KR20160036162A - An organoelectro luminescent compounds and organoelectro luminescent device using the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by chemical formula 1, and to an organic electroluminescent device comprising the same. The organic electroluminescent device applying the organic light emitting compound according to the present invention can be driven by a low voltage, and has high brightness and excellent lifespan properties.

Description

[0001] The present invention relates to an organic electroluminescent compound and an organic electroluminescent device using the same,

The present invention relates to an organic light emitting compound and an organic electroluminescent device including the same.

An organic light emitting phenomenon is a phenomenon that converts electric energy into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. In addition, the luminescent material can be classified into blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. On the other hand, when only one material is used as the light emitting material, there arises a problem that the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, the color purity drops, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material in order to increase the efficiency of light emission through the light emitting layer.

In order for the organic luminescent device to sufficiently exhibit the above-described excellent characteristics, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, development of a stable and efficient organic material layer material for an organic light emitting device has not been sufficiently developed yet. Therefore, the development of new materials is continuously required.

Accordingly, it is an object of the present invention to provide a novel organic electroluminescent compound included in an organic layer of a device and an organic electroluminescent device including the organic electroluminescent compound to enable an organic electroluminescent device to have a lower driving voltage, improved luminance, and longer life .

In order to solve the above-described problems, the present invention provides an organic light emitting compound represented by the following Chemical Formula 1 and an organic electroluminescent device including the same in an organic material layer.

[Chemical Formula 1]

The structures, substituents and characteristics of the above formula (1) will be described later.

The present invention also provides a method for producing a hole injection layer, a hole transport layer, a hole injecting and transporting layer, an electron transporting layer, an electron injecting layer, The organic electroluminescent device includes an organic electroluminescent compound represented by Formula

The organic electroluminescent device employing the organic electroluminescent compound according to the present invention has low driving voltage, high brightness, and excellent lifetime characteristics, so that it can be used not only for various display devices but also for monochromatic or white illumination.

1 is a conceptual diagram illustrating an organic electroluminescent device having a multilayer structure according to an embodiment of the present invention.

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

The present invention relates to an organic luminescent compound characterized by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

At least one of two or more adjacent R's in a plurality of R's is bonded to a single bond to form a ring, or is bonded to a substituted or unsubstituted methylene group to form a ring, or a substituted amino group (-NR ₁ -), an oxygen atom -O-), a sulfur atom (-S-) or a selenium atom (-Se-) is covalently bonded to form a ring.

X ₁ And X ₂ are the same or different from each other and each independently selected from the group consisting of S, O, NR ₁ , SiR ₂ R ₃ , GeR ₄ R ₅ , CR ₆ R ₇ , Se and Te.

Each of R and R ₁ to R ₇ independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C2- A substituted or unsubstituted C1-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted aryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, a phosphoryl group, A cyano group, a hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, an ether group and an ester group.

The "substituted" in the above "substituted or unsubstituted" means that the substituent defined by R and R ₁ to R ₇ can be further substituted by one or more substituents, Substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted C3- A substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1- Substituted or unsubstituted C1-C30 alkylthio groups, substituted or unsubstituted C1-C30 arylthio groups, substituted or unsubstituted C1-C30 alkylthio groups, A substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, a phosphoryl group, an amino group, a thiol group, a cyano group, , A halogen group, a selenium group, a tellurium group, an amide group, an ether group and an ester group.

In addition, the aryl group contained in the organic luminescent compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms And when a substituent is present in the aryl group, it may be fused with an adjacent substituent to further form a ring.

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, , Aromatic groups such as a pyrenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a perylene group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group. The aryl group may be further substituted with at least one substituent selected from the substituents described for R ₁ to R ₇ .

