invention, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20. Specific examples include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-yl group, But are not limited to, - (naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl-1-yl) vinyl-1-yl group, stilbenyl group, styrenyl group and the like.

In the present invention, the heteroaryl group is a hetero ring group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably 2 to 30 carbon atoms. Examples thereof include a thiophene group, a furan group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a dibenzofuranyl group, a phenanthroline group, An oxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and the like, but are not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically includes cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, Methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo An octyl group, and the like, but are not limited thereto.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In addition, various specific examples of the substituent according to the present invention can be clearly confirmed through the specific compounds described below.

The organic luminescent compound according to the present invention represented by the above formulas (I) to (III) can be used as an organic material layer of an organic light emitting device due to its structural specificity as described above, and more specifically, And can be used as a host compound in the light emitting layer depending on the characteristics of various substituents.

Specific preferred examples of the compounds represented by formulas (I) to (III) according to the present invention include the following [compounds 1] to [compound 260], but the scope of the present invention is not limited thereto.

An organic luminescent compound having the intrinsic characteristics of the substituent introduced by introducing various substituents into the core structure having the above structure can be synthesized. For example, by introducing a substituent used in a hole injecting layer material, a hole transporting layer material, a light emitting layer material, an electron transporting layer material and an electron blocking layer material used in manufacturing an organic electroluminescent device into the above structure, In particular, when the compounds of the formulas (I) to (III) according to the present invention are employed as the light emitting layer material, the luminescent properties such as the luminous efficiency of the device can be further improved.

The organic luminescent compound according to the present invention can be applied to an organic electroluminescent device according to a conventional production method.

The organic electroluminescent device according to one embodiment of the present invention may have a structure including a first electrode, a second electrode and an organic material layer disposed therebetween, and the organic electroluminescent compound according to the present invention may be used for an organic material layer And can be manufactured using conventional device manufacturing methods and materials.

The organic material layer of the organic electroluminescent device according to the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and an electron blocking layer. However, it is not so limited and may include fewer or greater numbers of organic layers.

Therefore, in the organic electroluminescent device according to the present invention, the organic material layer may include at least one of a hole transporting layer, an electron blocking layer, and a light emitting layer, and at least one of the layers may satisfy the following formulas (I) Lt; RTI ID = 0.0 > luminescent < / RTI >

The organic light emitting device according to the present invention may be formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation A hole transporting layer, an electron blocking layer, a light emitting layer, and an electron transporting layer on the anode, and then depositing a material usable as a cathode thereon.

In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer, but may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

As the anode material, a material having a large work function is preferably used so as to smoothly inject holes into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) metal oxides, ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT) , Conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or an alloy thereof; a multilayer such as LiF / Al or LiO ₂ / Structural materials, and the like, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazol-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and A benzimidazole-based compound, a poly (p-phenylene vinylene) (PPV) -based polymer, a spiro compound, polyfluorene, rubrene, and the like.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is highly mobile, is suitable. Specific examples thereof include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Also, the organic luminescent compound according to the present invention can act on a principle similar to that applied to an organic luminescent device in an organic electronic device including an organic solar cell, an organophotoreceptor, an organic transistor and the like.

Hereinafter, synthesis examples and device embodiments of preferred compounds are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthetic example  1: Synthesis of compound 1

(One) Manufacturing example  1: Synthesis of intermediate 1-1

35% hydrogen peroxide (25.67 g, 0.755 mol, Sigma aldrich), 2% aqueous sodium hydroxide solution (200 mL), and a solution of 9,9-dimethyl-9H-xanthene- 300 mL of THF was added, and the mixture was reacted for 21 hours with stirring. After completion of the reaction, ether and 2N HCl aqueous solution was added thereto. The organic layer was separated, extracted with ether, and subjected to column purification (N-HEXANE: EA) to obtain 10 g (yield 82%) of Intermediate 1-1.

(2) Manufacturing example  2: Synthesis of intermediate 1-2

(1.65 g, 0.050 mol, Sigma aldrich), potassium carbonate (8.56 g, 0.062 mol, Sigma aldrich), Copper (II) oxide (3.94 g, 0.050 mol), methyl 2- bromobenzoate mol, Sigma aldrich) and pyridine (100 mL) were added and reacted at 130 ° C for 6 hours. After the completion of the reaction, the filtrate was neutralized by adding HCl at 0 ° C, extracted with EtOAc, and subjected to column purification (N-HEXANE: EA) to obtain 8 g (yield 76%) of Intermediate 1-2.

