KR101601354B1 - Novel compounds and organic electro luminescence device using the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device including the same, and the compound according to the present invention is used for an organic compound layer, preferably a light emitting layer, of an organic electroluminescent device, And the like can be improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic electroluminescent device including the same. BACKGROUND OF THE INVENTION [0002]

TECHNICAL FIELD The present invention relates to a novel compound and an organic electroluminescent device including the same and more particularly to a compound used in an organic material layer of an organic electroluminescent device.

In 1950, the electroluminescent (EL) device which led to the blue electroluminescence using anthracene single crystal was continued with the observation of the organic thin film emission of the Bernanose in 1950. In 1987, an organic electroluminescent device having a multilayer structure divided by a functional layer of a hole layer and a light emitting layer was proposed by Tang. Thereafter, in order to make a high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a device, and the development of specialized materials used thereon has been continued.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.

The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials necessary for realizing better natural colors. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material.

The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. Phosphorescent materials can theoretically improve luminescence efficiency up to 4 times as compared with fluorescent materials, and therefore, studies on phosphorescent host materials as well as phosphorescent dopants have been conducted.

Up to now, hole injecting layer, hole transporting layer. NPB, BCP, Alq ₃ and the like are widely known as materials used as a hole blocking layer and an electron transporting layer, and anthracene derivatives as a luminescent material have been reported as a fluorescent dopant / host material. In particular, as the phosphorescent dopant material having a great advantage in improving the efficiency aspect of the luminescent material is a Ir metal complex compound, a phosphorescent host material including such as _{Firpic, Ir (ppy) 3,} (acac) Ir (btp) 2 CBP is used.

However, conventional luminescent materials are good in terms of luminescence characteristics, but have poor thermal stability due to low glass transition temperature, and thus are not satisfactory in terms of lifetime of an organic electroluminescent device. Therefore, development of a luminescent material having excellent performance is required.

WO 2010/010184

The present invention has been made to solve the above problems and it is an object of the present invention to provide a novel compound capable of improving the efficiency, lifetime and stability of the organic electroluminescent device and an organic electroluminescent device using the compound.

In order to achieve the above object, the present invention provides a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently CR ₂ or N, wherein at least one is N,

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ alkyloxy group of C _40, C C ₆ to C ₆₀ aryloxy groups, C ₁ to C ₄₀ alkylsilyl groups, C ₆ to C ₆₀ arylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C ₆ to C ₆₀ arylboron groups, C ₆ ~ C ₆₀ aryl phosphine is selected from the pingi, C ₆ ~ C ₆₀ aryl phosphine oxide group, and the group consisting of C ₆ ~ C ₆₀ aryl amine, the adjacent groups may form a fused ring,

A is selected from the group consisting of hydrogen, an aryl group having ₆ to ₆₀ carbon atoms and a heteroaryl group having 5 to 60 nuclear atoms,

L is a single bond, an arylene group having ₆ to ₆₀ carbon atoms or a heteroarylene group having 5 to 60 nuclear atoms, n is an integer of 0 to 3,

Cy ₁ is a compound represented by the following formula (2)

(2)

In Formula 2,

Y ₁ to Y ₄ are each independently CR ₅ or N, and Y ₁ And Y ₂ , Y ₂ And Y ₃ and Y ₃ And Y < ₄ > form a condensed ring represented by the following formula (3)

(3)

In Formula 3,

Y ₅ to Y ₈ each independently represent CR ₆ or N,

Z ₁ and Z ₂ are each independently selected from the group consisting of O, S, Se, N (Ar ₁ ), C (Ar ₂ ) (Ar ₃ ) and Si (Ar ₄ ) (Ar ₅ ) One is N (Ar ₁ )

Each of R ₃ to R ₆ is independently hydrogen, deuterium, halogen, cyano, nitro, amino, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, A C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, A C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, C ₆ ~ C ₆₀ aryl phosphine is selected from the pingi, C ₆ ~ C ₆₀ aryl phosphine oxide group, and the group consisting of C ₆ ~ C ₆₀ aryl amine, the adjacent groups may form a fused ring,

Wherein Ar ₁ to Ar ₅ are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkynyl group of C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyl silyl group, the group C ₆ ~ C ₆₀ aryl silyl, C ₁ ~ group alkylboronic of C _40, an aryl boronic a C ₆ ~ C _60, C ₆ ~ C ₆₀ is selected from the aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and the group consisting of C ₆ ~ C ₆₀ aryl group of an amine of,