In addition, the heteroaryl group contained in the organic luminescent compound according to the present invention may be any one selected from the following Structural Formulas 1 to 10:

[Structural formula 1] [Structural formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural Formula 5] [Structural Formula 6] [Structural Formula 7]

[Structural formula 8] [Structural Formula 9] [Structural Formula 10]

In the above Structural Formulas 1 to 10,

T ₁ to T ₁₂ are the same or different from each other and each independently represent C (R ₄₂ ), C (R ₄₃ ) (R ₄₄ ), N, N (R ₄₅ ), O, S, R ₄₆ ) (R ₄₇ ) and Ge (R ₄₈ ) (R ₄₉ ), and T ₁ to T ₁₂ may not all be carbon atoms at the same time, and R ₄₂ to R ₄₉ may be the same A substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 aryl group, and a substituted or unsubstituted C1- Or a heteroaryl group having 2 to 30 carbon atoms with unsubstituted and hetero atoms O, N, S, or P;

The above-mentioned [formula 3] may include a compound represented by the following formula [3] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In the above structural formula 3-1, T ₁ to T ₇ are the same as defined in [Structural formulas 1] to [Structural formula 10].

According to a preferred embodiment of the present invention, the above Structural Formulas 1 to 10 can be selected from the following Structural Formula 11.

[Structural Formula 11]

In the above structural formula 11,

X is the same as defined for R ₁ to R ₇ in the above formula (1), m is an integer of 1 to 11, and when m is 2 or more, plural Xs may be the same as or different from each other.

The organic luminescent compound of Formula 1 according to the present invention is not limited in its scope, but may be represented by the following compounds 1 to 57 more specifically as an embodiment, It can be utilized as a luminescent compound for various purposes.

In particular, the organic luminescent compound according to the present invention can realize an organic luminescent compound having intrinsic characteristics of the introduced substituent as well as intrinsic properties of the core structure by introducing various substituents into the core structure represented by the formula (1).

For example, a substance that meets the conditions required in each organic layer may be implemented by introducing a substituent used for the hole injecting layer material, the hole transporting layer material, the host or dopant emitting layer material, and the electron transporting layer material as the phosphorescent material into the core structure.

Further, the present invention relates to an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, At least one organic luminescent compound according to the present invention may be contained.

That is, the organic electroluminescent device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic material layer disposed therebetween, and the organic electroluminescent device of Formula 1 according to the present invention Can be produced by using a conventional device manufacturing method and materials, except that the organic material layer is used for the organic material layer of the device.

The organic material layer of the organic electroluminescent device according to the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. However, it is not so limited and may include fewer or greater numbers of organic layers.

Therefore, in the organic electroluminescent device of the present invention, the organic material layer may include at least one of a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes, 1]. ≪ / RTI >

In the organic electroluminescent device of the present invention, the organic material layer may include at least one of an electron injecting layer, an electron transporting layer, and a layer simultaneously performing electron injection and electron transporting, 1]. ≪ / RTI >

Further, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by the general formula (1). Here, the compound represented by Formula 1 may be included as a host material in the light emitting layer. When the compound represented by Formula 1 is included as a host material in the light emitting layer, the light emitting layer may further include at least one dopant compound. As described above, in the present invention, a dopant material may be used for the light emitting layer in addition to the host. When the light emitting layer comprises a host and a dopant, the dopant content may be selected in the range of about 0.01 to about 20 parts by weight, based on 100 parts by weight of the host.

In the organic compound layer having such a multi-layer structure, the compound represented by the general formula (1) may be used in combination with a light-emitting layer, a layer which simultaneously transports holes and holes, a layer which simultaneously transports light and light, And the like.

Hereinafter, an embodiment of the organic electroluminescent device according to the present invention will be described in more detail with reference to FIG.

The organic electroluminescent device according to the present invention includes an anode 20, a hole transporting layer 40, an organic light emitting layer 50, an electron transporting layer 60, and a cathode (80), and if necessary, may further include a hole injection layer (30) and an electron injection layer (70). In addition, one or two intermediate layers may be further formed, Or an electron blocking layer may be further formed, and an organic layer having various functions may be further included depending on the characteristics of the device.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG.

First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, a substrate used in a typical organic electroluminescent device is used, and an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injecting layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

The material for the hole injection layer may be any material that is commonly used in the art besides the organic light emitting compound according to the present invention. Specific examples thereof include 2-TNATA [4,4 ', 4 "-tris ( 2-naphthylphenyl-phenylamino) -triphenylamine], NPD [N, N'-di (1-naphthyl) -N, -methylphenyl) -1,1'-biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'- -biphenyl-4,4'-diamine] or the like can be used.

