KR20180042944A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound applied to an organic electroluminescent device. The organic light emitting compound is represented by the chemical formula I. The present invention relates to the organic electroluminescent compound, which can realize the organic light emitting device having remarkably excellent light-emitting efficiency and quantum efficiency compared to a conventional device by applying the organic light emitting compound to an electron blocking layer.

Description

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

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device employing the organic electroluminescent compound in an organic material layer of the device, thereby realizing a device having a remarkably excellent light emitting property such as luminous efficiency and quantum efficiency.

An organic light emitting phenomenon is a phenomenon that converts electric energy into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer has a multi-layer structure composed of different materials. For example, the organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, Layer or the like. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, a hole blocking material, . In addition, the luminescent material can be classified into blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color.

In order for the organic light emitting device to fully exhibit the above-described excellent characteristics, it is necessary that various materials constituting the organic material layer in the device are supported by stable and efficient materials. However, development of stable and efficient organic material layer materials for organic light emitting devices It is not done. Therefore, the development of new materials is continuously required, and the necessity of developing such materials is the same in other organic electronic devices.

The present invention provides a novel organic electroluminescent compound which is employed in an organic layer of an organic electroluminescent device and can realize excellent luminescent properties such as luminous efficiency and quantum efficiency, and an organic light emitting device comprising the same.

In order to solve the above problems, the present invention provides an organic light emitting device represented by the following formula (I).

(I)

The specific structure and substituent of the above-mentioned formula (I) will be described later.

The present invention also provides an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the organic light emitting compound And an organic electroluminescent device.

The device employing the organic luminescent compound according to the present invention in the electron blocking layer is superior to the conventional device in light emission characteristics such as luminous efficiency and quantum efficiency, and thus can be applied to various display devices.

Hereinafter, the present invention will be described more specifically.

One aspect of the present invention relates to an organic light-emitting compound which is employed in an organic material layer of an organic light-emitting device, preferably an electron-blocking layer, to realize excellent light-emitting properties such as luminous efficiency and quantum efficiency. .

(I)

In the above formula (I)

L ₁ to L ₃ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted Or a substituted or unsubstituted heteroarylene group containing at least one of N, O and S atoms, and n, m and o are each independently an integer of 1 to 4.

Ar ₁ and Ar ₂ are the same or different and each independently represents a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms wherein at least one of the substituted or unsubstituted C3 to C30 cycloalkyls is fused, Lt; RTI ID = 0.0 > Rl, < / RTI >

R ₁ to R _{9 each} represent a hydrogen atom, a heavy hydrogen atom, a cyano group, a halogen group, an amino group, a nitro group, a hydroxyl group, a silyl group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms substituted or unsubstituted with at least one fused cycloalkyl having 3 to 30 carbon atoms And a substituted or unsubstituted C2 to C50 heteroaryl group in which one or more substituted or unsubstituted C3 to C30 cycloalkyl is fused together.

In addition, R ₁ to R ₉ may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with each other or adjacent substituents.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of deuterium, halogen, nitrile, nitro, hydroxyl, alkyl, cycloalkyl, An arylamine group, an arylamine group, a fluorenyl group, a carbazole group, and at least one of N, O and S atoms, A substituted or unsubstituted heterocyclic group, and the like.

Specific examples of the substituted arylene group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group and a tetracenyl group. Anthracenyl group and the like are substituted with other substituents.

The substituted heteroarylene 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, A benzimidazole group, a benzimidazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzzcarbazole group, a dibenzothiophenyl group, a dibenzofurane group and the like are substituted with other substituents.

In the present invention, L ₁ to L ₃ , Ar ₁ , Ar ₂ and R ₁ to R ₉ of the above-mentioned formula (I) may further be substituted with further substituents. Examples thereof include deuterium, halogen, But are not limited to, an alkenyl group, an alkoxy group, a silyl group, an arylalkenyl group, an aryl group, a heteroaryl group, a carbazole group, an arylamine group, a fluorenyl group substituted or unsubstituted with an aryl group, It is not.