Of the A aryl group and heteroaryl group each independently selected from deuterium, halogen, a cyano group, a nitro group, an amino group, C alkyl group of ₁ ~ C ₄₀ (preferably an alkyl group of C ₁ ~ C _10), C for ₂ ~ C ₄₀ (Preferably a C ₂ to C ₁₀ alkenyl group), a C ₂ to C ₄₀ alkynyl group (preferably a C ₂ to C ₁₀ alkynyl group), a C ₃ to C ₄₀ cycloalkyl group C ₃ to C ₁₈ cycloalkyl groups), a heterocycloalkyl group having 3 to 40 nuclear atoms (preferably a heterocycloalkyl group having 3 to 18 nuclear atoms), a C ₆ to C ₄₀ aryl group (preferably C ₆ - an aryl group of C _18), the nuclear atoms of 5 to 40 heteroaryl group (preferably a number of nuclear atoms of 5 to 18 heteroaryl group), C ₁ ~ C ₄₀ alkyloxy group (preferably C ₁ ~ C ₁₀ alkyloxy group of), C ₆ ~ aryloxy C ₆₀ (preferably an aryloxy group of a _{C 6 ~ C 18), C} 1 ~ alkyl silyl group of C ₄₀ (preferably C ₁ ~ C ₁₀ Alkylsilyl group), C ₆ ~ (aryl silyl group of preferably a C ₆ ~ C ₁₈₎ C ₆₀ aryl silyl group, C ₁ ~ group alkylboronic of C ₄₀ (preferably a alkyl boronic of _{C 1 ~ C 10), C} 6 ~ C group ₆₀ arylboronic of (preferably a arylboronic a _{C 6 ~ C 18), C} 6 ~ C 60 aryl phosphine group (preferably a C ₆ ~ C ₁₈ aryl phosphine group), C ₆ ~ C ₆₀ aryl phosphine oxide groups of the group consisting of (preferably aryl phosphine oxide group of C ₆ ~ C _18), and C ₆ ~ arylamine group of C ₆₀ (preferably an arylamine group of C ₆ ~ C ₂₀₎ , Wherein the plurality of substituents may be the same or different from each other,

The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group and arylsilyl group of R ₁ to R ₆ and Ar ₁ to Ar ₅ , alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an arylamine group each independently selected from deuterium, halogen, a cyano group, a nitro group, an amino group, C ₁ ~ C ₄₀ alkyl group (preferably C ₁ ~ C ₁₀ alkyl group), C ₂ ~ C ₄₀ alkenyl group (preferably C ₂ ~ C ₁₀ alkenyl group), C alkynyl group of ₂ ~ C ₄₀ alkynyl groups (preferably C ₂ ~ C ₁₀ in) , A C ₃ to C ₄₀ cycloalkyl group (preferably a C ₃ to C ₁₈ cycloalkyl group), a heterocycloalkyl group having 3 to 40 nuclear atoms (preferably a heterocycloalkyl group having 3 to 18 nuclear atoms), C ₆ ~ C ₄₀ aryl group (preferably a C ₆ ~ C ₁₈ aryl group), the number of 5 to 40 heteroaryl group (preferably of atomic nuclei Aryloxy nuclear atoms of 5 to 18 heteroaryl group), C ₁ ~ C ₄₀ alkyloxy (preferably alkyloxy group of _{C 1 ~ C 10), C} 6 ~ C 60 (preferably C ₆ and aryloxy _{C 18), C 1 ~ C} 40 alkyl silyl group (preferably a C ₁ ~ C ₁₀ alkyl silyl), C ₆ to C ₆₀ aryl silyl group (preferably C ₆ to a aryl silyl group of C _18), C ₁ ~ group alkylboronic of C ₄₀ (preferably C ₁ ~ C group ₁₀ of the alkyl boron), C ₆ ~ aryl boronic of C ₆₀ (preferably C ₆ ~ C ₁₈ the arylboronic group), C ₆ ~ aryl phosphine group of C ₆₀ (preferably C ₆ ~ C ₁₈ aryl phosphine group), C of ₆ ~ C ₆₀ aryl phosphine oxide groups (preferably C ₆ ~ C ₁₈ And an arylamine group of C ₆ to C ₆₀ (preferably an arylamine group of C ₆ to C ₂₀ ), wherein a plurality of substituents Are the same or different from each other,

And L is linked to any one of Z ₁ , Z ₂ , R ₃ , R ₄ and Y ₁ to Y ₈ of Formula (2) to which Formula 3 is bonded.

The alkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl , Pentyl, iso-amyl, hexyl, and the like.

The alkenyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, and the like.

The alkynyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Non-limiting examples thereof include ethynyl, 2-propynyl, and the like.

The cycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon). Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

The heterocycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and includes at least one carbon of the ring, preferably 1 To three carbons are substituted with a heteroatom such as N, O or S; Non-limiting examples thereof include morpholine, piperazine, and the like.

The aryl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. At this time, the two or more rings may be attached to each other in a simple attached or condensed form. Non-limiting examples thereof include phenyl, biphenyl, triphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, indenyl and the like.

The heteroaryl used in the present invention is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms and is a monovalent group having at least one carbon atom, Carbon atoms are replaced by heteroatoms such as nitrogen (N), oxygen (O), sulfur (S), or selenium (Se). At this time, the heteroaryl may be attached in a form in which two or more rings are attached or condensed to each other, and may further include a condensed form with an aryl group. Non-limiting examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and the like. ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.

The alkyloxy used in the present invention means a monovalent functional group represented by RO-, wherein R is an alkyl having 1 to 40 carbon atoms and includes a linear, branched or cyclic structure . Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

The aryloxy used in the present invention means a monovalent functional group represented by R'O-, and R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy, and the like.

The alkylsilyl used in the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms, arylamine is substituted with aryl having 6 to 60 carbon atoms ≪ / RTI >

The condensed rings used in the present invention means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

According to another aspect of the present invention, cathode; And at least one organic material layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic material layers includes a compound represented by the above formula (1) Device.

Herein, the organic compound layer including the compound represented by Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer, and is preferably a light emitting layer. At this time, the compound represented by Formula 1 may be used as a phosphorescent host material of the light emitting layer.

The compound represented by the general formula (1) according to the present invention is excellent in thermal stability and phosphorescent properties, and thus can be applied to an organic material layer, preferably a light emitting layer, of an organic electroluminescent device. Therefore, when the compound represented by Formula 1 is included as the phosphorescent host material in the light emitting layer of the organic electroluminescent device, the efficiency (luminous efficiency and power efficiency), lifetime, brightness and driving voltage And the performance and lifetime of the full-color organic electroluminescence panel can be greatly improved.

Hereinafter, the present invention will be described in detail.

1. New compound

The novel compound according to the present invention has a basic skeleton formed by combining an indole derivative containing nitrogen (N) with an indole group-fused compound, and is represented by the above formula (1).

The compound represented by Formula 1 of the present invention has excellent phosphorescence properties and is excellent in electron and / or hole transporting ability. Therefore, the organic compound layer of the organic compound layer of the organic compound layer of the hole injecting layer, the hole transporting layer, the light emitting layer, And may be used as any of the electron injection layers. Preferably a material of any one of the hole injection layer, the hole transporting layer and the light emitting layer, more preferably the material of the light emitting layer (in particular, the phosphorescent host material).

Specifically, the compound represented by the formula (1) of the present invention is a compound in which an indole derivative containing nitrogen (N) to which various substituents are introduced is combined with an indole group-fused compound and has a bipolar characteristic, As a balance regulator, the efficiency of recombination of holes and electrons can be improved, which can exhibit excellent phosphorescence characteristics. The compound represented by formula (1) of the present invention has various substituents introduced into the basic skeleton composed of an indene derivative containing nitrogen (N) and an indole group-fused compound, and thus has a wide energy band gap red). Accordingly, when the compound of Formula 1 of the present invention is used in an organic electroluminescent device, the phosphorescent characteristics of the device are improved, and the hole injecting ability and / or transporting ability, luminous efficiency, driving voltage and lifetime characteristics can be improved.

In addition, the compound represented by the formula (1) of the present invention has a significantly increased molecular weight due to various substituents introduced into the basic skeleton, thereby improving the glass transition temperature. As a result, the conventional organic electroluminescence device material , CBP [4,4-dicarbazolybiphenyl]).