The hole transport layer material is not particularly limited as long as it is commonly used in the art besides the organic light emitting compound according to the present invention. For example, N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine (? -NPD) or a mixture of N, N'-di (naphthalene-1-yl) Etc. may be used.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

Wherein a material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq _2, OXD-7, Liq and [Formula 501] to [Chemical Formula 507] either, but one that can be used is selected from, this limited It is not.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(501) [502] ≪ EMI ID =

≪ EMI ID = ≪ EMI ID = ≪ EMI ID =

≪ EMI ID =

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

The electron transport layer material serves to stably transport electrons injected from an electron injection electrode, and besides the organic luminescent compound according to the present invention, a known electron transport material can be used. Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- materials such as olate: Bebq2), ADN, [Formula 401], [Formula 402], and oxadiazole derivatives PBD, BMD, BND and the like may be used.

TAZ BAlq

[Compound 401] [Compound 402] BCP

Further, the electron transporting layer used in the present invention can be used as the organometallic compound represented by the following formula (C) alone or in combination with the electron transporting layer material.

≪ RTI ID = 0.0 &

In the above formula (C)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond. M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom.

OA is a monovalent ligand capable of single bond or coordination bond with M, O is oxygen, A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C30 cycloalkyl An alkenyl group, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having a hetero atom O, N, or S.

When m is 1 or n = 0 when M is one metal selected from alkali metals and m is 1 or n = 1 when M is a metal selected from alkaline earth metals, or m = 2 and n = 0, and when M is boron or aluminum, m is any one of 1 to 3 and n is any of 0 to 2, and m + n = 3.

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

The Y may be the same or different and independently selected from the following formulas [C1] to [C39], but is not limited thereto.

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

L represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms A substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryl group having 3 to 20 carbon atoms, A heteroaryl group, a cyano group, a halogen group, deuterium, and hydrogen, and may be connected to an adjacent substituent by an alkylene or an alkenylene to form a spiro ring or a fused ring.

In the organic electroluminescent device according to the present invention, the organic layer may include a light emitting layer, and the light emitting layer may further include at least one dopant compound. In the organic electroluminescent device of the present invention, May be at least one compound selected from compounds represented by the following general formulas A-1 to J-1, although not particularly limited thereto.

[General Formula A-1]

Wherein M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. L ₁ , L ₂ and L ₃ are the same or different from each other as ligands, and each independently selected from the following structural formula [D], but are not limited thereto. In the following [Structural Formula D], * represents a site binding to the metal ion M.

[Structural formula D]

In the above structural formula D,

A substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, an unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms and a substituted or unsubstituted arylsilyl And the like.

Each R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen And may be further substituted with one or more substituents.

Further, the R may be connected to each adjacent substituent by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

As one example, the dopant represented by the above-mentioned [formula A-1] may be any one selected from the following compounds, but is not limited thereto.

[Formula B-1]

In the above general formula B-1,

M ^A1 represents the same metal ion as defined in [formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom, and Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, L ^A11 , L ^A12 , L ^A13 and L ^A14 each represent a linking group as defined above, and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonding to M ^A1 .

Exemplary structures of the compound represented by the above-mentioned general formula B-1 are shown below, but the present invention is not limited thereto.

[Formula C-1]

In the above general formula (C-1)

M ^B1 represents the same metal ion as defined from the following formula ^{A-1], Y B11,} Y B14, Y B15 and Y ^B18 each independently represents a carbon atom or a nitrogen ^{atom, Y B12, Y B13, Y} B16 And Y ^B17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom, L ^B11 , L ^B12 , L ^B13 and L ^B14 represent a linking group, Q ^B11 and Q ^B12 represent ^Represents a partial structure containing an atom bonding to M ^B1 .

Exemplary structures of the compound represented by the above-mentioned general formula C-1 are shown below, but the present invention is not limited thereto.