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 50. 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.

In the present invention, the alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 to 30, which does not cause steric hindrance. Specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an i-propyloxy group, a n-butoxy group, an isobutoxy group, a tert- , Neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n- , A benzyloxy group, a p-methylbenzyloxy group, and the like, but are not limited thereto.

In the present invention, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. 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 aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 60. [ 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.

In the present invention, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane 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 pyrazinopyrazinyl group, an isoquinoline group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolyl group, , An indole 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 dibenzofurancyl group, a phenanthroline group, An isothiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group and the like, but is not limited thereto.

In the present invention, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, a ptert- Anthryloxy group, 2-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, Anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group and the like. Examples of the arylthioxy group include phenylthioxy group, 2- A 4-tert-butylphenyloxy group, and the like. Examples of the arylsulfoxy group include benzene sulfoxy group and p-toluenesulfoxy group. However, the present invention is not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 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.

,

등이 있다.In the present invention, a fluorenyl group is a structure in which two cyclic organic compounds are connected via one atom,

,

.

,

등이 있다.In the present invention, a fluorenyl group includes a structure of an open fluorenyl group, wherein an open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected via one atom For example,

,

.

In the present invention, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methylphenylamine group, a 4-methylnaphthylamine group, But are not limited to, an amine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a carbazole group and a triphenylamine group.

In the present invention, the silyl group is specifically exemplified by trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, But are not limited thereto.

In the present invention, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present invention, the alkyloxy group in the alkylthio group and the alkyl group in the alkylsulfoxy group are the same as the aforementioned alkyl groups. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, But are not limited thereto.

The organic electroluminescent compound according to the present invention represented by the above formula (I) can be used as an organic material layer of an organic light emitting device due to its structural specificity, and more specifically, as an electron blocking layer material of an organic material layer.

Preferred examples of the compound represented by the formula (I) according to the present invention include, but are not limited to, the following compounds.

By introducing various substituents to the core structure having the above structure, it is possible to synthesize an organic luminescent compound having the intrinsic characteristics of the substituent introduced thereto, thereby manufacturing a material satisfying the requirements of various organic layers of the organic luminescent device have. The compound of the present invention can be applied to a device according to a conventional manufacturing method of an organic light emitting device.

The organic light emitting 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 uses the organic light emitting compound according to the present invention in an organic material layer of the device And can be produced using ordinary device manufacturing methods and materials.

The organic material layer of the organic light emitting 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, an electron blocking layer, a hole blocking layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as well as a layer having various functions. However, it is not limited to this and may include a smaller number of organic layers.

Accordingly, in the organic light emitting device according to the present invention, at least one of the layers may contain a compound represented by the above formula (I), and preferably the electron blocking layer is a compound represented by the above formula (I) .

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, preferred embodiments of the present invention will be described in order 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.

<Examples>

Synthetic example  1: Synthesis of Compound (16)

(One) Manufacturing example  1: Synthesis of intermediate 16-1

1-bromo-4-iodobenzene (34.69 g, 0.123 mol, Sigma Aldrich), potassium carbonate (39.11 g, 0.283 mol, Sigma _{aldrich), Pd (PPh 3)} 4 (5.45 g, 0.0047 mol, sigma aldrich), THF 150 mL, 50 mL of water was put into the reaction mixture was stirred at 60 ℃ for 12 hours. After completion of the reaction, layer separation was performed using H ₂ O: MC and column purification (N-HEXANE: MC) was performed to obtain 23.4 g (yield: 77%) of <Intermediate 16-1>.

(2) Manufacturing example  2: Synthesis of intermediate 16-2

Sodium tert-butoxide (5.95 g, 0.062 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (10 g, 0.031 mol), 4-amino-p- (0.89 g, 0.0015 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.63 g, 0.003 mol, Sigma aldrich) were added 100 mL of toluene and reacted at 100 ° C for 2 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 11.2 g (yield: 74%) of Intermediate 16-2.