Therefore, the compound according to the present invention can greatly contribute to improvement of the performance and lifetime of the organic electroluminescent device, and further, the lifetime of the organic electroluminescent device can maximize the performance of the full-color organic electroluminescent panel.

In the compound represented by the formula (1) of the present invention, X ₁ to X ₃ of indene derivatives containing nitrogen (N) are each independently CR ₂ or N, wherein at least one is preferably nitrogen (N) It is more preferable that all of them are nitrogen (N).

는 하기 S-1 내지 S-7로 표시되는 구조로 이루어진 군에서 선택되는 것이 바람직하며, 그 중에서도 트리아졸로피리딘 유도체인 S-7이 가장 바람직하다. 상기 S-1 내지 S-7로 표시되는 구조에서 R₂는 상기에서 정의한 바와 같으며, 복수개의 R₂는 서로 동일하거나 상이할 수 있다.Specifically, an indene derivative containing nitrogen (N)

Is preferably selected from the group consisting of the structures represented by the following structures S-1 to S-7, and among them, S-7, which is a triazole pyridine derivative, is most preferable. In the structures represented by S-1 to S-7, R ₂ is as defined above, and a plurality of R _{2 s} may be the same as or different from each other.

In the compound represented by the general formula (1) of the present invention, R ₁ and R ₂ are each independently hydrogen, a C ₆ to C ₆₀ aryl group (preferably a C ₆ to C ₂₅ aryl group) (Preferably a heteroaryl group having 5 to 32 nuclear atoms) and an arylamine group having ₆ to ₆₀ carbon atoms (preferably an arylamine group having ₆ to ₂₀ carbon atoms). , More preferably hydrogen.

Specifically, it is preferable that each of R ₁ and R ₂ and A bonded to the indene derivative is independently selected from the group consisting of hydrogen or a structure represented by the following Al-A70.

In the structure represented by the above-mentioned A1-A70, * means a site where the carbon (C) of the indene derivative is bonded.

In the compound represented by the formula (1) of the present invention, the compound represented by the formula (2) corresponding to Cy ₁ is preferably selected from the group consisting of the compounds represented by the following formulas (2a) to (2f).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

In the above formulas (2a) to (2f), Z ₁ , Z ₂ and R ₃ to R ₆ are as defined above. The plurality of R _{5 s} may be the same as or different from each other, and the plurality of R _{6 s} may be the same or different from each other.

In consideration of the efficiency and lifetime characteristics of the organic electroluminescent device, it is preferable that the compound represented by the general formula (1) of the present invention comprises an indene derivative containing the nitrogen (N) and a group consisting of the compounds represented by the general formulas , L is a single bond or phenylene. Further, in the compound represented by the above formula 2a) to (2f, wherein Z ₁ and Z ₂ are both and is preferably a N (Ar _1), coupled to the Ar ₁ and Z ₂ in N (Ar ₁₎ coupled to the Z ₁ N ₁ of Ar (Ar ₁₎ which may be the same or different from each other. Specifically, when both of Z ₁ and Z ₂ are N (Ar ₁ ), Ar ₁ is hydrogen, a C ₆ to C ₆₀ aryl group (preferably a C ₆ to C ₁₈ aryl group) (Preferably a heteroaryl group having 5 to 18 nucleus atoms), and the like.

In the compound represented by the formula (1) of the present invention, the linking position (bonding position) of L and the compound represented by the formula (2) is not particularly limited, but may be any one of Z ₁ and Z ₂ .

The compound represented by the formula (1) of the present invention is preferably a compound represented by the following formula (4) or (5).

[Chemical Formula 4]

[Chemical Formula 5]

In Formula 4 and Formula 5, A, L, Cy ₁ , R ₁ and n are as defined above, and a plurality of R _{1 s} are the same or different from each other.

The compound represented by formula (1) of the present invention may be specifically exemplified by the following compounds (1-70), but is not limited thereto.

The compound represented by formula (1) of the present invention can be synthesized in various ways with reference to the synthesis process of the following examples.

2. Organic Field  Light emitting element

The present invention provides an organic electroluminescent device comprising a compound represented by the above formula (1).

Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes And a compound represented by the above formula (1).

The organic material layer containing the compound represented by Formula 1 may be at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Preferably, the organic compound layer including the compound of Formula 1 may be a hole injection layer, a hole transporting layer, or a light emitting layer, more preferably a light emitting layer.