[Formula D-1]

In the above general formula (D-1)

M ^C1 represents a metal ion as defined in [formula A-1], R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, Each of R ^C13 and R ^C14 independently represents a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, or a substituent which does not have any one to be connected to each other, and G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituent Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonding to M ^C1 .

Exemplary structures of the compound represented by the above-mentioned general formula (D-1) are shown below, but the present invention is not limited thereto.

[Formula E-1]

In the above general formula E-1,

M ^D1 represents the same metal ion as defined from the following formula A-1], G ^D11, G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11, J ^D12, J ^D13 and J ^D14 each independently represents an atomic group necessary for forming a five-membered ring, and L ^D11 and L ^D12 represent a linking group.

Exemplary structures of the compound represented by the above-mentioned formula (E-1) are as follows, but are not limited thereto.

[Formula F-1]

In the above general formula F-1,

M ^E1 represents the same metal ion as defined in [Formula A-1], J ^E11 and J ^E12 each independently represent an atom group necessary for forming a 5-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom.

Exemplary structures of the compound represented by the above-mentioned general formula F-1 are shown below, but are not limited thereto.

[Formula G-1]

In the above general formula G-1,

M ^F1 represents the same metal ion as defined in [formula A-1].

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent substituents, R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be connected to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. And Q ^F11 and Q ^F12 represent a partial structure containing an atom bonding to M ^F1 .

Exemplary structures of the compound represented by the above-mentioned general formula G-1 are shown below, but the present invention is not limited thereto.

[Formula H-1] [Formula H-2] [Formula H-3]

In the above formulas H-1 to H-3,

R ¹¹ and R ¹² are substituents of alkyl, aryl or heteroaryl; And q11 and q12 may be an integer of 0 to 4, preferably 0 to 2, and may form a fused ring with substituents adjacent to each other.

When q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different.

L ¹ is a ligand which binds to platinum and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand or a halogen ligand, more preferably an ortho metal ) Ligand, a bipyridyl ligand or a phenanthroline ligand, which form a platinum complex.

n ¹ is an integer of 0 to 3, preferably 0, m ¹ is 1 or 2, and preferably 2.

It is preferable that n ¹ and m ¹ denote the metal complex represented by the general formula H-1 as a neutral complex.

In the above-mentioned general formula H-2,

R ²¹ , R ²² , n ² , m ² , q ²² and L ² are respectively the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² and L ¹ , q ²¹ is an integer of 0 to 2 , 0 is preferable.

In the above-mentioned general formula H-3,

R ³¹ , n ³ , m ³ and L ³ are the same as R ¹¹ , n ¹ , m ¹ and L ¹ , q ³¹ is an integer of 0 to 8, preferably 0 to 2, desirable.

Examples of the specific compounds of the above-mentioned general formulas H-1 to H-3 are shown below, but the present invention is not limited thereto.

[Formula I-1]

In the above general formula I-1,

Ring A, ring B, ring C and ring D represents a nitrogen-containing heterocyclic ring which may have a substituent, and the remaining two rings may be substituted with an aryl ring or a hetero ring which may have a substituent And may form a condensed ring with ring A and ring B, ring A and ring C and / or ring B and ring D, respectively. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them coordinate to a platinum atom, and the remaining two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (or a bond), but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. ^{Two of} Z ¹ , Z ² , Z ³ and Z ⁴ represent coordinate bond, and the remaining two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of the specific compounds of the above-mentioned general formula I-1 include, but are not limited to, the following.

[Formula J-1]

In the above general formula J-1,

M represents the same metal ion as defined in [formula A-1], Ar1 represents a substituted or unsubstituted cyclic structure, and two azomethine bonds (-C = N-) , The nitrogen atom (N) binds to the M, respectively, and forms a three-coordinate ligand which is bonded to the M at the 3-position as a whole.

Further, in Ar 1, C represents a carbon atom constituting a ring structure represented by Ar 1. R 1 and R 2 may be the same or different and each represents a substituted or unsubstituted alkyl or aryl group, and L represents a one-dimensional ligand.

