KR102264792B1 - 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 using 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 using the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted 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, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An 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. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

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

Korean Patent Publication No. 10-2013-073537

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

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ , X ₂ and X ₃ are each independently CH or N, provided that X ₁ , At least two of _{X 2} and X- _{3 are N,}

Y is S or O;

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _{6-60 aryl or C 5-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

L ₁ is a direct bond, substituted or unsubstituted C _{6-60 arylene or C 5-60} heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S,

L ₂ is a direct bond or a substituted or unsubstituted C _6-60 arylene,

R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted C _1-60 alkyl,

m and n are each independently an integer of 0 to 3.

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 organic material layer includes the compound of the present invention.

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

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 .
2 shows an example of an organic light emitting device including 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 did it

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

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ , X ₂ and X ₃ are each independently CH or N, provided that X ₁ , At least two of _{X 2} and X- _{3 are N,}

Y is S or O;

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _{6-60 aryl, or C 5-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

L ₁ is a direct bond, substituted or unsubstituted C _{6-60 arylene, or C 5-60} heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S,

L ₂ is a direct bond or a substituted or unsubstituted C _6-60 arylene,

R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted C _1-60 alkyl,

m and n are each independently an integer of 0 to 3.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but 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, in the ester group, the oxygen of the ester group may be substituted with a linear, 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 the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. 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 include 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 are 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 an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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, stilbenyl 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 carbon number of the cycloalkyl group is 3 to 20. 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 preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a 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 be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole 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 triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl 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, isoxazolyl group group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description of the above-described heterocyclic group may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of compounds represented by Formulas 2 to 5:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,

X ₁ , X ₂ , X ₃ , Y, L ₁ , L ₂ , R ₁ , R ₂ , Ar ₁ , Ar ₂ , m and n are as defined above.

Preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

.

.

Preferably, L ₁ may be a direct bond or phenylene.

Preferably, L ₂ may be a direct bond, phenylene or naphthylene.

Preferably, R ₁ and R ₂ may each independently be hydrogen.

Preferably, m and n may each independently be 0 or 1.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:

.

.

The compound represented by Formula 1 according to the present invention includes a triazine group on the benzene ring side of benzoxazole (benzothiazole) and an N-substituted carbazole group on the heterocyclic side, thereby significantly improving electron mobility, Accordingly, it can have high efficiency, low driving voltage, high brightness, long lifespan, and the like.

The compound represented by Formula 1 may be prepared through the following Reaction Schemes 1-1 to 1-2.

[Scheme 1-1]

[Scheme 1-2]

In Scheme 1, X is halogen, preferably, bromo or chloro, and the description of the remaining substituents is as defined above.

The reaction is preferably performed in the presence of a palladium catalyst and a base as a Suzuki coupling reaction, and the reactants and catalysts for the reaction can be changed according to known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. do.

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, etc. 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 layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 The compounds shown are included.

In addition, the organic layer may include an emission layer, and the emission layer includes the compound represented by Formula 1 above.

In addition, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously injects and transports electrons includes the compound represented by Formula 1 above. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, a high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic layer capable of simultaneously performing electron injection and electron transport, an n-type dopant used in the art may be mixed and used.

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

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Also, the organic light emitting device according to the present invention may be an inverted type organic light emitting device 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 .

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 Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting device including 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 did it In such a structure, the compound represented by 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 using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, 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, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed into 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode 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.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides 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 anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect with respect to the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. Preferably, 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 material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type compounds. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. As an electron transport material, it is a material that can receive electrons from the cathode and transfer them to the light emitting layer, and a material with high electron mobility is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, 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) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. It is not limited to this.

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

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

Preparation Example 1: Preparation of intermediate compound A1

Preparation of compound A1-1

2,6-dichlorobenzo[d]thiazole (30 g, 0.147 mol), 9H-carbazole (24.6 g, 0.147 mol) and potassium phosphate (62.40 g, 0.294 mol) were mixed with dimethylacetamide (300 mL) and refluxed. After refluxing for 12 hours, when the reaction is completed, it is cooled to room temperature. After filtration, washed with water and ethanol, and dried to obtain compound A1-1. (37.9 g, yield 77%; MS: [M+H] ⁺ =335)

Preparation of compound A1

Compound A1-1 (37.9 g, 88.9 mmol) is dissolved in 1,4-dioxane (500 ml). Bis(pinacolato)diboron (33.9 g, 133.4 mmol), potassium acetate (26.2 g, 266.7 mmol) and Pd(dppf)Cl ₂ (1.9 g, 2.68 mmol) were added thereto, and then at 120° C. Stirred for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The solvent is removed by distilling the filtered solution. After extraction with chloroform and water, the organic layer _{was dried over MgSO 4} , concentrated, and recrystallized from ethyl acetate to obtain an intermediate compound A1. (32.0 g, yield 85%; MS: [M+H] ⁺ =503)