The light emitting layer of the organic electroluminescent device according to the present invention may contain a host material (preferably, a phosphorescent host material), wherein a compound represented by the above formula (1) may be used as a host material. When the light emitting layer contains the compound represented by the above formula (1), the hole transporting ability is increased to increase the bonding force between the hole and the electron in the light emitting layer. Therefore, efficiency (luminous efficiency and power efficiency), lifetime, An excellent organic electroluminescent device can be provided.

The structure of the organic electroluminescent device according to the present invention is not particularly limited and may include, for example, a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode sequentially stacked. Here, the electron injection layer may be further stacked on the electron transporting layer. In addition, the organic electroluminescent device according to the present invention may have a structure in which an anode, one or more organic layers and an anode are sequentially stacked, and an insulating layer or an adhesive layer is interposed between the electrodes and the organic layer.

Examples of the material usable as the anode included in the organic electroluminescent device according to the present invention include, but are not limited to, 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); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black.

Examples of materials usable as an anode included in the organic electroluminescent device according to the present invention include, but are not limited to, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, Tin, or lead, or alloys thereof; And a multilayer structure material such as LiF / Al or LiO ₂ / Al.

The organic compound layer included in the organic electroluminescent device according to the present invention may be any one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer and the electron injecting layer, preferably the hole injecting layer, The light emitting layer can be formed using materials and methods known in the art, except for the use of any of the light emitting layers, more preferably the light emitting layer.

Materials that can be used as the substrate included in the organic electroluminescent device according to the present invention are not particularly limited, but examples thereof include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.

The organic electroluminescent device of the present invention may be manufactured by a method known in the art, and the luminescent layer included in the organic material layer may be prepared by a vacuum evaporation method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, and thermal transfer.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[ Inden  Derivative synthesis]

<Scheme 1>

<Scheme 2>

In Scheme 1 and 2, Ar and Ar 'are C ₆ to C ₆₀ aryl groups, and X is a halogen group.

[ Preparation Example  1] 5- bromo - [1,2,4] triazolopyridine -2- ylamine Synthesis of

&Lt; Step 1 > 1- (3- bromo - 피리딘 -2- yl ) -3- carboethoxy - thiourea Synthesis of

1.0 g of DCM was added to 100 g (0.58 mol) of 2-amino-3-bromopyridine. And 68.2 mL (0.58 mol) of ethoxycarbonyl isothiocyanate was slowly added dropwise over 15 minutes. The reaction solution was warmed to room temperature and stirred for 20 hours. The solvent was appropriately removed by distillation under reduced pressure and the mixture was filtered. And dried to obtain 158 g of the title compound (yield: 90%).

<Step 2> 5- bromo - [1,2,4] triazolopyridine -2- ylamine Synthesis of

A mixed solvent of EtOH / MeOH (1: 1, 1.5 L) was added to 180.5 g (2.60 mol) of hydroxylamine hydrochloride. 271 mL (1.56 mol) of N, N-diisopropylethylamine was added to the reaction solution and stirred for 1 hour. 158 g (0.52 mol) of 1- (3-bromo-pyridine-2-yl) -3-carboethoxy-thiourea synthesized above was added and the mixture was slowly heated to reflux for 3 hours. The temperature was cooled to room temperature and the resulting solid was filtered. The filtrate was distilled under reduced pressure and the resulting solid was filtered. The resulting solid product was combined, washed with purified water, EtOH / MeOH mixed solvent and n-hexane, and dried under a warm air stream to obtain 91 g (yield 82%) of the desired compound.

[ Preparation Example  2] 8 - ([1,1'- biphenyl ]-4- yl ) - [l, 2,4] triazolo [1,5-a] pyridine -2-amine

500 mL of toluene was added to 20 g (100 mmol) of 4-biphenylboronic acid and 23.7 g (111 mmol) of 5-bromo- [1,2,4] triazolopyridin-2- ylamine. _{Pd (PPh 3) 4 5.8 g} (5 mmol), Na 2 CO 3 32 g was added to the (303 mmol) it was refluxed with heating for 8 hours at 120?. The temperature was cooled to room temperature and 300 mL of purified water was added to the reaction solution. After stirring for 1 hour, the solid formed in the reaction solution was filtered under reduced pressure and washed with 100 mL of EA. The obtained solid was dried with aeration to obtain 20.8 g of the desired compound (yield: 72%).