In the above general formula J-1, it is preferable that M is Pt. The above-mentioned Ar1 is preferably selected from a 5-membered ring, a 6-membered ring and condensed ring group thereof.

Examples of the specific compounds of the above-mentioned general formula J-1 include, but are not limited to, the following.

In addition, the light emitting layer may further include various dopants and various hosts in addition to the dopant and the compound according to the present invention.

At least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process, Means a method of forming a thin film by evaporating a material used as a material for forming each of the layers by heating or the like under a vacuum or a low pressure state and the solution process is used as a material for forming each of the layers Means a method of forming a thin film by a method such as ink jet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating and the like.

Further, the organic electroluminescent device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat panel illumination device, and a single color or white flexible illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

[Synthesis Example 1] Synthesis of Compound 1

Synthesis of [Reaction Scheme 1-1] [Intermediate 1-a]

Dibenzo [bc, fg] [1,4] dithiapentalene structure was synthesized with reference to the synthesis method of M.B. Nielsen group (Tetrahedron Letters 52 (2011) 4045-4047).

100 g (467 mmol) of dibenzo [bci, fp] [1,4] dithiapentalene and 800 mL of tetrahydrofuran were added to a 2 L reactor and stirred. After cooling to -78 ° C, 350 mL (560 mmol) of en-butyllithium (1.6M hexane solution) was added dropwise, and the mixture was warmed to room temperature and stirred for 12 hours. After cooling to -78 ° C, 154.0 g (607 mmol) of iodine was added, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. An aqueous solution of sodium thiosulfate was added, and the organic layer was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 127.6 g of [intermediate 1-a] (yield: 80.4%).

[Synthesis of Reaction Scheme 1-2] [Intermediate 1-b]

49.2 g (145 mmol) of the compound represented by [Intermediate 1-a], 30.0 g (174 mmol) of 2-bromoaniline and 0.4 g (2.0 mmol) of dipalladium acetate were added to a 1 L reactor. ), 3.0 g (5.0 mmol) of zincphosphate, 65.9 g (202 mmol) of cesium carbonate, and 400 mL of toluene were placed and refluxed for 12 hours. After filtration at high temperature, the filtrate was concentrated under reduced pressure and then separated by column chromatography to obtain 64.3 g (yield 78.5%) of the compound represented by [Intermediate 1-b].

Synthesis of [Scheme 1-3] [Intermediate 1-c]

A reaction vessel was charged with 64.3 g (167 mmol) of the compound represented by [Intermediate 1-b], 1.2 g (3.0 mmol) of tricyclohexylphosphine tetrafluoroborate and 0.4 g of dipalladium acetate 0.4 g (2.0 mmol) of potassium carbonate, 46.2 g (335 mmol) of potassium carbonate and 643 mL of ene-dimethylacetamide, and the mixture was refluxed for 12 hours. After filtration at a high temperature, the filtrate was concentrated under reduced pressure and then separated by column chromatography to obtain 39.8 g (yield 78.4%) of a compound represented by [Intermediate 1-c].

Synthesis of [Scheme 1-4] [Compound 1]

8.0 g (26 mmol) of the compound represented by [Intermediate 1-c] obtained in the above Scheme 1-3, 2-chloro-4,6-diphenyl-1,3,5-triazine 9.2 0.5 g (0.5 mmol) of tris (dibenzylideneacetone) dipalladium, 0.8 g (2.6 mmol) of tetrabutylphosphonium tetrafluoroborate, 5.1 g (53 mmol) of sodium tertiarybutoxide ) And 40 mL of xylene, and the mixture was refluxed for 12 hours. After filtration at a high temperature, the filtrate was concentrated under reduced pressure and then separated by column chromatography to obtain 5.2 g (yield: 36.9%) of a compound represented by [Compound 1].

MS [M] ^< ⁺ & gt ^; : 535

[Synthesis Example 2] Synthesis of Compound 2

[Synthesis 2-1] Synthesis of [Compound 2]

Synthesis Example 1 Synthesis was conducted in the same manner as in [Scheme 1-4] except that 2-chloro-4-phenylquinazoline was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine To obtain 4.6 g (yield: 41.5%) of the compound represented by [Compound 2].