(3) Manufacturing example  3: Synthesis of intermediate 1-3

Intermediate 1-2 (10 g, 0.02 mol) and THF (200 mL) were added. Methylmagnesium chloride solution was slowly added dropwise at -78 ° C., stirred for 1 hour, slowly warmed to room temperature, and stirred for 10 hours. The reaction was terminated using 1N HCl and extracted with EA. The organic layer was subjected to column purification (N-HEXANE: EA) to obtain 7.6 g (yield 80%) of Intermediate 1-3.

(4) Manufacturing example  4: Synthesis of intermediate 1-4

MethaneSulfonic acid was added to 150 mL of the intermediate 1-3 (15 g, 0.031 mol) and the reaction was terminated with triethylamine 30 minutes later. Column purification (MC: EA) yielded 11.1 g (Intermediate 1-4) %).

(5) Manufacturing example  5: Synthesis of intermediate 1-5

Add intermediate 1-5 (10 g, 0.021 mol) and chloroform (200 mL), cool to 0 ° C and slowly drop the bromine (3.70 g, 0.023 mol, Sigma Aldrich) with stirring. The mixture was stirred at 0 ° C for 1 hour and reacted at room temperature for 12 hours. After completion of the reaction, an aqueous solution of sodium hydrogencarbonate was added thereto, the layers were separated, and recrystallization was conducted to obtain 9.2 g (yield: 78.9%) of Intermediate 1-5.

(6) Manufacturing example  6: Synthesis of intermediate 1-6

2,4,6-tribromopyridine (10 g, 0.032 mol, TCI), phenylboronic acid (8.88 g, 0.073 mol, sigma aldrich), potassium carbonate (17.51 g, 0.127 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.83 g, 0.002 mol, sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 8 g (yield: 81.4%) of Intermediate 1-6.

(7) Manufacturing example  7: Synthesis of intermediate 1-7

Intermediate 1-6 (10 g, 0.032 mol), Bis (pinacolato) dibron (10.64 g, 0.042 mol, Sigma aldrich), potassium acetate (6.33 g, 0.065 mol, Sigma aldrich), PdCl ₂ (dppf) 0.001 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was stirred at 95 ° C for 12 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 8.7 g (yield 75.5%) of Intermediate 1-7.

(8) Manufacturing example  8: Synthesis of compound 1

Intermediate 1-5 (10 g, 0.018 mol) , intermediate 1-7 (7.75 g, 0.022 mol) , potassium carbonate (6.24 g, 0.045 mol, sigma aldrich), Pd (PPh 3) 4 (1.04 g, 0.0009 mol, Sigma aldrich), 150 mL of Toluene, 30 mL of EtOH and 15 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 9.8 g (yield 77%) of Compound 1.

(8.20 / s, 7.47 / m, 7.26 / d, 7.25 / d, 7.23 / m, 7.09 / m, 6.90 / d) 8.30 / d, 7.54 / m) 18H (1.72 / s)

LC / MS: m / z = 703 [(M + 1) ^< ^{+ &}

Synthetic example  2: Compound 36 Synthesis

(One) Manufacturing example  1: Synthesis of Intermediate 36-1

Phenylboronic acid (7.31 g, 0.060 mol, Sigma Aldrich), potassium carbonate (15.07 g, 0.109 mol, Sigma Aldrich), Pd (PPh ₃ ) ₄ (3.15 g, 0.0027 mol, sigma aldrich), 150 mL of THF and 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 9.8 g (yield: 79.9%) of Intermediate 36-1.

(2) Manufacturing example  2: Synthesis of intermediate 36-2

Dibenzo [b, d] furan-3-ylboronic acid (10.36 g, 0.049 mol, Yurii), potassium carbonate (12.28 g, 0.089 mol, Sigma Aldrich), Pd (PPh ₃ ) ₄ (2.57 g, 0.001 mol, Sigma aldrich), 200 mL of Toluene, 40 mL of EtOH and 20 mL of H ₂ O were added and reacted by refluxing for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 12.2 g (yield: 77%) of Intermediate 36-2.

