KR102460834B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

[화학식 2]

The present invention is an organic light emitting compound comprising an organic light emitting compound represented by the following [Formula 1], an organic light emitting device comprising the same, a first compound represented by the following [Formula 1], and a second compound represented by the following [Formula 2] As a device, the organic light emitting device according to the present invention has a low driving voltage, excellent efficiency, and can implement long life characteristics, so that it can be usefully used in various display and lighting industries.
[Formula 1]

[Formula 2]

Description

An organic light emitting compound and an organic electroluminescent device comprising the same

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

An organic light emitting diode (OLED) is a self-luminous device, and has a wide viewing angle and excellent contrast, as well as a fast response time, excellent luminance, driving voltage and response speed characteristics, and multicolorization.

In an organic light emitting device, the most important factor that determines the light emitting characteristics such as efficiency is the light emitting material, and when only one material is used as the light emitting layer for the light emitting layer, the maximum emission wavelength moves to a longer wavelength due to intermolecular interaction, and the color purity decreases or light emission Since there is a problem that the efficiency of the device is reduced due to the attenuation effect, the two materials are co-deposited using a host/dopant system as a light emitting material in order to increase color purity and increase luminous efficiency through energy transfer. If necessary, two or more materials may be co-deposited.

In addition, although fluorescent materials have been widely used up to now, research on the development of phosphorescent materials has been widely conducted in that, due to the mechanism of organic light emission, phosphorescent materials can theoretically improve luminous efficiency up to 4 times compared to fluorescent materials. .

However, in the case of phosphorescence, it is difficult to synthesize a stable host and dopant compound despite high efficiency, and there are many problems in application due to instability due to a high energy barrier of the light emitting layer interface. In particular, the current efficiency is high, but the driving voltage is high, and thus the power efficiency is lowered, and the device lifespan is remarkably low, so a solution is urgently needed.

Accordingly, the problem to be solved by the present invention is to solve the above problems, and it is to provide an organic light emitting compound having superior luminous efficiency, driving voltage, and long lifespan characteristics than conventional materials.

In addition, an object of the present invention is to provide an organic light emitting device having characteristics of low voltage driving, high efficiency and long life by employing the organic light emitting compound as a light emitting material.

In order to solve the above problems, the present invention provides an organic light emitting compound represented by the following [Formula 1] and an organic light emitting device comprising the same.

[Formula 1]

In addition, the present invention is an organic light emitting comprising a first compound represented by the above [Formula 1] and a second compound represented by the following [Formula 2] in an organic layer interposed between the first and second electrodes facing each other provide the element.

[Formula 2]

The specific structures of the first compound and the second compound respectively represented by [Formula 1] and [Formula 2] will be described later.

The organic light emitting diode according to the present invention has a low driving voltage, excellent efficiency, and long lifespan characteristics, so that it can be usefully used in various display and lighting industries.

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

One aspect of the present invention relates to an organic light emitting compound represented by the following [Formula 1].

[Formula 1]

In the above [Formula 1],

X is CR', and at least one of the plurality of R's is represented by A.

L is a linking group, a single bond or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, a substituted or unsubstituted C 2 to C 60 alkynylene group, substituted or an unsubstituted C 3 to C 60 cycloalkylene group, a substituted or unsubstituted C 2 to C 60 heterocycloalkylene group, a substituted or unsubstituted C 6 to C 60 arylene group, and a substituted or unsubstituted C 2 to C 60 Any one selected from the heteroarylene group, n is an integer of 0 to 3, a plurality of L may be the same or different from each other.

Ar is hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl or heteroalkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted C 2 to C 30 heteroaryl group selected from It can be any one.

R′ and R ₁ to R ₉ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms , a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C5 to 30 arylamine group, substituted or unsubstituted C5 to C50 aryl group, substituted or unsubstituted and heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, substituted or unsubstituted silyl group , substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group, phosphoryl group, amino group, nitrile group, hydroxyl group, nitro group, halogen group, selenium group, tellurium group, It is any one selected from the group consisting of an amide group and an ester group, and may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other, and m is an integer of 0 to 2.

In addition, 'substitution' in 'substituted or unsubstituted' of [Formula 1] is deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a carbon number A heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, It means being substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 24 carbon atoms and an aryloxy group having 6 to 24 carbon atoms.