MS [M] ^< ⁺ & gt ^; : 508

[Synthesis Example 3] Synthesis of Compound 3

Synthesis of [Reaction Scheme 3-1] [Intermediate 3-a]

To a dried 2 L reactor was dissolved 139.8 g (1.236 mol) of ethyl cyanoacetate, 29.5 g (0.453 mol) of potassium cyanide, 46.2 g (0.824 mol) of potassium hydroxide and 920 mL of dimethylformamide under nitrogen, Lt; / RTI > for 20 minutes. 92 g (412 mol) of 1-nitronaphthalene is then added to the reaction mixture and stirred at 60 ° C for 4 hours. After completion of the reaction, the solvent was concentrated, 600 mL of a 10% sodium hydroxide aqueous solution was added, and the mixture was refluxed with stirring for 1 hour. The solid was filtered and subjected to column chromatography with methylene chloride and heptane to obtain 50 g (yield 60%) of the compound represented by [Intermediate 3-a].

Synthesis of [Reaction Scheme 3-2] [Intermediate 3-b]

2-Aminobenzonitrile (45.0 g, 232 mmol) and tetrahydrofuran (450 mL) were placed in a 2 L reactor and stirred. After cooling to 0 占 폚, 88.2 mL (487 mmol) of 3M-phenylmagnesium bromide was added dropwise, and the mixture was refluxed for 3 hours. After cooling to 0 캜, 44.3 g (732 mmol) of ethyl chloroformate was dissolved in 200 mL of tetrahydrofuran, and the mixture was refluxed for 2 hours. After cooling to 0 ° C, a saturated aqueous ammonium chloride solution was added, and then the organic layer was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 46.0 g (yield: 80.0%) of a compound represented by [Intermediate 3-b].

Synthesis of [Reaction Scheme 3-3] [Intermediate 3-c]

50 g (184 mmol) of the intermediate [3-b] obtained in the above Reaction Scheme 3-2 and 200 mL of phosphorus oxychloride were placed in a 2 L reactor and refluxed for 5 hours. After cooling to 0 占 폚, the solution was added dropwise to distilled water. After filtration of the reaction solution, the solid was separated by column chromatography to obtain 39.7 g (yield: 74.4%) of the compound represented by [Intermediate 3-c].

[Reaction Scheme 3-4] Synthesis of [Compound 3]

Synthesis Example 1 Except for using [Intermediate 3-c] obtained in [Scheme 3-3] instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in [Reaction Scheme 1-4] Synthesis was conducted in the same manner to obtain 3.9 g (yield: 43.1%) of the compound represented by [Compound 3].

MS [M] ^< ⁺ & gt ^; : 558

[Synthesis Example 4] Synthesis of Compound 26

Synthesis of [Reaction Scheme 4-1] [Intermediate 4-a]

100 g (294 mmol) of the compound [Intermediate 1-a] obtained in the above Reaction Scheme 1-1, 63.5 g (323 mmol) of benzophenone hydrazone and 6.6 g (29 mmol) of dipalladium acetate were added to a 2 L reactor. , 18.3 g (29 mmol) of 2,2'-bis (diphenylphosphino) -1,1-binaphthyl, 39.6 g (412 mmol) of sodium pentachloride butoxide and 800 mL of toluene were added and refluxed for 12 hours . After filtration at a high temperature, the filtrate was concentrated under reduced pressure and then subjected to column chromatography to obtain 107.3 g (yield: 89.4%) of the compound represented by [Intermediate 4-a].

Synthesis of [Reaction Scheme 4-2] [Intermediate 4-b]

A mixture of 50.4 g (184 mmol) of the compound represented by [Intermediate 4-a] obtained from the above-mentioned Reaction Scheme 4-1, 29.4 g (184 mmol) of 3,3-dimethyl-2,3-dihydro- 184 mmol) were added acetic acid (300 mL) and hydrochloric acid (90 mL), and the mixture was refluxed for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and the product was separated by column chromatography to obtain 28.3 g (yield: 62.6%) of a compound represented by [Intermediate 4-b].