(3) Manufacturing example  3: Synthesis of intermediate 36-3

(9.25 g, 0.064 mol, Sigma Aldrich), potassium acetate (5.50 g, 0.056 mol, Sigma Aldrich), PdCl ₂ (dppf) (0.62 g, 0.064 mol) 0.0008 mol, Sigma aldrich) and 1,4-dioxane (200 ml), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 9.4 g (yield: 74.8%) of Intermediate 36-3.

(4) Manufacturing example  4: Synthesis of Compound 36

Intermediate 1-5 (10 g, 0.018 mol) , intermediate 36-3 (9.72 g, 0.022 mol) , potassium carbonate (7.49 g, 0.054 mol, sigma aldrich), Pd (PPh 3) 4 (1.04 g, 0.0009 mol, sigma aldrich), 200 mL of Toluene, 40 mL of EtOH and 20 mL of H ₂ O, and the mixture was stirred under reflux for 8 hours. After completion of the reaction, the mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 11 g (yield 76.6%) of Compound 36.

M, 7.38 / m, 7.75 / d, 7.75 / d, 7.66 / d, 7.64 / s, 7.46 / s, 7.41 / 7.32 / m) 2H (7.79 / d, 7.51 / m, 7.26 / d, 7.25 / d, 7.23 /

LC / MS: m / z = 794 [(M + 1) ^< ^{+ &}

Synthetic example  3: Compound 73 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 73-1

2,4,6-trichloro-1,3,5-triazine (10 g, 0.054 mol, Sigma aldrich), phenylboronic acid (7.93 g, 0.065 mol, SigmaAldrich), potassium carbonate (18.74 g, 0.136 mol, Sigma Aldrich _{), Pd (PPh 3) 4} (3.13 g, 0.0027 mol, sigma aldrich), THF 150 mL, H 2 O 40 mL placed and reacted by stirring under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 9.5 g (yield: 77.5%) of Intermediate 73-1.

(2) Manufacturing example  2: Synthesis of Intermediate 73-2

(12.64 g, 0.053 mol, Sigma Aldrich), potassium carbonate (15.28 g, 0.111 moles, Sigma Aldrich), 9,9-dimethyl-9H-fluoren- _{Pd (PPh 3) 4 (2.56} g, 0.0022 mol, sigma aldrich), THF 150 mL, H 2 O 40 mL placed and reacted by stirring under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 13.3 g (yield: 78.3%) of Intermediate 73-2.

(3) Manufacturing example  3: Synthesis of intermediate 36-3

Potassium acetate (5.11 g, 0.052 mol, Sigma Aldrich), PdCl ₂ (dppf) (0.57 g, 0.034 mol) were added to a solution of intermediate 73-2 (10 g, 0.026 mol), Bis (pinacolato) dibron 0.0008 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 9.4 g (yield: 75.9%) of Intermediate 73-3.

(4) Manufacturing example  4: Synthesis of Compound 73

Intermediate 1-5 (10 g, 0.018 mol) , intermediate 73-3 (10.31 g, 0.022 mol) , potassium carbonate (6.24 g, 0.045 mol, sigma aldrich), Pd (PPh 3) 4 (1.04 g, 0.0009 mol, sigma aldrich), 150 mL of Toluene, 30 mL of EtOH and 150 mL of H ₂ O, and the mixture was stirred under reflux for 8 hours. After completion of the reaction, layer separation was performed using H ₂ O: EA and column purification (N-HEXANE: EA) was conducted to obtain 12 g (yield 80.8%) of Compound 73.

M, 7.38 / m, 7.28 / m) < 1 > H-NMR (200MHz, CDCl3): ppm, 1H (7.93 d, 7.87 d, 7.77 s, 7.63 d, 7.55 d, 7.46 s, 7.41 m, 7.29 / m, 6.90 / d) 24H (1.72 / s)

LC / MS: m / z = 821 [(M + 1) ^< ^{+ &}

Synthetic example  4: Compound 108 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 108-1

2,4,6-tribromopyridine (10 g, 0.032 mol, TCI), phenylboronic acid (4.63 g, 0.038 mol, sigma aldrich), potassium carbonate (10.94 g, 0.079 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.83 g, 0.0016 mol, sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, layer separation was carried out using H ₂ O: EA and column purification (N-HEXANE: EA) was conducted to obtain 8 g (yield: 80.7%) of Intermediate 108-1.

