KR102107086B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device comprising the same.

Description

Novel compound and organic light emitting device comprising the same

The present invention relates to a novel compound and an organic light emitting device comprising the same.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound and an organic light emitting device comprising the same.

The present invention provides compounds of Formula 1

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,

R ₁ and R ₂ together form the structure of Formula 2a or Formula 2b:

R ₃ and R ₄ together form a structure of Formula 2a or Formula 2b:

[Formula 2a]

[Formula 2b]

A and B together form a structure of Formula 3a or Formula 3b,

[Formula 3a]

[Formula 3b]

In the formulas 3a and 3b,

R ₅ and R ₆ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 haloalkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _{6- 60} aryl, substituted or unsubstituted C _6-60 aryloxy, or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S, or R ₅ and R ₆ are connected to each other to form a C _6-12 aromatic ring group, or a C _2-12 heterocyclic group including one or more heteroatoms selected from the group consisting of N, O and S.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound of Formula 1, and provides an organic light emitting device.

The compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and / or life characteristics in the organic light emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Figure 2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is done.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups and dibenzofuranyl groups, and the like, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described alkyl group. In the present specification, the description of the heteroaryl group among heteroarylamines may be applied. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and a description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

On the other hand, the present invention provides a compound of Formula 1:

A compound of Formula 1

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,

R ₁ and R ₂ together form the structure of Formula 2a or Formula 2b:

R ₃ and R ₄ together form a structure of Formula 2a or Formula 2b:

[Formula 2a]

[Formula 2b]

A and B together form a structure of Formula 3a or Formula 3b,

[Formula 3a]

[Formula 3b]

In the formulas 3a and 3b,

R ₅ and R ₆ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 haloalkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _{6- 60} aryl, substituted or unsubstituted C _6-60 aryloxy, or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S, or R ₅ and R ₆ are connected to each other to form a C _6-12 aromatic ring group, or a C _2-12 heterocyclic group including one or more heteroatoms selected from the group consisting of N, O and S.

Specifically, in Formula 1, when A and B are connected to form a hexagonal ring, a structure of Formula 3a or Formula 3b may be formed. If, when the A and B are connected to form a pentagonal ring, there may be a problem that the stability of the molecule is lowered due to steric hindrance between the structures formed by Formula 2a or Formula 2b. However, according to the present invention, because the A and B of Formula 1 form a hexagonal ring by Formula 3a or Formula 3Bdp, the angle between structures becomes larger than that of a pentagonal ring, thereby reducing the steric hindrance in the molecule, thereby improving the stability of the molecule. There is an advantage that can be increased. Therefore, the organic light emitting device using the compound of Formula 1 may have a long life characteristic.

More specifically, the compound of Formula 1 may be any one of the compounds of Formulas 4 to 28 below.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

In Formulas 4 to 28, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl group; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

In addition, in Formula 1, Ar ₁ to Ar ₄ may be each independently, any one selected from the group consisting of.

Representative examples of the compound represented by Formula 1 are as follows:

On the other hand, the compound of Formula 1, for example, may be prepared by the same method as in Scheme 1. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In Reaction Scheme 1, description of Ar ₁ and Ar ₂ is as defined in Chemical Formula 1.

On the other hand, the present invention provides an organic light emitting device comprising the compound of Formula 1 above. In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. .

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 It includes the compound displayed.

Further, the organic material layer may include a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.

Further, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously performs electron injection and electron transport includes the compound represented by Chemical Formula 1.

In addition, the organic material layer includes a light emitting layer and an electron transport layer, and the light emitting layer may include a compound represented by Chemical Formula 1.

Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

Figure 2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is done. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this 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.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

The positive electrode material is usually a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode 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 metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in a light emitting layer A compound that prevents migration of the excited excitons to the electron injection layer or the electron injection material, and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light emitting layer, and is a material that can transport holes to the light emitting layer by receiving holes from the anode or the hole injection layer as a hole transport material and has a large mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto. The content of the dopant may be from 1% to 99% compared to the host amount of the light emitting layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transport material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As a material capable of receiving electrons well and transferring them to the light emitting layer, a material having high mobility for electrons is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

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

In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Example 1: Synthesis of Compound 1

Step 1-1) Synthesis of Compound 1-1

[Compound 1-1]

1-bromodibenzo [b, d] furan-1-amine (40.0g, 152.6mmol) and Bi (NO ₃ ) ₃ 5H ₂ O (74.0g, 152.6mmol), CH ₂ Cl ₂ 763 ml and acetic anhydride (87 ml, 915.6 mmol) were added and stirred at room temperature for 5 hours. After the reaction was completed, saturated NaHCO ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 42.6 g of Compound 1-1 in the solid phase (yield 80%, MS [M + H] ⁺ = 349).

Step 1-2) Synthesis of Compound 1-2

[Compound 1-2]

In a two-necked flask, Compound 1-1 (42.0 g, 120.3 mmol), 241 ml of 2M HCl, 480 ml of THF, and 240 ml of EtOH were heated in an argon atmosphere under reflux conditions for 8 hours. After the reaction, the organic solvent was concentrated under reduced pressure after cooling to room temperature. After neutralizing the concentrate with 2M NaOH aqueous solution, it was transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried with MgSO ₄ and purified by silica gel column chromatography to obtain 28.4 g of Compound 1-2 as a solid (yield 77%, MS [M + H] ⁺ = 307).

Step 1-3) Synthesis of Compound 1-3

[Compound 1-3]

Compound 1-2 (28.0g, 91.2mmol), 182ml of 1M HCl and 300ml of water were added to a 3-neck flask, cooled to 0 ° C, and stirred for 1 hour. NaNO ₂ at the same temperature (12.6 g, 182.4 mmol) 300 ml of the aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. Then, 400 ml of potassium iodide (68.5 g, 273.5 mmol) aqueous solution was slowly added dropwise and stirred for 5 hours. After the reaction was completed, an aqueous Na ₂ S ₂ O ₃ solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 32.4 g of solid compound 1-3 (yield 85%, MS [M + H] ⁺ = 418).

Step 1-4) Synthesis of Compound 1-4

[Compound 1-4]

After the compound 1-3 (32.0g, 76.6mmol) and DMF 180ml were dissolved in a 3-neck flask, 24g of Cu powder was added and stirred under reflux conditions. After 3 hours, another 24 g of Cu powder was added and stirred for 24 hr. After the reaction was completed, after cooling to room temperature, water (1000 ml) was added, the solid was filtered, and then transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 16.3 g of Compound 1-4 as a solid (yield 73%, MS [M + H] ⁺ = 582).

Step 1-5) Synthesis of Compound 1-5

[Compound 1-5]

Compound 1-4 (16.0g, 27.5mmol), iron powder (7.7g, 137.4mmol), acetic acid 65ml and EtOH 90mL were added to a 3-neck flask, and the mixture was stirred for 10 hours under reflux conditions. After the reaction was completed, 200 ml of water was added and diluted, neutralized with an aqueous potassium carbonate solution, transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 13.1 g of Compound 1-5 (Yield 91%, MS [M + H] ⁺ = 522).

Step 1-6) Synthesis of Compound 1-6

[Compound 1-6]

Compound 1-5 (13.0g, 24.9mmol), 100ml of 1M HCl and 150ml of water were added to a 3-neck flask and cooled to 0 ° C and stirred for 1 hour. At the same temperature, 150 ml of a NaNO ₂ (6.9 g, 99.6 mmol) aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. Then, 200 ml of an aqueous potassium iodide (37.4 g, 149.4 mmol) solution was slowly added dropwise and stirred for 5 hours. After the reaction was completed, Na ₂ S ₂ O ₃ aqueous solution was added and transferred to a separatory funnel, followed by extraction with ethyl acetate. The extract was dried with MgSO 4 and purified by silica gel column chromatography to obtain 15.4 g of Compound 1-6 in the solid phase (yield 83%, MS [M + H] ⁺ = 744).