(3) Manufacturing example  3: Synthesis of intermediate 16-3

4-bromophenylboronic acid (7.53 g, 0.038 mol, Sigma aldrich), potassium carbonate (12.95 g, 0.094 mol, Sigma Aldrich), 1-iodo-9,9-dimethyl-9H- _{, Pd (PPh 3) 4 (} 1.8 g, 0.0016 mol, sigma aldrich), THF 100 mL, 30 mL of water was put into the reaction mixture was stirred at 60 ℃ for 6 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 8.7 g (yield 80%) of Intermediate 16-3.

(4) Manufacturing example  4: Synthesis of Compound 16

Intermediate 16-3 (6 g, 0.017 mol), Intermediate 16-2 (10 g, 0.021 mol), Sodium tert-butoxide (3.30 g, 0.034 mol, Sigma aldrich), Pd (dba) ₂ (0.49 g, , Sigma aldrich) and tri-tert-Bu-phosphine (0.35 g, 0.0017 mol, Sigma aldrich) were added 70 mL of toluene and reacted at 90 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 10.0 g (yield 79%) of Compound 16.

7.87 d, 7.85 d, 7.83 d, 7.81 d, 7.66 d, 7.55 d, 7.53 d, 7.44 m, (7.54 / d, 6.69 / d, 1.72 / s) 2H (7.52 / d, 7.51 / m) 3H (7.38 /

LC / MS: m / z = 755 [(M + 1) ^&lt; ^{+ &}

Synthetic example  2: Synthesis of Compound 51

(One) Manufacturing example  1: Synthesis of Intermediate 51-1

Sodium tert-butoxide (8.25 g, 0.086 mol, Sigma Aldrich), Pd (dba) ₂ (1.23 g, 0.015 mol, Sigma Aldrich), 4-aminobiphenyl 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.87 g, 0.0043 mol, Sigma aldrich) and reacted at 90 ° C for 4 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 10.9 g (yield 79%) of Intermediate 51-1.

(2) Manufacturing example  2: Synthesis of intermediate 51-2

(10.69 g, 0.037 mol, TCI), sodium tert-butoxide (5.98 g, 0.062 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.90 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.63 g, 0.003 mol, Sigma aldrich) and reacted at 100 ° C for 4 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 11.4 g (yield 69%) of Intermediate 51-2.

(3) Manufacturing example  3: Synthesis of Intermediate 51-3

Potassium acetate (5.62 g, 0.057 mol, Sigma aldrich), PdCl ₂ (dppf) (0.63 g, 0.037 mol) was added to a solution of intermediate 16-3 (10 g, 0.029 mol), Bis (pinacolato) dibron 0.0009 mol, Sigma aldrich) and 1,4-dioxane (120 mL), and the mixture was reacted at 95 ° C for 7 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 8.3 g (yield: 73%) of Intermediate 51-3.

(4) Manufacturing example  4: Synthesis of Compound 51

Intermediate 51-2 (8 g, 0.015 mol) , intermediate 51-3 (7.83 g, 0.020 mol) , potassium carbonate (6.3 g, 0.046 mol, sigma aldrich), Pd (PPh 3) 4 (0.9 g, 0.0008 mol, sigma aldrich) and 80 mL of toluene, and the mixture was reacted at 90 DEG C for 6 hours with stirring. After completion of the reaction, the mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 8.5 g (yield 78%) of Compound 51.

7.38 / d, 7.78 / d, 7.58 / d, 7.44 / m, 7.38 / m, 7.28 / m, 7.54 / d) 2H (7.53 / m, 7.41 / m) 4H (7.52 / d, 7.51 /

LC / MS: m / z = 715 [(M + 1) ^&lt; ^{+ &}

Synthetic example  3: Synthesis of Compound 66

(One) Manufacturing example  1: Synthesis of intermediate 66-1

Intermediate 16-1 (10 g, 0.031 mol, TCI), 4-aminobiphenyl (6.28 g, 0.037 mol, sigma aldrich), Sodium tert-butoxide (5.95 g, 0.062 mol, sigma aldrich), catalyst Pd (dba) ₂ ( Tetrabutylphosphine (0.63 g, 0.0031 mol, Sigma aldrich), and the mixture was reacted at 100 ° C. for 4 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 11 g (yield 86%) of <Intermediate 16-1>.