(2) Manufacturing example  2: Synthesis of intermediate 108-2

Dibenzo [b, d] furan-4-ylboronic acid (10.78 g, 0.051 mol, Yurii), potassium carbonate (14.65 g, 0.106 mol, Sigma Aldrich), 1,4-dibromobenzene (10 g, 0.042 mol, Sigma Aldrich) , Pd (PPh ₃ ) ₄ (2.45 g, 0.0021 mol, Sigma aldrich), 150 mL of THF and 40 mL of H ₂ O were added and reacted by refluxing for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 10.8 g (yield: 78.8%) of Intermediate 108-2.

(3) Manufacturing example  3: Synthesis of Intermediate 108-3

(10 g, 0.031 mol), Bis (pinacolato) dibron (10.21 g, 0.040 mol, Sigma Aldrich), potassium acetate (6.07 g, 0.062 mol, Sigma aldrich), PdCl ₂ (dppf) 0.0009 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 9.2 g (yield: 80.3%) of Intermediate 108-3.

(4) Manufacturing example  4: Synthesis of intermediate 108-4

Intermediate 108-1 (10 g, 0.032 mol) , intermediate 108-2 (14.20 g, 0.038 mol) , potassium carbonate (11.04 g, 0.080 mol, sigma aldrich), Pd (PPh 3) 4 (1.85 g, 0.0016 mol, sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, layer separation was performed using H ₂ O: EA and column purification (N-HEXANE: EA) was conducted to obtain 8 g (yield 80%) of <Intermediate 108-4>.

(5) Manufacturing example  5: Synthesis of intermediate 108-5

Intermediate 108-4 (10 g, 0.021 mol) , 1,4-phenylenediboronic acid (4.18 g, 0.02 5mol, sigma aldrich), potassium carbonate (7.25 g, 0.052 mol, sigma aldrich), Pd (PPh 3) 4 (1.21 g, 0.0010 mol, sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 8.6 g (yield 79%) of Intermediate 108-5.

(6) Manufacturing example  6: Synthesis of Compound 108

Intermediate 1-5 (10 g, 0.018 mol) , intermediate 108-6 (11.22 g, 0.022 mol) , potassium carbonate (6.24 g, 0.045 mol, sigma aldrich), Pd (PPh 3) 4 (1.04 g, 0.0009 mol, Sigma aldrich), 150 mL of Toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 14 g (yield 81.9%) of Compound 108.

8.81 / d, 8.30 / d, 7.85 / d, 7.81 / d, 7.66 / d, 7.47 / m, 7.46 / s, 7.32 / d, 8.20 s, 7.54 m, 7.38 m, 7.28 d, 7.26 d, 7.23 m, 7.09 m, 6.90 d)

LC / MS: m / z = 945 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Synthesis of compound 124

(One) Manufacturing example  1: Synthesis of intermediate 124-1

Intermediate 73-1 (10 g, 0.0442 mol) , 9-Phenanthracenylboronic acid (11.79 g, 0.053 mol), potassium carbonate (18.34 g, 0.133 mol, sigma aldrich), Pd (PPh 3) 4 (2.56 g, 0.0022 mol, sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 6 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 12.5 g (yield: 76.8%) of Intermediate 124-1.

(2) Manufacturing example  2: Synthesis of intermediate 124-2

(10 g, 0.031 mol), Bis (pinacolato) dibron (10.21 g, 0.040 mol, Sigma aldrich), potassium acetate (6.07 g, 0.062 mol, Sigma aldrich), PdCl ₂ (dppf) 0.0009 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O, layered, and purified by column (N-HEXANE: MC) to obtain 9.5 g (yield: 76%) of Intermediate 124-2.

(3) Manufacturing example  3: Synthesis of Compound 124

Intermediate 1-5 (10 g, 0.018 mol) , Intermediate 124-2 (9.96 g, 0.022 mol) , potassium carbonate (6.24 g, 0.045 mol, sigma aldrich), Pd (PPh 3) 4 (1.04 g, 0.0009 mol, Sigma aldrich), 150 mL of Toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 12.5 g (yield 78.4%) of Compound 124.

