KR20190021129A - 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). When the organic light-emitting compound is applied in an organic layer such as a light-emitting layer as a compound, 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 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, it is an object of the present invention to provide a novel organic light-emitting compound which can be employed as a light-emitting layer compound in an organic electroluminescent device to significantly improve light-emitting properties such as luminous efficiency and an organic electroluminescent device including the same.

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 in the light emitting layer has remarkably excellent luminescent properties such as longevity and luminous efficiency as compared with the conventional device, and thus 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 relates to an organic electroluminescent device having an organic electroluminescent device represented by the following formula (I) and having improved light emission characteristics such as quantum efficiency and luminous efficiency when used in an organic material layer such as a light emitting layer in an organic electroluminescent device Do.

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 is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 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 cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroarylene group in which one or more substituted or unsubstituted C 6 to C 50 arylene groups and substituted or unsubstituted C 3 to C 30 cycloalkyls are fused together, (N is an integer of 1 to 3).

Ar ₁ and Ar ₂ each independently represent 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 cycloalkyl having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroaryl group, and a substituted or unsubstituted C2 to C50 heteroaryl group wherein at least one of the substituted or unsubstituted C3 to C30 cycloalkyl is fused.

Ar ₁ and Ar ₂ and substituents thereof may be bonded to each other or may be connected with adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring, and the formed alicyclic or aromatic monocyclic or polycyclic ring May be substituted with any one or more heteroatoms selected from N, S and O.

In the definitions of L, Ar ₁ and Ar ₂ , the substituted or unsubstituted groups are those in which L, Ar ₁ and Ar ₂ are deuterium, cyano group, halogen group, hydroxyl group, nitro group, 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, a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 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, which is substituted with one or two or more selected substituents, Substituted with a substituent is 2 or more substituents, or associated, it means having no road or 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 in 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 diode due to its structural specificity as described above. More specifically, the organic luminescent compound according to the present invention has a characteristic structure, Triplet-triplet annihilation (TTA) can be efficiently performed in the light emitting layer, thereby improving the internal quantum efficiency (IQE). .

Specific preferred examples of the compound represented by the formula (I) according to the present invention include the following [compounds 1] to [215], 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 performed in the light emitting layer when the compound of 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

(9.84 g, 0.039 mol, Sigma Aldrich), potassium acetate (5.84 g, 0.060 mol, Sigma Aldrich), PdCl ₂ (dppf), 1,8-dibromoanthracene (10 g, 0.030 mol, Sigma Aldrich) (0.65 g, 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 9.4 g (yield: 73%) of Intermediate 1-1.

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

1,8-dibromoanthracene (10 g, 0.030 mol, sigma aldrich), intermediate 1-1 (14.08 g, 0.033 mol) , potassium carbonate (12.34 g, 0.089 mol, sigma aldrich), Pd (PPh 3) 4 (1.72 g , 0.0015 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 7.2 g (yield: 68.7%) of Intermediate 1-2.

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

Intermediate 1-2 (10 g, 0.028 mol) and 200 mL of chloroform are added, and the mixture is cooled to 0 ° C and bromine (9.52 g, 0.060 mol, Sigma aldrich) is slowly dropped while 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, followed by layer separation and recrystallization. Thus, 12 g (yield: 82.9%) of Intermediate 1-3 was obtained.

(4) Manufacturing example  4: Synthesis of compound 1

Intermediate 1-3 (10 g, 0.020 mol) , phenylboronic acid (5.26 g, 0.043 mol, sigma aldrich), potassium carbonate (10.84 g, 0.078 mol, sigma aldrich), Pd (PPh 3) 4 (1.13 g, 0.001 mol , sigma aldrich), Tol 150 mL, EtOH 30 mL, H ₂ O 15 mL, and the mixture was stirred under reflux for 12 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 8 g (yield 80.9%) of Compound 1.