Preparation Example 2: Preparation of intermediate compound B1

Preparation of compound B1-1

(4-(9H-carbazol-9-yl)phenyl)boronic acid (25 g, 87.1 mmol) and 2,6-dichlorobenzo[d]thiazole (17.8 g, 87.1 mmol) are added to dioxane (300 ml). Then, cesium carbonate (85.1 g, 261.2 mmol) was dissolved in water (100 mL), put in a round-bottom flask, and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (1.4g, 2.6mmol) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol and dried to obtain compound B1-1. (28.5 g, yield 80%; MS: [M+H] ⁺ =411)

Preparation of compound B1

B1-1 (18 g, 43.8 mmol) is dissolved in 1,4-dioxane (500 ml). Bis(pinacolato)diboron (16.7 g, 65.7 mmol), potassium acetate (12.9 g, 131.41 mmol) and Pd(PCy)2.(OAc)2 (1 g, 1.31 mmol) were added. Then, the mixture was stirred at 120 °C for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The solvent is removed by distilling the filtered solution. After extraction with chloroform and water, the organic layer _{was dried over MgSO 4} , concentrated, and recrystallized from ethanol to obtain compound B1. (18.3 g, yield 83%; MS: [M+H] ⁺ =411)

Preparation Example 3: Preparation of intermediate compound C1

Preparation of compound C1-1

(3-(9H-carbazol-9-yl)phenyl)boronic acid (20 g, 69.7 mmol) and 2,6-dichlorobenzo[d]thiazole (14.2 g, 69.7 mmol) were added to dioxane (250 ml). Then, cesium carbonate (68.1 g, 209.0 mmol) was dissolved in water (100 mL), put in a round-bottom flask, and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (1.1g, 2.1mmol) was added, refluxed for 3 hours, and when the reaction was completed, it was cooled to room temperature. After filtration, it was washed with water and ethanol and dried to obtain compound C1-1. (20 g, yield 70%; MS: [M+H] ⁺ =395)

Preparation of compound C1

Dissolve C1-1 (20 g, 48.7 mmol) in 1,4-dioxane (500 ml). Bis(pinacolato)diboron (18.5 g, 73.0 mmol), potassium acetate (14.3 g, 146.0 mmol) and Pd(PCy)2.(OAc)2 (1.1 g, 1.46 mmol) were added. Then, the mixture was stirred at 120 °C for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The solvent is removed by distilling the filtered solution. After extraction with chloroform and water, the organic layer _{was dried over MgSO 4} , concentrated, and recrystallized from ethanol to obtain compound C1. (18 g, yield 74%; MS:[M+H] ⁺ =487)

Example 1: Preparation of compound 1

The intermediate compound 1A (15 g, 35.2 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (9.4 g, 35.2 mmol) synthesized in Preparation Example 1 was added to tetrahydrofuran (150ml). . Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), put in a round-bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare Compound 1 (12.5 g, 67%, MS: [M+H] ⁺ =532).

Example 2: Preparation of compound 2

Intermediate compound 1A (15 g, 35.2 mmol) synthesized in Preparation Example 1, 2-([1,1'-biphenyl]-4-yl)-4-(4-bromophenyl)-6-phenyl-1,3, Add 5-triazine (16.3 g, 35.2 mmol) to tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), put in a round-bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare Compound 2 (17.6 g, 73%, MS: [M+H] ⁺ =684).

Example 3: Preparation of compound 3

Intermediate compound 1A (15 g, 35.2 mmol) synthesized in Preparation Example 1, 2-(4-bromophenyl)-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5 -triazine (16.8 g, 35.2 mmol) is placed in tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), put in a round-bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 3 (10.3 g, 42%, MS: [M+H] ⁺ =698).

Example 4: Preparation of compound 4

Intermediate compound 1A (15 g, 35.2 mmol) synthesized in Preparation Example 1, 9-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (16.8 g, 35.2 mmol) in tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), put in a round-bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 4 (11.5 g, 47%, MS: [M+H] ⁺ =697).

Example 5: Preparation of compound 5

Intermediate compound A1 (15 g, 35.2 mmol) synthesized in Preparation Example 1, 2-(4-bromophenyl)-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5 -triazine (17.4 g, 35.2 mmol) is placed in tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), put in a round-bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 5 (16.1 g, 64%, MS: [M+H] ⁺ =714).

Example 6: Preparation of compound 6

The intermediate compound B1 (15 g, 29.9 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.0 g, 29.9 mmol) synthesized in Preparation Example 2 was added to tetrahydrofuran (150ml). . Then, calcium carbonate (16.5 g, 119.5 mmol) was dissolved in water (40 mL), put in a round-bottom flask, and refluxed. Then, tetrakis (triphenylphosmine) palladium (0) (1.0 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 6 (12.7 g, 70%, MS: [M+H] ⁺ =608).