(2) Manufacturing example  2: Synthesis of Intermediate 66-2

Intermediate 51-3 (10 g, 0.025 mol) , 1-bromo-4-iodobenzene (9.28 g, 0.033 mol, sigma aldrich), potassium carbonate (10.46 g, 0.076 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.46 g, 0.0013 mol, Sigma aldrich) and 100 mL of tetrahydrofuran, and the mixture was reacted at 60 ° C for 6 hours with stirring. 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: EA) to obtain 8.2 g (yield 76%) of Intermediate 66-2.

(3) Manufacturing example  3: Synthesis of Compound 66

Intermediate 66-2 (7 g, 0.017 mol), Intermediate 66-1 (8.13 g, 0.020 mol), Sodium tert-butoxide (3.16 g, 0.033 mol, Sigma aldrich), Pd (dba) ₂ (0.47 g, , Sigma aldrich) and tri-tert-Bu-phosphine (0.33 g, 0.002 mol, Sigma aldrich) were added 70 mL of toluene and reacted at 90 ° C for 6 hours with stirring. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 10.1 g (yield 81%) of Compound 66.

7.87 d, 7.85 d, 7.83 d, 7.81 d, 7.66 d, 7.55 d, 7.53 d, 7.44 m, (7.54 / d, 6.69 / d, 1.72 / s) 2H (7.52 / d, 7.51 / d) 3H (7.38 /

LC / MS: m / z = 755 [(M + 1) ^&lt; ^{+ &}

Synthetic example  4: Synthesis of Compound 100

(One) Manufacturing example  1: Synthesis of intermediate 100-1

Phenylboronic acid (9 g, 0.074 mol, Sigma Aldrich), potassium carbonate (15.7 g, 0.114 mol, Sigma Aldrich), 1,8-dibromo-9,9-dimethyl-9H- , Pd (PPh ₃ ) ₄ (3.28 g, 0.0028 mol, sigma aldrich) and 200 mL of tetrahydrofuran were added and reacted at 60 ° C for 3 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 12.3 g (yield 62%) of Intermediate 100-1.

(2) Manufacturing example  2: Synthesis of intermediate 100-2

PdCl ₂ (dppf) (0.75 g, 0.045 mol, Sigma Aldrich), potassium acetate (6.74 g, 0.069 mol, 0.001 mol, Sigma aldrich) and 1,4-dioxane (120 mL), and the mixture was reacted at 95 ° C for 8 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 9.6 g (yield: 73%) of Intermediate 100-2.

(3) Manufacturing example  3: Synthesis of intermediate 100-3

Intermediate 100-2 (9 g, 0.023 mol) , 1-bromo-4-iodobenzene (8.35 g, 0.030 mol, sigma aldrich), potassium carbonate (9.42 g, 0.068 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.31 g, 0.0011 mol, Sigma aldrich) and 100 mL of tetrahydrofuran, and the mixture was reacted at 60 DEG C for 4 hours with stirring. 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: EA) to obtain 7 g (yield 70%) of Intermediate 100-3.

(4) Manufacturing example  4: Synthesis of intermediate 100-5

Sodium tert-butoxide (6.72 g, 0.070 mol, Sigma aldrich), Pd (dba) ₂ (1.01 g, 0.042 mol), 1,4-dibromonaphthalene (10 g, 0.035 mol, TCI) , 0.0017 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, Sigma aldrich) were added 100 mL of Toluene and reacted at 90 ° C for 4 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 17.5 g (yield: 81%) of <Intermediate 100-4>.