(8.93 / d, 8.28 / d, 8.12 / d, 7.88 / m, 7.85 / d, 7.82 / d) m, 7.51 / m, 7.26 / d, 7.23 / m, 7.09 / m, 6.90 /

LC / MS: m / z = 881 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Compound 138 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 138-1

Add bromine (7.07 g, 0.044 mol, Sigma Aldrich) slowly with stirring to 0 ° C and stir with 200 mL of chloroform. The mixture was stirred at 0 ° C for 1 hour and reacted at room temperature for 12 hours. After completion of the reaction, an aqueous solution of sodium hydrogencarbonate was added thereto, followed by layer separation and recrystallization. Thus, 10.3 g (yield: 77%) of Intermediate 138-1 was obtained.

(2) Manufacturing example  2: Synthesis of Intermediate 138-2

Intermediate 138-1 (10 g, 0.032 mol) , phenylboronic acid (2.31 g, 0.019 mol, sigma aldrich), potassium carbonate (5.46 g, 0.040 mol, sigma aldrich), Pd (PPh 3) 4 (0.91 g, 0.0008 mol , sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, layer separation was performed using H ₂ O: EA and column purification (N-HEXANE: EA) was conducted to obtain 8 g (yield 80.4%) of Intermediate 138-2.

(3) Manufacturing example  3: Synthesis of Intermediate 138-3

Bis (pinacolato) dibron (10.58 g, 0.042 mol, Sigma Aldrich), potassium acetate (6.29 g, 0.042 mol, Sigma Aldrich), 2-bromo-4,6-diphenyl- 0.064 mol, Sigma aldrich), PdCl ₂ (dppf) (0.70 g, 0.0010 mol, sigma aldrich) and 1,4-dioxane (200 mL) were added and reacted at 95 ° C for 12 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 8.4 g (yield: 73%) of Intermediate 138-3.

(4) Manufacturing example  4: Synthesis of Compound 138

Intermediate 138-2 (10 g, 0.016 mol) , Intermediate 138-3 (6.85 g, 0.020 mol) , potassium carbonate (5.49 g, 0.040 mol, sigma aldrich), Pd (PPh 3) 4 (0.92 g, 0.0008 mol, Sigma aldrich), 150 mL of Toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: EA, followed by column purification (N-HEXANE: EA) to obtain 9.3 g (yield 78.4%) of Compound 138.

(7.42 / d, 7.26 / d, 7.25 / d, 7.23 / m, 7.09 / m) 3H (7.41 / m) 4H (8.28 / d) 6H (7.51 / m) 18H (1.72 / s)

LC / MS: m / z = 781 [(M + 1) ^&lt; ^{+ &}

Device Example

In the embodiment according to the present invention, the ITO transparent electrode is formed by patterning an ITO glass substrate having an ITO transparent electrode on a glass substrate of 25 mm x 25 mm x 0.7 mm so as to have a light emitting area of 2 mm x 2 mm And then washed. After the substrate was mounted in a vacuum chamber and the base pressure was adjusted to 1 × 10 ^-6 torr, organic matter and metal were deposited on the ITO by the following structure.

Device Embodiments 1 through 12

An organic electroluminescent device having the following device structure was prepared using the compound to be implemented according to the present invention as a host compound in the light emitting layer, and the luminescent characteristics including the light emitting efficiency were measured.

A light emitting layer (CBP, Ir (ppy) ₃ 30 nm) / an electron transport layer (Alq ₃ 30 nm) / LiF (1 nm) / Al (hole transporting layer) (100 nm)

A hole injection layer was formed on the ITO transparent electrode by a vacuum thermal deposition method so as to have a thickness of 5 nm, and then the hole transport layer was formed using? -NPB. Ir (ppy) ₃ as a dopant compound is used as the host compound in the light emitting layer using the compounds represented by Chemical Formula 1, 36, 53, 73, 108, 124, 138, 166, 191, 220, 230, (Alq ₃ ) 30 nm, LiF 1 nm and aluminum 100 nm were deposited by vapor deposition to form an organic electroluminescent device.

Device Comparative Example 1

The organic electroluminescent device for element comparison example 1 is the same as that of embodiment 1 except that CBP known as a conventional phosphorescent host compound is used instead of the compound according to the present invention as a host material in the device structure of the embodiment 1 Respectively.