Step 1-7) Synthesis of Compound 1-7

[Compound 1-7]

Compound 1-6 (15.0 g, 20.2 mmol) and 1,2-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene ( 7.0g, 21.2mmol) in THF 200ml and K ₂ CO ₃ (11.1 g, 80.6 mmol) was dissolved in 100 ml of water and added. Here Pd (PPh ₃ ) ₄ (0.2 g, 0.2 mmol) was added, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and 300 mL of water was added and extracted with CH ₂ Cl ₂ . After drying the extract with MgSO ₄ , filtering and concentrating, the sample was purified by silica gel column chromatography to obtain 9.1 g of solid compound 1-7 (yield 80%, MS [M + H] ⁺ = 566). .

Step 1-8) Synthesis of Compound 1

[Compound 1]

Dissolve compound 1-7 (9.0g, 15.9mmol) and naphthalene-1-ylboronic acid (6.0g, 35.0mmol) in 135 ml dioxane in a three-neck flask and K ₂ CO ₃ (8.8 g, 63.6 mmol) is dissolved in 70 ml of H ₂ O. Here Pd (PPh ₃ ) ₄ (0.7g, 0.6mmol) was added, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with water and ethyl acetate. After the extract was dried with MgSO ₄ , filtered and concentrated, the sample was purified by silica gel column chromatography, and 3.2 g of Compound 1 was obtained through a sublimation tablet. (Yield 30%, MS [M + H] ⁺ = 661)

Example  2: Synthesis of Compound 2

Step 2-1) Synthesis of Compound 2-1

[Compound 2-1]

Compound 1-7 (15.0 g, 26.5 mmol) and phenylboronic acid (3.4 g, 27.8 mmol) were dissolved in 225 ml of THF in a three-necked flask and K ₂ CO ₃ (1.2 g, 1.1 mmol) was dissolved in 113 ml of water and added. Here Pd (PPh ₃ ) ₄ (1.2 g, 1.2 mmol) was added, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, 200 mL of water was added, and extracted with CH ₂ Cl ₂ . After drying the extract with MgSO ₄ , filtering and concentration, the sample was purified by silica gel column chromatography to obtain 11.6 g of compound 2-1 as a solid (yield 78%, MS [M + H] ⁺ = 637). .

Step 2-2) Synthesis of Compound 2

 [Compound 2]

Dissolve compound 2-1 (9.0g, 16.0mmol), [1,1'-biphenyl] -4-ylboronic acid (3.5g, 17.6mmol) in dioxane in 135 ml in a three-necked flask, and K ₂ CO ₃ (8.8 g, 63.6 mmol) is dissolved in 70 ml of water. Here Pd (PPh ₃ ) ₄ (0.7g, 0.6mmol) was added, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with water and ethyl acetate. After the extract was dried with MgSO ₄ , filtered and concentrated, the sample was purified by silica gel column chromatography, and 3.1 g of Compound 2 was obtained through a sublimation tablet. (Yield 30%, MS [M + H] ⁺ = 637)

Example  3: Synthesis of Compound 3

Step 3-1) Synthesis of Compound 3-1

[Compound 3-1]

In the synthesis of compound 1-7 of step 1-7) of Example 1, 1,2-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene 8.9 g of compound 3-1 was synthesized by the same method, except that it was used by changing to furan-3,4-diyldiboronic acid (yield 78%, MS [M + H] ⁺ = 566).

Step 3-2) Synthesis of Compound 3

[Compound 3]

The compound 3 was synthesized in the same manner as in Example 1, except that Compound 3-1 was used instead of Compound 1-7 in Compound 1 synthesis in Step 1-8), and 3.6 g of Compound 3 was synthesized. (Yield 35%, MS [M + H] ⁺ = 651)

Example  4: Synthesis of Compound 4

Step 4-1) Synthesis of Compound 4-1

[Compound 4-1]

4-bromonaphthalen-1-amine (35.0g, 157.6mmol) and Bi (NO ₃ ) ₃ · 5H ₂ O (76.4g, 157.6mmol), CH ₂ Cl ₂ 800ml, acetic unhydride in a 3-neck flask (89ml, 945.6mmol) was added and stirred at room temperature for 5hr. After the reaction was completed, saturated NaHCO ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 38.0 g of solid compound 4-1 (yield 78%, MS [M + H] ⁺ = 309).