[ Preparation Example  3] 8 - ([1,1'- biphenyl ]-4- yl )-2- bromo - [1,2,4] triazolo [1,5-a] pyridine

15 g (52.4 mmol) of CuBr _2, 3.5 g (15.7 mmol) of 8- ([1,1'-biphenyl] -4-yl) - [1,2,4] triazolo [1,5- mmol), 100 mL of HBr and 100 mL of purified water were mixed. Cooled to 0 ° C and 10.8 g (157 mmol) of NaNO ₂ dissolved in 50 mL of purified water and slowly added dropwise. The reaction solution was stirred at room temperature for 12 hours. 100 mL of an aqueous solution of sodium carbonate was added to the reaction mixture, and the mixture was stirred for 1 hour, and the resulting solid was filtered. The resulting solid was recrystallized from 150 mL of EA to obtain 16.0 g (yield 87%) of the target compound.

[ Preparation Example  4] 8 - ([1,1'- biphenyl ]-4- yl ) -2- (4- klorophenyl ) - [l, 2,4] triazolo [1,5-a] pyridine

15 g (42.8 mmol) of 8 - ([1,1'-biphenyl] -4-yl) -2-bromo- [1,2,4] triazolo [ (47.1 mmol) was added 300 mL of toluene. _{Pd (PPh 3) 4 2.5 g} (2.1 mmol), K 2 CO 3 17.8 g was added to the (128 mmol) was heated to reflux at 120? For 3 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain the desired compound (13.9 g, yield 85%).

[ Preparation Example  5] 8 - ([1,1'- biphenyl ]-4- yl ) -2- (3- klorophenyl ) - [l, 2,4] triazolo [1,5-a] pyridine

The procedure of Preparation Example 4 was repeated except that 3-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid to obtain 13.1 g (yield 80%) of the desired compound.

[ Preparation Example  6] 2- (4- klorophenyl ) -8- (4- ( naphthalen -One- yl ) phenyl ) - [l, 2,4] triazolo [1,5-a] pyridine

A solution of 2-bromo-8- (4- (naphthalen-1-yl) -2,3- (Yield: 72%) was obtained by carrying out the same processes as in [Preparation Example 4], except that 1-yl) phenyl) - [1,2,4] triazolo [ &Lt; / RTI &gt;

[ Preparation Example  7] 8 - ([1,1 ': 3', 1 &quot; - 테 페렌 ] -5'- yl ) -2- (4- klorophenyl ) - [l, 2,4] triazolo [1,5-a] pyridine

8 - ([1,1'-biphenyl] -4-yl) -2-bromo- [1,2,4] triazolo [ 1 '' -terphenyl] -5'-yl) -2-bromo- [1,2,4] triazolo [1,5-a] pyridine was used in place of [ 10.3 g (yield 70%) of the desired compound was obtained.

[ Preparation Example  8] 8- (4- ( naphthalen -One- yl ) phenyl ) - [l, 2,4] triazolo [1,5-a] pyridine -2-amine

The procedure of Preparation Example 2 was repeated except that 4- (naphthalen-1-yl) phenyl) boronic acid was used instead of 4-biphenylboronic acid to obtain 23.1 g (yield 73%) of the desired compound.

[ Preparation Example  9] 2- bromo -8- (4- ( naphthalen -One- yl ) phenyl ) - [l, 2,4] triazolo [1,5-a] pyridine

8- (4- (naphthalen-1-yl) - [1,1'-biphenyl] -4-yl) - [1,2,4] triazolo [1,5- a] pyridine- (yield: 88%) was obtained by carrying out the same procedure as in [Preparation Example 3], except that 1-phenyl- [1,2,4] triazolo [1,5-a] pyridin- &Lt; / RTI &gt;

[ Preparation Example  10] 8- (3- phenylpyrrolo [3,2-a] carbazole-10 (3H) - yl ) - [1,2,4] triazolo [1,5-a] pyridin-2-amine

300 mL of dioxane was added to 20 g (93.9 mmol) of 5-bromo- [1,2,4] triazolopyridin-2-ylamine and 29.1 g (103 mmol) of 3-phenyl-3,10- dihydropyrrolo [3,2- And 100 mL of purified water. 3.4 g (4.7 mmol) of PdCl ₂ dppf and 38.9 g (282 mmol) of K ₂ CO ₃ were added, and the mixture was refluxed at 120 ° C for 12 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain the desired compound (28.0 g, yield 72%).