(5) Manufacturing example  5: Synthesis of Compound 100

Intermediate 100-5 (7 g, 0.011 mol) , Intermediate 100-4 (6.97 g, 0.015 mol) , potassium carbonate (3.14 g, 0.023 mol, sigma aldrich), Pd (PPh 3) 4 (0.66 g, 0.0006 mol, sigma aldrich) and 100 mL of toluene, and the mixture was reacted at 90 ° C for 6 hours with stirring. After completion of the reaction, the mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 7.5 g (yield 75%) of Compound 100.

7.81 d, 7.78 d / d, 7.66 d, 7.32 dm, 7.04 d). (7.53 / m) 2H (7.83 / d, 7.44 / m, 7.41 / m, 7.38 / 1.72 / s)

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

Synthetic example  5: Synthesis of Compound 105

(One) Manufacturing example  1: Synthesis of intermediate 105-1

Phenylboronic acid (5.50 g, 0.045 mol, Sigma aldrich), potassium carbonate (10.39 g, 0.075 mol, Sigma), and 1-bromo-6-iodo-9,9- _{aldrich), Pd (PPh 3)} 4 (2.17 g, 0.0019 mol, sigma aldrich), Tetrahydrofuran 100 mL placed and reacted by stirring at 60 ℃ for 3 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 10.5 g (yield 80%) of Intermediate 105-1.

(2) Manufacturing example  2: Synthesis of intermediate 105-2

PdCl ₂ (dppf) (0.63 g, 0.037 mol, Sigma Aldrich), potassium acetate (5.62 g, 0.057 mol, Sigma aldrich), Bis (pinacolato) dibron (9.45 g, 0.0009 mol, Sigma aldrich) and 1,4-dioxane (120 mL), and the mixture was reacted at 95 ° C. for 6 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O and the layers were separated and purified by column (N-HEXANE: MC) to obtain 9 g (yield: 79%) of Intermediate 105-2.

(3) Manufacturing example  3: Synthesis of intermediate 105-3

Intermediate 105-2 (9 g, 0.023 mol) , 1-bromo-4-iodobenzene (7.71 g, 0.027 mol, sigma aldrich), potassium carbonate (6.28 g, 0.045 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.31 g, 0.0011 mol, sigma aldrich) and 100 mL of Toluene, and the mixture was reacted at 90 DEG C for 3 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: Tol and then subjected to column purification (N-HEXANE: MC) to obtain 8 g (yield: 82.8%) of Intermediate 105-3.

(4) Manufacturing example  4: Synthesis of Compound 105

Intermediate 105-3 (8 g, 0.019 mol), Intermediate 66-1 (9.29 g, 0.023 mol), Sodium tert-butoxide (3.61 g, 0.038 mol, Sigma aldrich), Pd (dba) ₂ (0.54 g, , Sigma aldrich) and tri-tert-Bu-phosphine (0.38 g, 0.0019 mol, Sigma aldrich) were added 100 mL of toluene and reacted at 90 ° C for 6 hours with stirring. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 11.4 g (yield 80%) of Compound 105.

(8.06 / s, 7.89 / d, 7.85 / d, 7.83 / d, 7.81 / d, 7.66 / d, 7.61 / d, 7.44 / m, 7.32 / m) 6H (7.54 / d, 6.69 / d, 1.72 / s) 2H (7.53 / d, 7.41 /

LC / MS: m / z = 755 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Synthesis of Compound 107

(One) Manufacturing example  1: Synthesis of intermediate 107-1

Bis (pinacolato) dibron (15.38 g, 0.061 mol, Sigma Aldrich), potassium acetate (9.14 g, 0.093 mol), 1-bromo-11,11-dimethyl- PdCl ₂ (dppf) (1.02 g, 0.0014 mol, Sigma aldrich) and 1,4-dioxane (200 mL) were added and reacted at 95 ° C for 8 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O, layer separation was performed, and 12.8 g (yield: 74%) of <Intermediate 107-1> was obtained by column purification (N-HEXANE: MC).