Step 4-2) Synthesis of Compound 4-2

[Compound 4-2]

In a 2-neck flask, Compound 2-1 (38.0 g, 122.9 mmol), 246 ml 2M HCl, 500 ml THF, and 250 ml EtOH were heated in an argon atmosphere under reflux for 8 hours. After the reaction was completed, the organic solvent was concentrated under reduced pressure after cooling to room temperature. The concentrate was neutralized with 2M NaOH aqueous solution and then transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried with MgSO 4 and purified by silica gel column chromatography to obtain 28.4 g of solid compound 4-2 (yield 80%, MS [M + H] ⁺ = 267).

Step 4-3) Synthesis of Compound 4-3

[Compound 4-3]

Compound 4-2 (25.0 g, 93.6 mmol), 187 ml of 1M HCl, and 300 ml of water were added to a three-necked flask, cooled to 0 ° C., and stirred for 1 hour. At the same temperature, 300 ml of a NaNO ₂ (12.9 g, 187.2 mmol) aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. Thereafter, 400 ml of an aqueous potassium iodide (70.3 g, 280.8 mmol) solution was slowly added dropwise and stirred for 5 hours. After the reaction was completed, Na ₂ S ₂ O 3 aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried with MgSO 4 and purified by silica gel column chromatography to obtain 25.5 g of solid compound 4-3 (yield 72%, MS [M + H] ⁺ = 378).

Step 4-4) Synthesis of Compound 4-4

[Compound 4-4]

Compound 4-3 (25.0g, 66.1mmol) and DMF 140ml were dissolved in a three-necked flask, and then 21g of Cu powder was added and stirred under reflux conditions. After 3 hours, another 21 g of Cu powder was added and stirred for 24 hr. After the reaction was completed, after cooling to room temperature, water (800 ml) was added, the solid was filtered, and then transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 14.1 g of Compound 4-4 as a solid (yield 85%, MS [M + H] ⁺ = 502).

Step 4-5) Synthesis of Compound 4-5

[Compound 4-5]

Compound 4-4 (14.0g, 27.9mmol), iron powder (7.8g, 139.4mmol), acetic acid 63ml and EtOH 90ml were added to a 3-neck flask and stirred for 10 hours under reflux conditions. After the reaction was completed, 200 ml of water was added and diluted, neutralized with an aqueous calcium carbonate solution, transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 11.7 g of compound 4-5 (yield 95%, MS [M + H] ⁺ = 442).

Step 4-6) Synthesis of Compound 4-6

[Compound 4-6]

Compound 4-5 (11.0 g, 24.9 mmol), 100 ml of 1M HCl, and 150 ml of water were added to a 3-neck flask and cooled to 0 ° C. and stirred for 1 hour. At the same temperature, 150 ml of NaNO ₂ (6.9 g, 99.6 mmol) aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. Thereafter, 200 ml of potassium iodide (37.4 g, 149.4 mmol) aqueous solution was slowly added dropwise and stirred for 6 hours. After the reaction was completed, an aqueous Na ₂ S ₂ O ₃ solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried with MgSO 4 and purified by silica gel column chromatography to obtain 12.7 g of a solid of compound 4-6 (yield 77%, MS [M + H] ⁺ = 664).

Step 4-7) Synthesis of Compound 4-7

[Compound 4-7]

Dissolve compound 4-6 (12.0g, 18.1mmol), furan-2,3-diyldiboronic acid (3.0g, 19.0mmol) in THF 180ml in a 3-neck flask and dissolve K ₂ CO ₃ (10.0g, 72.3mmol). Dissolve in 90 ml of water. Pd (PPh ₃ ) ₄ (0.2 g, 0.2 mmol) was added thereto, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (250 mL) was added, and CH ₂ Cl ₂ was extracted. The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to obtain 7.6 g of a compound 4-7 as a solid (yield 88%, MS [M + H] ⁺ = 476).