[ Preparation Example  11] 10- (2- bromo - [1,2,4] triazolo [1,5-a] pyridine -8- yl ) -3- phenyl -3,10-dihydropyrrolo [3,2-a] carbazole

8- (3-phenylpyrrolo [3,2-a] pyridine instead of 8- ([1,1'- biphenyl] -4-yl) - [1,2,4] triazolo [ ] carbazol-10 (3H) -yl) - [1,2,4] triazolo [1,5-a] pyridin-2-amine was used in place of [ 14.9 g (yield: 86%) was obtained.

[ Synthetic example  1] Synthesis of Compound 8

([1,1'-biphenyl] -4-yl) -2-bromo (3-phenyl-3,10-dihydropyrrolo [ - [1,2,4] triazolo [1,5-a] pyridine (16.4 g, 46.8 mmol) was added 250 mL of 1,4-dioxane. 1.9 g (2.1 mmol) of Pd ₂ (dba) ₃ , 1.3 g (2.1 mmol) of BINAP and 27.7 g (85 mmol) of Cs ₂ CO ₃ were added and the mixture was refluxed at 120 ° C for 24 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure and purified by silica gel column chromatography to obtain the desired compound (11.2 g, yield 48%).

[ Synthetic example  2] Synthesis of Compound 32

1-yl) phenyl) - [1, 3-phenyl-3,10-dihydropyrrolo [3,2- 2,4] triazolo [1,5-a] pyridine (16.8 g, 39.0 mmol) was added with 200 mL of toluene. 0.4 g (1.8 mmol) of Pd (OAc) ₂ , 0.34 g (1.8 mmol) of P (t-Bu) _{3 and} 10.2 g (106 mmol) of NaOt-Bu were added and the mixture was refluxed at 120? For 24 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and purified by silica gel column chromatography to obtain the desired compound (13.9 g, yield 58%).

[ Synthetic example  3] Synthesis of Compound 40

A solution of 8 - ([1,1 ': 3'] thiophene was used instead of 2- (4-chlorophenyl) -8- (4- (naphthalen- [Synthesis Example 2] Synthesis was conducted in the same manner as in [Synthesis Example 2], except that [1 '' - terphenyl] -5'-yl) -2- (4-chlorophenyl) - [1,2,4] triazolo [ The target compound (11 g, yield: 55%) was obtained.

[ Synthetic example  4] Synthesis of Compound 51

Was obtained in the same manner as in the preparation example 5, except that 8- (4-chlorophenyl) -8- (4- (naphthalen-1- Synthesis Example 2] was repeated except that [1,1'-biphenyl] -4-yl) -2- (3-chlorophenyl) - [1,2,4] triazolo [1,5- The same procedure was followed to obtain 10.7 g (yield: 60%) of the desired compound.

[ Synthetic example  5] Synthesis of Compound 64

The same procedure as in [Synthesis Example 1] was repeated except that 1-phenyl-1,6-dihydropyrrolo [3,2-c] carbazole was used in place of 3-phenyl-3,10-dihydropyrrolo [3,2- To obtain 11.8 g (yield 55%) of the desired compound.

[ Synthetic example  6] Synthesis of Compound 69

3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole and 9H-pyrazolo [ -carbazole was used to carry out the same procedure as in [Synthesis Example 2] to obtain the desired compound (5.5 g, yield 42%).

[ Example  1 to 6] Red organic Field  Fabrication of light emitting device

Compounds 8, 32, 40, 51, 64, and 69 synthesized in Synthesis Examples 1 to 6 were subjected to high purity sublimation purification by a conventionally known method, and red organic electroluminescent devices were fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

(60 nm) / NPB (20 nm) / Compound 8, 32, 40, 51, 64 and 69 respectively + 10% (piq) ₂ Ir (acac) BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate a red organic electroluminescent device.

[ Comparative Example ] Red organic Field  Fabrication of light emitting device

A red organic electroluminescent device was fabricated in the same manner as in Example 1, except that CBP was used instead of Compound 8 as a luminescent host material in the formation of the light emitting layer.