[Reaction Scheme 4-3] Synthesis of [Compound 26]

Synthesis Example 1 [Intermediate 4-b] obtained in [Reaction Scheme 4-2] was used instead of [Intermediate 1-c] in [Reaction Scheme 1-4], and 2-chloro-4,6- Was synthesized in the same way except that 2-chloro-4-phenylquinazoline was used instead of 5-triazine to obtain 2.8 g (yield 39.1%) of the compound represented by [26].

MS [M] ^< ⁺ & gt ^; : 574

[Synthesis Example 5] Synthesis of Compound 29

Synthesis of [Reaction Scheme 5-1] [Intermediate 5-a]

Synthesis Example 4 In the same manner as in [Reaction Scheme 4-1] except that methyl-2-aminobenzoate was used instead of benzophenone hydrazone, 51.8 g of the compound represented by [Intermediate 5-a] (yield: 87.3% ).

Synthesis of [Reaction Scheme 5-2] [Intermediate 5-b]

50.0 g (138 mmol) of the intermediate [5-a] obtained in the above Reaction Scheme 5-1 and 500 mL of tetrahydrofuran were added to a 2 L reactor and stirred. After cooling to 0 占 폚, 481.5 mL (481 mmol) of 3M-methylmagnesium bromide was added dropwise and the mixture was refluxed for 3 hours. Saturated ammonium chloride aqueous solution was added, and organic layer was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and 175 mL of phosphoric acid was added thereto, followed by stirring for 12 hours. The organic layer was extracted with methylene chloride and distilled water, and then concentrated under reduced pressure, followed by separation by column chromatography to obtain 35.8 g (yield 75.3%) of the compound represented by [Intermediate 5-b].

[Reaction Scheme 5-3] Synthesis of [Compound 29]

Synthesis Example 1 [Intermediate 5-b] obtained in [Scheme 5-2] instead of [Intermediate 1-c] in [Scheme 1-4] was replaced with 2-chloro-4,6-diphenyl-1,3,5-tri (2-chloro-4-phenylquinazoline was used in place of azine, 4.5 g (yield: 42.7%) of the compound represented by [Compound 29] was obtained.

MS [M] ^< ⁺ & gt ^; : 550

[Synthesis Example 6] Synthesis of Compound 30

Synthesis of [Reaction Scheme 6-1] [Intermediate 6-a]

A 2 L reactor was charged with 50.0 g (147 mmol) of the intermediate [1-a] obtained in the above Reaction Scheme 1-1, 31.9 g (191 mmol) of 2-nitrophenylboronic acid, 4.2 g of tetrakis (triphenylphosphine) palladium (4.0 mmol), potassium carbonate (50.8 g, 367 mmol), 1,4-dioxane (250 mL), toluene (250 mL) and distilled water (64 mL). After cooling to room temperature, the organic layer was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 42.3 g (yield: 85.8%) of the compound represented by [Intermediate 6-a].

Synthesis of [Reaction Scheme 6-2] [Intermediate 6-b]

42.3 g (126 mmol) of the compound represented by [Intermediate 6-a] obtained in the above Reaction Scheme 6-1, 99.2 g (378 mmol) of triphenylphosphine and 200 mL of dichlorobenzene were placed and refluxed for 12 hours. When the reaction was completed, the reaction mixture was filtered under reduced pressure in a hot state. The solution was dried under reduced pressure and then separated by column chromatography to obtain 31.2 g (yield 81.5%) of the compound represented by [Intermediate 6-b].

Synthesis of [Scheme 6-3] [Compound 30]

Synthesis Example 1 [Intermediate 6-b] obtained in [Scheme 6-2] instead of [Intermediate 1-c] in [Scheme 1-4] was replaced with 2-chloro-4,6-diphenyl-1,3,5-tri Was synthesized in the same way except that 2-chloro-4-phenylquinazoline was used instead of azine to obtain 7.1 g (yield: 45.2%) of the compound represented by [Compound 30].