(2) Manufacturing example  2: Synthesis of intermediate 107-2

Intermediate 107-2 (12 g, 0.032 mol) , 1-bromo-4-iodobenzene (11 g, 0.039 mol, sigma aldrich), potassium carbonate (8.96 g, 0.065 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.87 g, 0.0016 mol, sigma aldrich) and 150 mL of Toluene, and the mixture was reacted at 90 DEG C for 3 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: Tol and purified by column (N-HEXANE: MC) to obtain 9.8 g (yield: 75.7%) of Intermediate 107-2.

(3) Manufacturing example  3: Synthesis of Compound 107

Intermediate 107-2 (9 g, 0.023 mol), Intermediate 66-1 (11.13 g, 0.027 mol), Sodium tert-butoxide (4.33 g, 0.045 mol, Sigma aldrich), Pd (dba) ₂ , Sigma aldrich) and tri-tert-Bu-phosphine (0.46 g, 0.0023 mol, Sigma aldrich) were added and reacted at 90 ° C for 6 hours with stirring. After the completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 13.2 g (yield 80%) of Compound 107.

D, 7.89 / d, 7.85 / d, 7.81 / d, 7.66 / d, 7.58 / m, 8.08 / 7.51 / m, 7.49 / d, 7.41 / m, 7.32 / m) 2H (7.51 / m, 7.38 /

LC / MS: m / z = 729 [(M + 1) ^&lt; ^{+ &}

Synthetic example  7: Synthesis of Compound 113

(One) Manufacturing example  1: Synthesis of intermediate 113-1

(14.22 g, 0.145 mol, Sigma Aldrich), PdCl ₂ (dppf) (1.59 g, 0.094 mol, Sigma Aldrich), 1-bromonaphthalene (15 g, 0.072 mol, SigmaAldrich), Bis (pinacolato) dibron g, 0.0022 mol, sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 6 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O and the layers were separated, and 13.5 g (yield: 73%) of <Intermediate 113-1> was obtained by column purification (N-HEXANE: MC).

(2) Manufacturing example  2: Synthesis of intermediate 113-2

Intermediate 113-1 (12 g, 0.047 mol) , 4-bromoaniline (9.75 g, 0.057 mol, sigma aldrich), potassium carbonate (13.05 g, 0.094 mol, sigma aldrich), Pd (PPh 3) 4 (2.73 g, 0.0024 mol, Sigma aldrich) and 150 mL of Toluene. The mixture was reacted at 90 ° C for 3 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: Tol and then subjected to column purification (N-HEXANE: MC) to obtain 7.9 g (yield: 76%) of Intermediate 113-2.

(3) Manufacturing example  3: Synthesis of intermediate 113-3

Intermediate 16-1 (9 g, 0.028 mol) , Intermediate 113-2 (7.33 g, 0.033 mol) , Sodium tert-butoxide (5.35 g, 0.056 mol, sigma aldrich), Pd (dba) 2 (0.80 g, 0.0014 mol , Sigma aldrich) and tri-tert-Bu-phosphine (0.56 g, 0.0028 mol, Sigma aldrich) were added 100 mL of toluene and reacted at 90 ° C for 6 hours with stirring. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 10.2 g (yield 79%) of Intermediate 113-3.

(4) Manufacturing example  4: Synthesis of compound 113

Intermediate 113-3 (9 g, 0.020 mol) , Intermediate 107-2 (9.34 g, 0.023 mol) , Sodium tert-butoxide (3.75 g, 0.039 mol, sigma aldrich), Pd (dba) 2 (0.56 g, 0.0010 mol , Sigma aldrich) and tri-tert-Bu-phosphine (0.39 g, 0.0019 mol, Sigma aldrich) were added 100 mL of toluene and reacted at 90 ° C for 6 hours with stirring. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 12 g (yield 79%) of Compound 113.

D, 8.09 / d, 8.01 / d, 7.97 / d, 7.89 / d, 8.08 / d, 8.08 / d, 8.08 / d, 7.58 / m, 7.49 / d, 7.32 / m) 2H (7.38 / m) 3H (7.55 / 7.54 / d, 6.69 / d, 1.78 / s)

LC / MS: m / z = 779 [(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 Example  1 to 7

A blue light emitting organic electroluminescent device having the following device structure was prepared by using the compound represented by Formula (I) according to the present invention as a compound of the electron blocking layer, and the luminescent characteristics including the luminescent efficiency were measured.

