KR20190082590A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by chemical formula I, and an organic electroluminescent device comprising the same. When the organic light emitting compound is used as a compound in an organic material layer such as a light emitting layer, an electron transport layer, or the like, the organic electroluminescent device having excellent light emitting characteristics such as quantum efficiency, light emitting efficiency or the like 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 compound employing an organic electroluminescent compound in an organic electroluminescent device and a light emitting device using the same.

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, the present invention is to provide a novel organic luminescent compound and an organic electroluminescent device including the organic luminescent compound, which can be used as a compound in an organic layer such as a luminescent layer in an organic electroluminescent device to remarkably improve luminescent properties such as luminous efficiency.

In order to solve the above problems, the present invention provides an organic electroluminescent compound represented by the following formula (I) and an organic electroluminescent device comprising the same.

(I)

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

The organic electroluminescent device employing the organic electroluminescent compound according to the present invention as a host compound in the luminescent layer has remarkably excellent luminescent properties such as luminescent efficiency as compared with the conventional device and can be usefully used in 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 can be applied to an organic electroluminescent device having an organic electroluminescent device represented by the following formula (I), wherein the electroluminescent device has a significantly improved luminescence efficiency such as luminous efficiency when used in an organic layer such as a luminescent layer in an organic electroluminescent device.

In addition, when the organic electroluminescent compound represented by the formula (I) according to the present invention is employed in the light emitting layer, triplet-triplet annihilation (TTA) can be efficiently performed in the light emitting layer, Thereby improving internal quantum efficiency (IQE).

In order to facilitate the transition from triplet to singlet using the TTA phenomenon, the following conditions must be satisfied. The transition energy (singlet-triplet exchange energy, DELTA Est) between the singlet and triplet of each host and dopant employed in the light emitting layer must be small, and in order to effectively block the triplet exciton in the light emitting layer, Of the triplet energy of the host should be higher than the triplet energy of the host. Here, when the organic luminescent compound represented by the formula (I) according to the present invention is employed as the host compound in the luminescent layer, the above condition is satisfied and the internal quantum efficiency is improved.

(I)

In the above formula (I)

L ₁ and L ₂ are the same or different from each other and each independently represents a single bond, 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 in which at least one of the substituted or unsubstituted C 3 -C 30 cycloalkyl is fused and a substituted or unsubstituted C 3 -C 30 cycloalkyl in which at least one of the substituted or unsubstituted C2- To 50 heteroarylene groups (p and q are each an integer of 0 to 3).

Ar ₁ and Ar ₂ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted group having 2 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 C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, 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, (N and m are each an integer of 0 to 3).

In the definition of L ₁ , L ₂ , Ar ₁ and Ar ₂ , the substituted or unsubstituted L ₁ , L ₂ , Ar ₁ and Ar ₂ are each an alkyl 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, an alkylamino group having 1 to 24 carbon atoms, and an arylamino group having 1 to 24 carbon atoms, which is substituted with one or more selected substituents or two or more substituents Substituted with a substituent, or have no 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.

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 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 formula (I) can be used as an organic material layer of an organic light emitting device due to its structural specificity as described above. More specifically, depending on the characteristics of various substituents introduced, Triplet-triplet annihilation (TTA) can be efficiently performed in the light emitting layer, thereby improving the internal quantum efficiency (IQE) of the compound or the electron transport layer. .

Preferred examples of the compound represented by the formula (I) according to the present invention include the following [compounds 1] to [compound 70], 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, Triplet-triplet annihilation (TTA) can be efficiently produced in the light emitting layer when the compound of the formula (I) according to the present invention is employed as a light emitting layer material. Thereby improving the internal quantum efficiency (IQE), thereby further improving the luminescence characteristics such as the luminous efficiency of the device.

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 be an organic light emitting ≪ / RTI > compounds.

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

Sodium tert-butoxide (10.38 g, 0.108 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.55 g, 0.0027 mol) were added to a solution of phenoxyazine (10 g, 0.054 mol, SigmaAldrich), bromobenzene 150 mL of Toluene was added to tri-tert-Bu-phosphine (1.09 g, 0.0054 mol, Sigma aldrich) and reacted at 100 ° C for 4 hours. 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 11.3 g (yield 80%) of Intermediate 1-1.