MS [M] ^< ⁺ & gt ^; : 508

[Synthesis Example 7] Synthesis of Compound 31

Synthesis of [Reaction Scheme 7-1] [Compound 31]

10.0 g (33 mmol) of the intermediate 1-c obtained in the above Scheme 1-3, 12.7 g (40 mmol) of 2-iodo-9,9-dimethylfluorene and 0.3 g of copper iodide (2.0 mmol), potassium phosphate (14.7 g, 69 mmol), 1,2-cyclohexyldiamine (7.9 g, 69 mmol) and 1,4-dioxane (100 mL) were added and stirred at 100 ° C for 12 hours. After filtration at a high temperature, the product was separated by column chromatography to obtain 7.8 g (yield: 47.7%) of a compound represented by [Compound 31].

MS [M] ^< ⁺ & gt ^; : 496

Example: Preparation of organic light emitting diode

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was set to have a pressure of 1 x 10 < ^-6 > Torr, and DNT (700 ANGSTROM), NPD (300 ANGSTROM) (300 Å), Compound E: Liq = 1: 1 (250 Å), Liq (10 Å) and Al (1,000 Å) were deposited in this order and measured at 0.4 mA.

The structures of DNTPD, NPD, RD-1, compound E and Liq are as follows.

<DNTPD> <NPD>

<RD-1><CompoundE><Liq>

Comparative Example

The organic light emitting diode device for the comparative example was fabricated in the same manner as the organic light emitting diode device of the present invention except that BAlq, which is generally known as a phosphorescent host material, was used instead of the compound according to the present invention.

<BAlq>

The voltage, the current density, the luminance, the color coordinate, and the lifetime of the organic EL device manufactured according to Examples 1 to 7 and Comparative Example 1 were measured, and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (3000 cd / m &lt; 2 &gt;) to 95%.

division Host Doping concentration% V Cd / ㎡ CIEx CIEy T ₉₅ (Hr) Comparative Example 1 BAlq 10 6.2 1470 0.665 0.334 40 Example 1 2 10 4.3 2270 0.655 0.335 400 Example 2 3 10 4.2 2100 0.665 0.335 400 Example 3 26 10 4.3 2190 0.665 0.335 400 Example 4 30 10 4.1 2020 0.665 0.335 300 Example 5 42 10 4.0 2150 0.665 0.335 270 Example 6 49 10 4.0 2200 0.665 0.335 320 Example 7 51 10 4.2 2100 0.665 0.335 300

As shown in Table 1, the device employing the organic compound according to the present invention has a lower driving voltage, a higher luminance, and particularly a longer life characteristic than a device using BAlq, which is well known as a phosphorescent host material in the prior art .

Claims (6)

An organic light-emitting compound represented by the following Formula 1:
[Chemical Formula 1]

In the above formula (1)
At least one of two or more adjacent R's in a plurality of R's may form a ring through a single bond to form a ring or form a ring by bonding with a substituted or unsubstituted methylene group or a substituted amino group (-NR ₁ -), an oxygen atom -O-), a sulfur atom (-S-) or a selenium atom (-Se-) is covalently bonded to form a ring,
X ₁ And X ₂ are the same or different from each other and each independently selected from the group consisting of S, O, NR ₁ , SiR ₂ R ₃ , GeR ₄ R ₅ , CR ₆ R ₇ , Se and Te,
Wherein R and R ₁ to R ₇ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted aryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, a phosphoryl group, A hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, an ether group and an ester group. The method according to claim 1,
The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is selected from the following compounds 1 to 57:

1. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic layers comprises an organic electroluminescent compound represented by Formula 1 according to Claim 1. The method of claim 3,
Wherein the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes,
Wherein at least one of the layers comprises an organic light-emitting compound represented by the formula (1). The method of claim 3,
Wherein the organic material layer comprises a light emitting layer, and the light emitting layer comprises an organic light emitting compound represented by the following formula (1). The method of claim 3,
Wherein at least one of the organic light emitting layers emitting red, green or blue light is further included in the organic material layer to emit white light.

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