Electron transport layer (201 nm Liq 30 nm) / LiF (1 nm) / ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (α-NPB 100 nm) / electron blocking layer (10 nm) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, a hole injection layer was formed by a vacuum thermal deposition method with a thickness of 5 nm from the hole injection layer using HAT_CN, and then the hole transport layer was formed using a-NPB Respectively. The electron blocking layer was formed to a thickness of 10 nm by using the chemical formulas 16, 51, 66, 100, 105, 107, and 113 implemented by the present invention. Further, an electron transport layer (doped with Liq 50% of the following compound [201]) was further formed in the light emitting layer so as to have a thickness of about 20 nm by using [BH1] as a host compound and [BD1] 30 nm, LiF 1 nm and aluminum 100 nm were deposited by vapor deposition to produce an organic electroluminescent device.

[HAT_CN] [? -NPB] [BH1] [BD1] [201]

device Comparative Example  One

An organic electroluminescent device for Device Comparison Example 1 was fabricated in the same manner except that the electron blocking layer was not used in the device structure of Example 1 above.

Experimental Example  1: element Example  Luminescence characteristics of 1 to 7

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.

division Electronic stop layer V cd / A QE (%) CIEx CIEy Example 1 Formula 16 4.24 8.09 7.64 0.144 0.154 Example 2 Formula 51 4.25 8.13 7.66 0.145 0.155 Example 3 66 4.22 8.25 7.75 0.145 0.154 Example 4 100 4.24 8.12 7.62 0.144 0.154 Example 5 105 4.23 8.14 7.68 0.145 0.155 Example 6 Formula 107 4.22 8.23 7.72 0.145 0.155 Example 7 Formula 113 4.25 8.11 7.65 0.146 0.154 Comparative Example 1 not used 4.14 5.4 4.6 0.147 0.156

In the results shown in Table 1, it was confirmed that the organic luminescent device in which the compound according to the present invention was applied to the electron blocking layer was significantly superior in luminescence properties such as luminous efficiency and quantum efficiency as compared with the conventional device (comparative example) have.

Claims (6)

An organic light-emitting compound represented by the following formula (I):
(I)

In the above formula (I)
L ₁ to L ₃ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted Or a substituted or unsubstituted heteroarylene group containing at least one of N, O and S atoms,
Ar ₁ and Ar ₂ are the same or different and each independently represents a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted C3- A substituted or unsubstituted C2 to C50 heteroaryl group having at least one substituted or unsubstituted aryl group having 5 to 50 carbon atoms and at least one substituted or unsubstituted C3 to C30 cycloalkyl, An aryl group,
R ₁ to R ₉ independently represent hydrogen, deuterium, cyano, halogen, amino, nitro, hydroxyl, silyl, alkyl having 1 to 24 carbon atoms, halogenated alkyl having 1 to 24 carbon atoms, A substituted or unsubstituted aryl group having 3 to 50 carbon atoms, a substituted or unsubstituted aryl group having 3 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms in which at least one unsubstituted C 3 -C 30 cycloalkyl is fused,
R ₁ to R ₉ may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with each other or adjacent substituent,
n, m and o are each independently an integer of 1 to 4. The method according to claim 1,
Wherein the compound represented by the formula (I) is any one selected from the group consisting of the following compounds 1 to 129:

1. An organic light emitting device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises an organic light emitting compound represented by the general formula (I) of claim 1. The method of claim 3,
Wherein the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, an electron transporting layer, and an electron injecting layer,
Wherein at least one of the layers comprises an organic luminescent compound represented by the formula (I). 5. The method of claim 4,
Wherein the electron blocking layer comprises an organic luminescent compound represented by the formula (I). The method of claim 3,
Wherein at least one of the organic light emitting layers emitting red, green or blue light is further included in the organic material layer to emit white light.