Step 4-8) Synthesis of Compound 4

[Compound 4]

In the synthesis of compound 1 of step 1-8) of Example 1, compound 4-7 was used instead of compound 1-7, and phenylboronic acid was used instead of naphthalene-1-ylboronic acid, followed by the same method. 2.5g of 4 was synthesized. (Yield 28%, MS [M + H] ⁺ = 487)

Experimental example  One

The glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1,400 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum evaporator.

The following [HI-A] and hexanitrile hexaazatriphenylene (HAT) were sequentially thermally vacuum-deposited to a thickness of 650 Pa and 50 Pa on the prepared ITO transparent electrode to form a hole injection layer. Then, the following [HT-A] as a hole transport layer was vacuum-deposited to a thickness of 600 MPa, and then the following [HT-B] as an electron blocking layer was thermally vacuum-deposited to a thickness of 50 MPa. Subsequently, 96% by weight of the following host [Compound 1] and 4% by weight of [BD1] were vacuum deposited as a light emitting layer to a thickness of 200 Pa. Subsequently, the following [ET-A] and [Liq] were thermally vacuum-deposited to a thickness of 360 MPa at a ratio of 1: 1 as the electron transport layer and the electron injection layer, and then [Liq] was vacuum-deposited to a thickness of 5 MPa. On the electron injection layer, magnesium and silver were sequentially deposited at a thickness of 220 로 at a ratio of 10: 1, and aluminum was deposited at a thickness of 1000 음극 to form a cathode, thereby manufacturing an organic light emitting device.

[HI-A] [HAT]

[HT-A] [HT-B]

[Compound 1] [BD1]

 [ET-A] [Liq]

Experimental example  2 to 4, Comparative Experimental Example  1 and 2

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that each of the compounds shown in Table 1 below was used instead of Compound 1 as a host. The voltage, efficiency, and color coordinates were measured by applying a current density of 10 mA / cm ² to the organic light emitting device manufactured in Experimental Examples and Comparative Experimental Examples, and a life was measured by applying a current density of 20 mA / cm ² , and the results were obtained. It is shown in Table 1 below. At this time, the lifetime means the time until the initial luminance decreases to 90%.

Host @ 10mA / cm ² @ 20mA / cm ² Voltage (V) Efficiency (cd / A) Color Coordinate (CIE-x) Color Coordinate (CIE-y) Life (hr) Experimental Example 1 Compound 1 4.01 5.19 0.138 0.130 135 Experimental Example 2 Compound 2 3.98 5.21 0.138 0.130 152 Experimental Example 3 Compound 3 4.05 5.15 0.138 0.131 147 Experimental Example 4 Compound 4 4.01 5.19 0.138 0.130 129 Comparative Experimental Example 1 BH1 4.54 4.87 0.138 0.130 100 Comparative Experimental Example 2 BH2 4.73 5.08 0.141 0.130 10

 [BH1] [BH2]

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (7)

Compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,
R ₁ and R ₂ together form the structure of Formula 2a or Formula 2b:
R ₃ and R ₄ together form a structure of Formula 2a or Formula 2b:
[Formula 2a]

[Formula 2b]

A and B together form a structure of Formula 3a or Formula 3b,
[Formula 3a]

[Formula 3b]

In the formulas 3a and 3b,
R ₅ and R ₆ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 haloalkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _6-60 aryloxy, or substituted or unsubstituted N , C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of O and S, or R ₅ and R ₆ are linked to each other to form a C _6-12 aromatic ring group, or N, O and It forms a C _2-12 heterocyclic group containing one or more heteroatoms selected from the group consisting of S.
According to claim 1,
In Formula 1, R ₁ and R ₂ , and R ₃ and R ₄ are connected to each other to form a structure of Formula 2b, a compound.
According to claim 1,
Formula 1 is any one of the compounds of Formulas 4 to 28, Compound:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

In Formulas 4 to 28, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl group; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
In Formula 1, Ar ₁ and Ar ₂ are each independently, any one selected from the group consisting of:

According to claim 1,
A compound selected from the group consisting of the following compounds:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 5. That is, an organic light emitting device.
The method of claim 6,
The organic material layer containing the compound is an organic light emitting device, a light emitting layer.

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