M, 8H (7.39 / m), 8.07 / s, 7.41 / m) 4H (7.91 / d, 7.52 / d, 7.51 /

LC / MS: m / z = 504 [(M + 1) ^< ^{+ &}

Synthetic example  2: Compound 33 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 33-1

The mixture was stirred at 40 ° C for 30 minutes, and 2.5 M n-BuLi (3.05 g, 0.0476 mol, Sigma Aldrich) was added to the solution. The reaction mixture was heated to room temperature and stirred for 8 hours. The reaction mixture was cooled to -78 ° C, and trimethyl (trimethylethyl) ethylamine dissolved in THF was added thereto. borate (5.44 g, 0.0523 mol, Sigma aldrich) was slowly added dropwise, followed by stirring at room temperature for 8 hours, cooling again to 0 ° C, adding 2N HCl aqueous solution, and stirring at room temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with ether, concentrated, and recrystallized to obtain 7.7 g (yield: 63.7%) of Intermediate 33-1.

(2) Manufacturing example  2: Synthesis of intermediate 33-2

1-bomo-4-iodobenzene ( 10 g, 0.035 mol), intermediate 33-1 (10.78 g, 0.042 mol) , potassium carbonate (12.21 g, 0.088 mol, sigma aldrich), Pd (PPh 3) 4 (2.04 g, 0.0018 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 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 10.4 g (yield: 80.5%) of Intermediate 33-2.

(3) Manufacturing example  3: Synthesis of intermediate 33-3

To a solution of intermediate 33-2 (10 g, 0.027 mol), Bis (pinacolato) dibron (8.34 g, 0.033 mol, Sigma Aldrich), potassium acetate (5.37 g, 0.055 mol, Sigma Aldrich), PdCl ₂ (dppf) 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, layer separation was carried out, and column purification (N-HEXANE: MC) was conducted to obtain 8 g (yield: 70.9%) of Intermediate 33-3.

(4) Manufacturing example  4: Synthesis of intermediate 33-4

Intermediate 1-3 (10 g, 0.020 mol) , phenylboronic acid (2.63 g, 0.022 mol, sigma aldrich), potassium carbonate (6.77 g, 0.049 mol, sigma aldrich), Pd (PPh 3) 4 (1.13 g, 0.001 mol , sigma aldrich), Tol 150 mL, EtOH 30 mL, H ₂ O 15 mL, 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 7.7 g (yield: 77.4%) of Intermediate 33-4.

(5) Manufacturing example  5: Synthesis of Compound 33

Intermediate 33-4 (10 g, 0.020 mol) , intermediate 33-3 (9.75 g, 0.024 mol) , potassium carbonate (6.81 g, 0.050 mol, sigma aldrich), Pd (PPh 3) 4 (1.14 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 11 g (yield 78.3%) of Compound 33.

M, 2H) (8.27 / s, 7.52 / d, 7.23 / m, 7.22 / d, d, 7.51 / m) 4H (7.91 / d) 5H (7.25 / d)

LC / MS: m / z = 712 [(M + 1) ^< ^{+ &}

Synthetic example  3: Compound 54 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 54-1

Bis (pinacolato) dibron (8.50 g, 0.034 mol, Sigma Aldrich), potassium acetate (10 g, 0.02 mol, 5.06 g, 0.052 mol, Sigma aldrich), PdCl ₂ (dppf) (0.89 g, 0.0012 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 8.9 g (yield: 79.4%) of Intermediate 54-1.

(2) Manufacturing example  2: Synthesis of compound 54

1,4-dibromobenzene (10 g, 0.042 mol, sigma aldrich), intermediate 81-1 (14.96 g, 0.051 mol) , potassium carbonate (17.58 g, 0.127 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, and the mixture was stirred under reflux for 12 hours. 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 11 g (yield: 80.3%) of Compound 54.