Example 7: Preparation of compound 6

Intermediate compound C1 (15 g, 30.9 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.2 g, 30.9 mmol) synthesized in Preparation Example 3 was added to tetrahydrofuran (150ml). . Then, calcium carbonate (17.1 g, 123.4 mmol) was dissolved in water (40 mL), put in a round-bottom flask, and refluxed. Then, tetrakis (triphenylphosmine) palladium (0) (1.1 g, 3 mol%) was added and refluxed for 3 hours, and then cooled to room temperature when the reaction was completed. After filtration, the mixture was washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried over magnesium sulfate. Then, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 7 (6.0 g, 33%, MS: [M+H] ⁺ =592).

[Experimental example]

Experimental Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,300 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

A hole injection layer was formed by thermal vacuum deposition of the following HI-1 compound to a thickness of 50 Å on the ITO transparent electrode prepared as described above. On the hole injection layer, the following HT-1 compound was thermally vacuum deposited to a thickness of 250 Å to form a hole transport layer, and the following HT-2 compound was vacuum deposited to a thickness of 50 Å on the HT-1 deposited film to form an electron blocking layer. Compound 1 prepared in Example 1, the following YGH1 compound, and a phosphorescent dopant YGD-1 were co-deposited on the HT-2 deposited film at a ratio of 44:44:12 as a light-emitting layer to form a light-emitting layer with a thickness of 400 Å. The following ET-1 compound was vacuum-deposited to a thickness of 250 Å on the light emitting layer, and the following ET-2 compound was co-deposited with Li in a weight ratio of 2% to a thickness of 100 Å to form an electron transport layer and an electron injection layer. A cathode was formed by depositing aluminum to a thickness of 1000 Å on the electron injection layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 ~ 5 × 10 ^-8 torr did.

Experimental Examples 2-7

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1 of Example 1 in Experimental Example 1.

Comparative Experimental Examples 1-1 to 1-4

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1 of Example 1 in Experimental Example 1. The compounds of CE1 and CE2 in Table 1 below are as follows.

In the Experimental Example and Comparative Experimental Example, the driving voltage and luminous efficiency of the ^{organic light emitting diode were measured at a current density of 10 mA/cm 2} , and the time at which the initial luminance was 95% at a current density of ^{50 mA/cm 2 (LT95)} was measured. The results are shown in Table 1 below.

division compound Voltage (V)
(@10mA/cm2) Efficiency (Cd/A)
(@10mA/cm2) color coordinates
(x,y) Life (h)
LT95 at 50mA/cm2 Experimental Example 1-1 compound 1 4.22 70 0.45, 0.51 110 Experimental Example 1-2 compound 2 4.29 68 0.44, 0.52 115 Experimental Example 1-3 compound 3 4.33 67 0.44, 0.53 130 Experimental Example 1-4 compound 4 4.35 66 0.44, 0.51 124 Experimental Example 1-5 compound 5 4.41 69 0.44, 0.52 135 Experimental Example 1-6 compound 6 4.05 67 0.45, 0.52 125 Experimental Example 1-7 compound 7 4.00 68 0.45, 0.52 105 Comparative Experimental Example 1-1 CE 1 4.8 60 0.46, 0.50 90 Comparative Experimental Example 1-2 CE 2 4.9 59 0.48, 0.52 75 Comparative Experimental Example 1-3 CE 3 5.7 55 0.49, 0.51 11 Comparative Experimental Example 1-4 CE 4 6.1 57 0.50, 0.51 5

As shown in Table 1, when the compound of the present invention was used as a material for the light emitting layer, it was confirmed that the efficiency and lifespan were superior to those of Comparative Experimental Examples.

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 (9)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X ₁ , X ₂ and X ₃ are each independently CH or N, provided that X ₁ , At least two of _{X 2} and X- _{3 are N,}
Y is S or O;
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _{6-60 aryl or C 5-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
L ₁ is a direct bond, substituted or unsubstituted C _{6-60 arylene or C 5-60} heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S,
L ₂ is a direct bond, or a substituted or unsubstituted C _6-60 arylene;
R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted C _1-60 alkyl,
m and n are each independently an integer of 0 to 3.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of compounds represented by the following Formulas 2 to 4, the compound:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,
X ₁ , X ₂ , X ₃ , Y, L ₁ , L ₂ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , m and n are as defined in claim 1.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

.
The method of claim 1,
L ₁ is a direct bond or phenylene.
The method of claim 1,
L ₂ is a direct bond, phenylene or naphthylene.
The method of claim 1,
R ₁ and R ₂ are each independently hydrogen.
The method of claim 1,
m and n are each independently 0 or 1.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 8 which is an organic light emitting device.

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