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

(5.64 g, 0.088 mol, Sigma aldrich) was slowly added dropwise at -78 ° C, and triethyl borate (16.76 g, 0.088 mmol) was added dropwise. mol, sigma aldrich) was added and reacted by stirring. After completion of the reaction, the reaction mixture was heated to room temperature, extracted with HCl, ethyl acetate and H ₂ O, and recrystallized to obtain 10.6 g (yield 79.4%) of Intermediate 1-2.

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

, Potassium carbonate (8.48 g, 0.061 mol, Sigma Aldrich), Pd (PPh ₃ ), 10-bromo-1,8-dichloroanthracene (10 g, 0.030 mol, Yurii), 4-biphenylboronic acid ) ₄ (1.77 g, 0.0015 mol, Sigma aldrich), 200 mL of toluene, 40 mL of EtOH and 20 mL of H ₂ O were added, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain <Intermediate 1-3> (9.8 g, yield 80%).

(4) Manufacturing example  4: Synthesis of compound 1

Intermediate 1-3 (10 g, 0.025 mol) , intermediate 2-6 (10.49 g, 0.030 mol, sigma aldrich), potassium carbonate (13.84 g, 0.10 mol, sigma aldrich), Pd (PPh 3) 4 (1.45 g, 0.0013 mol, Sigma aldrich), 200 mL of Tol, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 12 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 6.6 g (yield: 66%) of Compound 1.

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.27 / s, 7.87 / d, 7.79 / d, 7.61 / d, 7.45 / m, 7.43 / d, 7.41 / m, 7.34 / m, 7.04 / m M, 7.31 / m, 6.98 / d, 6.77 / m, 6.43 / d, 6.26 / d, 5.90 / m, 5.80 / ) 4H (7.25 / d)

LC / MS: m / z = 587 [(M + 1) ^&lt; ^{+ &}

Synthetic example  2: Synthesis of compound 3

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

Sodium tert-butoxide (10.38 g, 0.108 mol, Sigma aldrich), Catalyst Pd (dba), Phenoxazine (10 g, 0.054 mol, Sigma aldrich), 1-bromo-4-phenylnaphthalene (18.35 g, 0.065 mol, _{2 (1.55 g, 0.0027 mol,} sigma aldrich), tri-tert-Bu-phosphine into a 200 mL Toluene in (1.09 g, 0.0054 mol, sigma aldrich) was reacted under stirring at 100 ℃ for 4 hours. 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 16 g (yield 76.5%) of <Intermediate 3-1>.

(2) Manufacturing example  2: Synthesis of intermediate 3-2

(3.8 g, 0.059 mol, Sigma aldrich) was slowly added dropwise at -78 ° C, and triethyl borate (11.3 g, 0.077 mol) was added dropwise. mol, sigma aldrich) was added and reacted by stirring. After completion of the reaction, the reaction mixture was heated to room temperature, extracted with HCl, ethyl acetate and H ₂ O and recrystallized to obtain 9.4 g (yield: 76.7%) of Intermediate 3-2.

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

10-bromo-1,8-dichloroanthracene ( 10 g, 0.031 mol, Yurui), phenylboronic aicd (4.49 g, 0.037 mol, sigmaldrich), potassium carbonate (8.48 g, 0.061 mol, sigma aldrich), Pd (PPh 3) 4 (1.77 g, 0.0015 mol, Sigma aldrich), 200 mL of toluene, 40 mL of EtOH and 20 mL of H ₂ O were added, and the mixture was stirred under reflux 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 7.8 g (yield 78.7%) of Intermediate 3-3.

(4) Manufacturing example  4: Synthesis of Compound 3

Intermediate 3-3 (10 g, 0.031 mol) , intermediate 3-2 (17.64 g, 0.037 mol) , potassium carbonate (17.10 g, 0.124 mol, sigma aldrich), Pd (PPh 3) 4 (1.79 g, 0.001 mol, sigma aldrich), 200 mL of toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 12 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 10 g (yield: 50.7%) of Compound 3.