(8.28 / d, 7.91 / d), 6H (7.51 (d, 2H). / m) 8H (7.39 / m)

LC / MS: m / z = 735 [(M + 1) ^< ^{+ &}

Synthetic example  4: Compound 97 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 97-1

2-bromophenylboronic acid (9.56 g, 0.0476 mol, Sigma aldrich), potassium carbonate (16.45 g, 0.119 mol, Sigma aldrich), catalyst Pd (PPh ₃ ) ₄ (2.29 g, 0.002 mol, sigma aldrich) were added 200 mL of THF and 80 mL of water, and the mixture was reacted at 60 DEG 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 11 g (yield: 84.5%) of Intermediate 97-1.

(2) Manufacturing example  2: Synthesis of intermediate 97-2

300 mL of the intermediate 97-1 (20 g, 0.061 mol), triphenylphosphine (47.96 g, 0.183 mol, sigma aldrich) and 1,2-dichlorobenzene were added and reacted at 180 ° C for 12 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) to obtain 10.6 g (yield: 80%) of Intermediate 97-2.

(3) Manufacturing example  3: Synthesis of Compound 97

Intermediate 33-4 (10 g, 0.020 mol), intermediate 97-2 (5.1 g, 0.0236 mol), potassium carbonate (6.81 g, 0.049 mol, sigma aldrich), Cu (2.5 g, 0.039 mol, Sigma aldrich), dibenzo -18-crown-6 (0.71 g, 0.002 mol, Sigma Aldrich) and 200 mL of dimethylformamide, and the mixture was reacted at 150 ° C for 12 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 10 g (yield 78.8%) of Compound 97.

D, 7.65 d, 7.63 d, 7.41 dl, 7.41 dl, 8.3 dl, 8.27 dl, 8.16 dl, 7.31 / m, 7.25 / m) 2H (7.91 / d, 7.90 / d, 7.67 / m, 7.52 / d, 7.51 /

LC / MS: m / z = 643 [(M + 1) ^< ^{+ &}

Synthetic example  5: Compound 133 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 133-1

Phenanthren-9-ylboronic acid (9.32 g, 0.042 mol, Sigma aldrich), potassium carbonate (12.08 g, 0.087 mol, Sigma aldrich), catalyst Pd (PPh ₃ ) ₄ (2.02 g, 0.0017 mol, Sigma aldrich) were added 200 mL of THF and 80 mL of water, and the mixture was reacted at 60 ° 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 <Intermediate 133-1> (10.6 g, yield 79%).

(2) Manufacturing example  2: Synthesis of intermediate 133-2

PdCl ₂ (dppf) (0.57 g, 0.034 mol, Sigma Aldrich), potassium acetate (5.12 g, 0.052 mol, SigmaAldrich), Bis (pinacolato) dibron (8.61 g, 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 8.2 g (yield: 73%) of Intermediate 133-2.

(3) Manufacturing example  3: Synthesis of Compound 133

Intermediate 33-4 (10 g, 0.020 mol) , intermediate 133-2 (10.18 g, 0.024 mol) , potassium carbonate (6.81 g, 0.049 mol, sigma aldrich), Pd (PPh 3) 4 (1.14 g, 0.001 mol, sigma aldrich), Tol 150 mL, EtOH 30 mL, H ₂ O 15 mL, 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 11.5 g (yield: 79.8%) of 133.

D, 8.01 / d, 7.88 / m, 7.82 / d, 8.08 / dl, m, 7.55 / m, 7.52 / d, 7.51 / m), 4H (7.91 / d)

LC / MS: m / z = 730 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Compound 188 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 188-1

4-ylboronic acid (5 g, 0.024 mol, Sigma aldrich), potassium carbonate (6.77 g, 0.049 mol, SigmaAldrich), Pd _{PPh 3) 4 (1.13 g,} 0.001 mol, sigma aldrich), Tol 150 mL, EtOH 30 mL, H 2 O 15 mL placed and reacted by stirring under reflux for 7 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 g (yield: 76.8%) of Intermediate 188-1.