EXPERIMENTAL EXAMPLE 1: Luminescent characteristics of element embodiments 1 to 12

The voltage, current and luminous efficiency of the organic EL device were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research). The current density was 10 mA / Is defined as " driving voltage " The results are shown in Table 1 below.

Example Host V cd / A QE (%) CIEx CIEy One Formula 1 3.86 55.1 15.01 0.324 0.614 2 Formula 36 3.79 61.3 19.12 0.315 0.592 3 Formula 53 3.85 57.6 16.82 0.331 0.609 4 Formula 73 3.92 56.7 16.10 0.320 0.611 5 (108) 3.95 58.4 17.35 0.327 0.599 6 124 3.80 60.6 18.88 0.324 0.594 7 138 3.77 56.2 15.93 0.325 0.617 8 166 4.01 55.7 15.42 0.329 0.615 9 191 3.86 59.4 18.05 0.326 0.608 10 Formula 220 3.98 56.9 16.41 0.327 0.621 11 Formula 230 3.88 58.3 17.37 0.321 0.609 12 257 3.94 57.8 16.97 0.330 0.616 Comparative Example 1 CBP 3.91 40.3 13.87 0.316 0.606

In the results shown in Table 1, it can be confirmed that the luminescent layer host compound according to the present invention is significantly superior to the conventional device (comparative example) in light emission efficiency and quantum efficiency.

[HAT_CN] [? -NPB] [CBP] [Ir (ppy) ₃ ]

Claims (8)

An organic luminescent compound represented by any one of the following formulas (I) to (III):
(I) &lt; RTI ID = 0.0 &gt; (II)

[Formula (III)

In the above formulas (I) to (III), the formulas (I) to (III) each have an asymmetric structure based on L --- L '
X ₁ to X ₃ and Z ₁ to Z ₂ are each independently a single bond or any one selected from O, S and R ₃ -CR ₄ (wherein R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms)
R ₁ and R ₂ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms A substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C6 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl, A substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C1 to C24 alkylamino group, a C6 to C24 arylamino group and a substituted or unsubstituted C2 to C24 heteroaryl group in which at least one unsubstituted C3 to C30 cycloalkyl is fused, And a heteroarylamino group having 6 to 24 carbon atoms. The method according to claim 1,
Wherein X ₁ to X ₃ are each independently 0 and each of Z ₁ to Z ₂ is independently R ₃ -CR ₄ (wherein R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms) Luminescent compound. The method according to claim 1,
Wherein R &lt; ₁ &gt; is hydrogen and R &lt; ₂ &gt;
[Structural formula 1]

In the above formula 1,
L is a single bond or a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, A substituted or unsubstituted C 6 -C 50 arylene group and a substituted or unsubstituted C 3 -C 30 cycloalkyl wherein at least one of the substituted or unsubstituted C 3 -C 30 cycloalkyl is fused or a substituted or unsubstituted carbon 2 to 50 heteroarylene groups, wherein n is an integer of 1 to 3,
Ar ₁ represents a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted carbon number 3 A substituted or unsubstituted C6 to C50 aryl group and at least one substituted or unsubstituted C3 to C30 cycloalkyl wherein at least one of the substituted or unsubstituted C2 to C30 cycloalkyl is fused, (Wherein m is an integer of 1 to 3). The method according to claim 1 or 3,
Each of R ₁ to R ₂ , L and Ar ₁ is independently selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, An arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms, and is substituted with one or two or more selected substituents, or two or more substituents Or substituted with a substituent is connected, or an organic light-emitting compound, which means that also does not have any substituent. The method according to claim 1,
The organic electroluminescent compound represented by any of the above Chemical Formulas (I) to (III) is any one selected from the following Chemical Formulas 1 to 260:

1. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic layers comprises at least one organic luminescent compound represented by any one of formulas (I) to (III) according to claim 1. The method according to claim 6,
Wherein the organic material layer includes at least one of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer and a light emitting layer,
Wherein at least one of the layers comprises an organic light emitting compound represented by the above formulas (I) to (III). 8. The method of claim 7,
The organic electroluminescent device according to any one of claims 1 to 3, wherein the luminescent compound represented by the above formulas (I) to (III) is included in the luminescent layer.

Images