7.87 d, 7.78 d, 7.61 d, 7.54 m, 7.53 m, 7.45 m (1 H-NMR (200 MHz, CDCl ₃ ) M, 7.34 / m, 6.98 / d, 6.43 / d, 6.26 / d, 5.90 / m, 5.80 / m, 4.58 / s, 3.78 / ) 3H (7.79 / d) 4H (7.51 / m)

LC / MS: m / z = 637 [(M + 1) ^&lt; ^{+ &}

Synthetic example  3: Compound 20 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 20-1

(Dibenzofuranyl) boronic acid (8.99 g, 0.042 mol, Sigma Aldrich), potassium carbonate (12.21 g, 0.088 mol, SigmaAldrich), Pd (PPh ₃ ) ₄ (2.04 g, 0.002 mol, sigma aldrich), 200 mL of toluene, 40 mL of EtOH and 20 mL of H ₂ O were added and the mixture was stirred under reflux for 12 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 8.7 g (yield: 76.1%) of Intermediate 20-1.

(2) Manufacturing example  2: Synthesis of intermediate 20-2

Sodium tert-butoxide (10.38 g, 0.108 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.55 g, 0.0027 mol), Phenoxazine (10 g, 0.054 mol, sigma aldrich) 200 mL of toluene was added to tri-tert-Bu-phosphine (1.09 g, 0.0054 mol, Sigma aldrich) and reacted at 100 ° C for 4 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: EA) to obtain 17 g (yield 76.6%) of Intermediate 3-1.

(3) Manufacturing example  3: Synthesis of intermediate 20-3

(3.3 g, 0.052 mol, Sigma aldrich) was slowly added dropwise at -78 ° C, and triethyl borate (10.25 g, 0.070 mol) was added dropwise. mol, sigma aldrich) was added and reacted by stirring. After completion of the reaction, the reaction mixture was heated to room temperature, extracted with HCl, ethyl acetate and H ₂ O, and recrystallized to obtain 8.5 g (yield 70.5%) of Intermediate 20-3.

(4) Manufacturing example  4: Synthesis of Compound 20

Intermediate 3-3 (10 g, 0.020 mol) , intermediate 20-3 (19.12 g, 0.024 mol) , potassium carbonate (19.24 g, 0.139 mol, sigma aldrich), Pd (PPh 3) 4 (1.79 g, 0.001 mol, sigma aldrich), 200 mL of toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 12 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 11.4 g (yield: 54.3%) of Compound 20.

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.27 / s, 7.89 / d, 7.87 / d, 7.85 / d, 7.81 / d, 7.79 / d, 7.66 / d, 7.61 / d, 7.45 / m M, 7.32 / m, 7.04 / m, 6.98 / d, 6.43 / d, 6.26 / d, 5.90 / m, 5.80 / m, 4.58 / s, 3.78 / (7.57 / d, 7.52 / d, 7.51 / m, 7.38 / m, 6.66 / d)

LC / MS: m / z = 677 [(M + 1) ^&lt; ^{+ &}

Synthetic example  4: Compound 42 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 42-1

4-bromophenylboronic acid (14.4 g, 0.072 mol, Sigma aldrich), potassium carbonate (20.66 g, 0.150 mol, Sigma Aldrich), Cu (7.60 g, 0.120 mol, Sigma aldrich), dibenzo-18-crown-6 (2.16 g, 0.006 mol, sigma aldrich) and 200 mL of DMF were added and reacted by refluxing for 12 hours. After completion of the reaction, the reaction mixture was extracted and subjected to column purification (N-HEXANE: MC) to obtain 13.1 g (yield: 76.3%) of Intermediate 42-1.

(2) Manufacturing example  2: Synthesis of intermediate 42-2

10-bromo-1,8-dichloroanthracene ( 10 g, 0.031 mol, Yurui), intermediate 42-1 (10.57 g, 0.037 mol) , potassium carbonate (12.72 g, 0.092 mol, sigma aldrich), Pd (PPh 3) 4 (1.77 g, 0.0015 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 reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 11.4 g (yield: 76.1%) of Intermediate 42-2.

(3) Manufacturing example  3: Synthesis of Compound 42

Intermediate 42-2 (10 g, 0.021 mol) , intermediate 1-2 (8.57 g, 0.025 mol) , potassium carbonate (12.73 g, 0.092 mol, sigma aldrich), Pd (PPh 3) 4 (1.18 g, 0.001 mol, sigma aldrich), 200 mL of toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 12 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: 57.7%) of Compound 42.