(2) Manufacturing example  2: Synthesis of compound 188

Intermediate 188-1 (10 g, 0.017 mol) , intermediate 54-1 (8.74 g, 0.020 mol) , potassium carbonate (5.78 g, 0.042 mol, sigma aldrich), Pd (PPh 3) 4 (0.97 g, 0.008 mol, sigma aldrich), Tol 150 mL, EtOH 30 mL, H ₂ O 15 mL, 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 79.6%) of Compound 188.

M, 7.38 / m, 7.25 / d). 1H-NMR (200MHz, CDCl3):? Ppm, 1H (7.89 / d, 7.81 / 7.85 / d) 4H (8.28 / d, 7.51 / m, 7.91 / d) 8H (7.39 / m)

LC / MS: m / z = 825 [(M + 1) ^&lt; ^{+ &}

Device Example

In the embodiment of the present invention, an ITO transparent electrode is attached on a glass substrate of 25 mm x 25 mm x 0.7 mm, and an ITO glass substrate with an ITO transparent electrode is used to have a light emitting area of 2 mm x 2 mm And then cleaned. 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 manufactured using the compound of the present invention as a compound of the emitting layer, and the luminescent characteristics including the luminous efficiency were measured.

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

In order to form a hole injection layer on the ITO transparent electrode, a 5 nm thick layer was formed by vacuum thermal evaporation using HAT_CN, and then the hole transport layer was formed by using α-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, 33, 54, 70, 97, 111, 133, 188 and 204 of the present invention is used and the dopant compound has a thickness of about 20 nm And 30 nm of an electron transport layer (doping with Liq 50% of compound [201] below), 1 nm of LiF and 100 nm of aluminum were deposited by vapor deposition to produce 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 4.18 7.28 5.76 0.144 0.154 2 Formula 33 4.20 7.35 5.82 0.145 0.154 3 54 4.19 7.22 5.70 0.144 0.155 4 70 4.25 7.10 5.62 0.145 0.156 5 97 4.22 7.19 5.66 0.145 0.154 6 Formula 111 4.21 7.10 5.63 0.145 0.155 7 (133) 4.20 7.17 5.64 0.145 0.155 8 188 4.18 7.23 5.72 0.144 0.154 9 Formula 204 4.16 7.30 5.79 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 is applied to a device, the light emitting efficiency, the quantum efficiency, and the like can be improved compared with the device (comparative example) in which a conventional anthracene derivative is employed as the host compound (BH1) It can be confirmed that the luminescent properties are remarkably 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 is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 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 cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroarylene group in which one or more substituted or unsubstituted C 6 to C 50 arylene groups and substituted or unsubstituted C 3 to C 30 cycloalkyls are fused together, (N is an integer of 1 to 3),
Ar ₁ and Ar ₂ each independently represent 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 cycloalkyl having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroaryl group which is fused or fused with at least one of an aryl group having 6 to 50 carbon atoms and a substituted or unsubstituted C3 to 30 cycloalkyl,
Ar ₁ and Ar ₂ and substituents thereof may be bonded to each other or may be connected with adjacent substituents to form a single alicyclic or aromatic ring or a polycyclic ring, and the carbon atom of the alicyclic or aromatic single ring or polycyclic ring formed May be substituted with any one or more heteroatoms selected from N, S and O. The method according to claim 1,
The substitution or unsubstitution means that the L, Ar ₁ and Ar ₂ are each 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 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, or an aryl group having 2 to 24 carbon atoms, or an alkoxy 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 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 from 1 to 24 carbon atoms, and an aryloxy group having from 1 to 24 carbon atoms, and is substituted with one or two or more selected substituents selected from the group consisting of The organic light emitting compound means that the group is substituted with a substituent is connected, or does not have any substituent. The method according to claim 1,
The organic electroluminescent compound represented by Formula (I) is any one selected from the following Formulas (1) to (215):

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 layer of the organic material layer contains 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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