The structures of m-MTDATA, NPB, (piq) ₂ Ir (acac), BCP and CBP used in Examples 1 to 6 and Comparative Examples are as follows.

[ Evaluation example ]

The driving voltage, current efficiency and emission peak at current densities of 10 mA / cm 2 were measured for each of the organic electroluminescent devices manufactured in Examples 1 to 6 and Comparative Example, and the results are shown in Table 1 below.

Sample Host The driving voltage (V) Current efficiency (cd / A) Example 1 Compound 8 4.65 13.5 Example 2 Compound 32 4.57 13.3 Example 3 Compound 40 4.60 12.5 Example 4 Compound 51 4.65 13.0 Example 5 Compound 64 4.70 12.6 Example 6 Compound 69 4.66 13.1 Comparative Example CBP 5.25 8.2

As shown in Table 1, the red organic electroluminescent devices (Examples 1 to 6) using the compound of the present invention as a light emitting layer exhibited a higher driving voltage and a lower driving voltage than the red organic electroluminescent device using the conventional CBP as the light emitting layer It can be seen that it shows excellent performance in terms of current efficiency.

Claims (11)

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

In Formula 1,
X ₁ to X ₃ are each independently N,
R &lt; ₁ &gt; is hydrogen,
A is selected from the group consisting of heteroaryl, C ₆ ~ C ₆₀ aryl group and the nuclear atoms of 5 to 60,
L is a single bond or an arylene group having ₆ to ₆₀ carbon atoms,
n is an integer of 3,
Cy ₁ is a compound represented by the following formula (2)
(2)

In Formula 2,
Y ₁ to Y ₄ are each independently CR ₅ , and _one of Y ₁ and Y ₂ , Y ₂ and Y _3, and Y ₃ and Y ₄ is a condensed ring represented by the following formula (3)
(3)

In Formula 3,
The dotted line represents a site where condensation is performed with the compound of Formula 2, Y ₅ to Y ₈ each independently represent CR ₆ ,
Z ₁ and Z ₂ are each independently N (Ar ₁ ), wherein Ar ₁ is the same as or different from each other,
Each of R ₃ to R ₆ is independently hydrogen,
Wherein Ar ₁ is selected from the group consisting of hydrogen, a C ₆ to C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms,
The aryl group and the heteroaryl group of A each independently may be substituted with a C ₆ to C ₄₀ aryl group,
The aryl and heteroaryl groups of Ar ₁ are each independently selected from the group consisting of deuterium, halogen, cyano, nitro, amino, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl , A C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group , A C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group , C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group, and the amine may be substituted with at least one member selected from the group consisting of a,
The L is connected to any one of Z ₁ , Z ₂ , R ₃ , R ₄ and Y ₁ to Y ₈ in the formula (2). delete delete The method according to claim 1,
Wherein A is selected from the group consisting of the structures represented by the following formulas A1-A12, A17-A19, A24-A26, A31-A50, A53-A63, A65-A67 and A69-A70.

The method according to claim 1,
Wherein the compound represented by Formula 2 is selected from the group consisting of compounds represented by Chemical Formulas 2a to 2f.
(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

In the above Chemical Formulas (2a) to (2f)
Z ₁ , Z ₂ and R ₃ to R ₆ are as defined in claim 1, a plurality of R _{5 s} are the same as or different from each other, and a plurality of R _{6 s} are the same or different from each other. 6. The method of claim 5,
Wherein L in Formula 1 is a single bond or phenylene. The method according to claim 1,
Wherein L is connected to any one of Z ₁ and Z ₂ in the above formula (2). The method according to claim 1,
The compound represented by the formula (1) is a compound represented by the following formula (4) or (5):
[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)
A, L, Cy ₁ , R ₁ and n are as defined in claim ₁ , and a plurality of R _{1 s} are the same as or different from each other. anode; cathode; And at least one organic material layer interposed between the anode and the cathode, the organic electroluminescent device comprising:
Wherein at least one of the one or more organic layers includes a compound according to any one of claims 1 to 8. 10. The method of claim 9,
Wherein the organic compound layer containing the compound is selected from the group consisting of a hole injecting layer, a hole transporting layer, and a light emitting layer. 10. The method of claim 9,
The organic compound layer containing the compound is a light emitting layer,
Wherein the compound is a phosphorescent host material of the light emitting layer.