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.55 / d, 8.27 / s, 8.12 / d, 7.94 / d, 7.87 / d, 7.63 / d, 7.61 / d, 7.50 / m, 7.45 / m M, 7.29 / m, 7.04 / m, 6.98 / m, 6.77 / m, 6.43 / d, 6.26 / d, 5.90 / m, 5.80 m, 4.58 / d, 3.78 / m) 2H (7.68 / d, 7.23 / m) 3H (7.79 / d, 7.33 / m)

LC / MS: m / z = 676 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Compound 53 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 53-1

Bis (pinacolato) dibron (8.50 g, 0.034 mol, Sigma Aldrich), potassium acetate (10 g, 0.021 mol, TCI), 2- (4-bromophenyl) -4,6-diphenyl- 5.06 g, 0.052 mol, sigma aldrich), PdCl ₂ (dppf) (0.57 g, 0.0008 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, layer separation was performed, and column purification (N-HEXANE: MC) was conducted to obtain 8.2 g (yield: 73.1%) of Intermediate 53-1.

(2) Manufacturing example  2: Synthesis of intermediate 53-2

(16.02 g, 0.037 mol), potassium carbonate (10.60 g, 0.077 mol, Sigma aldrich), Pd (PPh ₃ ) ₄ (10 g, 0.031 mol, Yurui), 10-bromo-1,8-dichloroanthracene (1.77 g, 0.0015 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 reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 13.4 g (yield 78.8%) of Intermediate 53-2.

(3) Production Example 3  : Synthesis of Compound 53

Intermediate 53-2 (10 g, 0.018 mol) , intermediate 1-2 (7.55 g, 0.022 mol, sigma aldrich), potassium carbonate (11.22 g, 0.081 mol, sigma aldrich), Pd (PPh 3) 4 (1.04 g, 0.0009 mol, Sigma aldrich), 200 mL of toluene, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 12 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 7.6 g (yield: 56.7%) of Compound 53.

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.27 / s, 7.87 / d, 7.79 / d, 7.61 / d, 7.45 / m, 7.43 / d, 7.34 / m, 7.04 / m, 6.98 / d M, 7.31 / m, 6.43 / d, 6.26 / d, 5.90 / m, 5.80 / m) 4H (8.28 / d, 7.51 / m)

LC / MS: m / z = 742 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Compound 64 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 64-1

Benzene-1,4-diboronic acid (7.68 g, 0.046 mol, SigmaAldrich), potassium carbonate (13.34 g, 0.096 mol, Sigma Aldrich), 5-bromo- _{, Pd (PPh 3) 4 (} 2.23 g, 0.002 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H 2 O 20 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: MC and then subjected to column purification (N-HEXANE: MC) to obtain 9.2 g (yield: 79.4%) of Intermediate 64-1.

(2) Manufacturing example  2: Synthesis of intermediate 64-2

10-bromo-1,8-dichloroanthracene ( 10 g, 0.031 mol, Yurui), intermediate 64-1 (11.05 g, 0.037 mol) , potassium carbonate (10.60 g, 0.077 mol, sigma aldrich), Pd (PPh 3) 4 (1.77 g, 0.0015 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 reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 12 g (yield 78%) of Intermediate 64-2.

(3) Manufacturing example  3: Synthesis of Compound 64

Intermediate 64-2 (10 g, 0.020 mol) , intermediate 1-2 (8.35 g, 0.024 mol, sigma aldrich), potassium carbonate (13.78 g, 0.100 mol, sigma aldrich), Pd (PPh 3) 4 (1.15 g, 0.0010 mol, Sigma aldrich), 200 mL of Tol, 40 mL of EtOH, 20 mL of H ₂ O, and the mixture was stirred under reflux for 12 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 7.5 g (yield: 54.5%) of Compound 64.

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.48 / d, 8.38 / d, 8.27 / s, 7.87 / d, 7.79 / d, 7.65 / s, 7.61 / d, 7.45 / m, 7.43 / d M, 6.98 / d, 6.77 / m, 6.43 / d, 6.26 / d, 5.90 / d, 5.80 / m, 4.58 / m, 3.78 / , 7.33 / s, 7.23 / m) 4H (7.25 / d)

LC / MS: m / z = 689 [(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 to 9

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 host compound in the luminescent layer, and the luminescent characteristics including the luminescent efficiency were measured.

A hole injection layer (HAT_CN 5 nm) / a hole transport layer (-NPB 100 nm) / an electron blocking layer (TCTA 10 nm) / a light emitting layer (20 nm) / an electron transport layer (201: Liq 30 nm) / LiF (1 nm) / Al (100 nm)

A hole injecting layer of 5 nm thick was formed on the ITO transparent electrode by HAT_CN using a vacuum thermal deposition method, and then the hole transporting layer was formed by using -NPB. The electron blocking layer was deposited to a thickness of 10 nm by TCTA. As the host compound of the light emitting layer, the compound represented by Chemical Formula 1, 3, 12, 20, 27, 35, 42, 53 and 64 of the present invention is used and the dopant compound is prepared by using [BD1] And 30 nm of an electron transport layer (doped with Liq 50% of the compound [201] below), 1 nm of LiF and 100 nm of aluminum were deposited by vapor deposition to prepare an organic electroluminescent device.

Device Comparative Example 1

The organic electroluminescent device for Device Comparison Example 1 was fabricated in the same manner as in Example 1, except that BH1 was used instead of the compound according to the present invention as the light emitting layer compound in the device structure of Example 1 above.

EXPERIMENTAL EXAMPLE 1: Luminescent characteristics of element embodiments 1 to 9

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 Emitting layer host V cd / A QE (%) CIEx CIEy One Formula 1 4.15 7.30 5.79 0.144 0.154 2 (3) 4.18 7.23 5.72 0.144 0.155 3 Formula 12 4.19 7.27 5.76 0.144 0.154 4 20 4.22 7.22 5.71 0.145 0.156 5 27 4.23 7.18 5.68 0.145 0.155 6 (35) 4.26 7.11 5.62 0.145 0.154 7 Formula 42 4.17 7.29 5.78 0.145 0.155 8 Formula 53 4.18 7.24 5.71 0.144 0.154 9 (64) 4.18 7.20 5.70 0.145 0.154 Comparative Example 1 BH1 4.24 5.2 4.34 0.147 0.156

When the light emitting layer compound according to the present invention was applied to the device, the luminescence efficiency such as the luminescence efficiency and the quantum efficiency was remarkably higher than that of the conventional device (Comparative Example, when an anthracene derivative was used as the host compound) It can be confirmed that it is excellent.

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

Claims (7)

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

In the above formula (I)
L ₁ and L ₂ are the same or different from each other and each independently represents a single bond, 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 in which at least one of the substituted or unsubstituted C 3 -C 30 cycloalkyl is fused and a substituted or unsubstituted C 3 -C 30 cycloalkyl in which at least one of the substituted or unsubstituted C2- (Wherein p and q are each an integer of 0 to 3),
Ar ₁ and Ar ₂ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted group having 2 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 C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, 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, (N and m are each an integer of 0 to 3). The method according to claim 1,
The substitution or unsubstitution means that the L ₁ , L ₂ , Ar ₁ and Ar ₂ are each an alkyl 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, an alkyl group having 1 to 24 carbon atoms An amino group and an arylamino group having 1 to 24 carbon atoms and is substituted with one or two or more selected substituents selected from the group consisting of an organic luminescent group and an organic luminescent group, compound. The method according to claim 1,
The organic electroluminescent compound represented by the above formula (I) is any one selected from the following formulas (1) to (70):

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 material layers comprises at least one organic light emitting compound represented by Formula (I) according to Claim 1. 5. The method of claim 4,
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 formula (I). 6. The method of claim 5,
The organic electroluminescent device according to claim 1, wherein the luminescent compound represented by Formula (I) is included in the luminescent layer. 6. The method of claim 5,
The luminescent layer containing the luminescent compound represented by the above-mentioned formula (I) is characterized in that the transition energy (? Est) between singlet and triplet is small so that the triplet exciton can be transferred to singlet in the triplet-triplet extinction phenomenon To the organic electroluminescent device.

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