In addition, the carbon number range of the alkyl group or aryl group in the 'substituted or unsubstituted alkyl group having 1 to 30 carbon atoms', 'substituted or unsubstituted aryl group having 6 to 40 carbon atoms', etc., considers the portion in which the substituent is substituted. It refers to the total number of carbon atoms constituting the alkyl part or the aryl part when viewed as unsubstituted. For example, a phenyl group substituted with a butyl group at the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

Meanwhile, specific examples of the alkyl group used in the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-amyl group, a hexyl group, a heptyl group. , octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, and the like, and at least one hydrogen atom of the alkyl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (referred to as "alkylsilyl group" in this case), a substituted or unsubstituted amino group (-NH ₂ , -NH(R), -N(R')(R"), where R, R' and R" are each Independently an alkyl group having 1 to 24 carbon atoms (referred to as “alkylamino group” in this case), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 alkyl group Halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C5-C24 aryl group, C6-C24 arylalkyl group, C3-C24 hetero It may be substituted with an aryl group or a heteroarylalkyl group having 3 to 24 carbon atoms.

Specific examples of the alkoxy group used in the present invention include a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an iso-amyloxy group, a hexyloxy group, and the like. , may be substituted with the same substituents as in the case of the alkyl group.

Specific examples of the halogen group used in the present invention include fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the like.

The aryloxy group used in the present invention refers to an -O- aryl radical, wherein the aryl group is as defined above, and specific examples thereof include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy and the like, and one or more hydrogen atoms included in the aryloxy group may be further substituted.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl and the like.

The aryl group used in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, and the aryl group When there is a substituent, it may be fused with a neighboring 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, phenanthryl group and aromatic groups such as , pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, the aryl group may also be further substituted with one or more substituents, and more specifically, at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R"), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 hetero It may be substituted with an alkyl group, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, or the like.

The heteroaryl group used in the present invention may be any one selected from the following [Structural Formula 1] to [Structural Formula 14].

In the [Structural Formula 1] to [Structural Formula 10],

T ₁ to T ₁₂ are the same as or different from each other, and each independently may be any one selected from C(R ₁₀₁ ), C(R ₁₀₂ )(R ₁₀₃ ), N, N(R ₁₀₄ ), O and S and T ₁ to T ₁₂ are not all carbon atoms at the same time, and R ₁₀₁ to R ₁₀₄ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, substituted or an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a heteroatom. is chosen

In addition, the [Structural Formula 3] may include a compound represented by the following [Structural Formula 3-1] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In [Structural Formula 3-1], T ₁ to T ₇ are the same as defined in [Structural Formula 1] to [Structural Formula 10].

According to a preferred embodiment of the present invention, the [Structural Formula 1] to [Structural Formula 10] may be selected from the following [Structural Formula 11].

[Structural Formula 11]

In the [Structural Formula 11],

X is the same as the definition of R ₁ to R ₉ in [Formula 1], m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs may be the same or different from each other.

The first compound represented by [Formula 1] according to the present invention may be any one specifically selected from the following [Compound 1] to [Compound 116], whereby the scope of [Formula 1] is not limited thereto.

In addition, another aspect of the present invention relates to an organic light emitting device comprising the organic light emitting compound according to the above [Formula 1], comprising an organic layer between the opposed first electrode and the second electrode, the organic layer is a light emitting layer It relates to an organic light emitting device comprising a hole transport layer between the light emitting layer and the first electrode, and an electron transport layer between the light emitting layer and the second electrode, wherein the electron transport layer or hole transport layer according to the present invention It is characterized in that it contains an organic light emitting compound represented by Formula 1].

Another aspect of the present invention includes an organic layer between the opposing first electrode and the second electrode, the organic layer includes a light emitting layer, and a hole transport layer between the light emitting layer and the first electrode, the light emitting layer and the second electrode It relates to an organic light emitting device comprising an electron transport layer between two electrodes, wherein the light emitting layer comprises a first compound represented by [Formula 1] and a second compound represented by the following [Formula 2] according to the present invention do it with

[Formula 2]

In the above [Formula 2],

L ₁ is a linking group, a single bond or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, a substituted or unsubstituted C 2 to C 60 alkynylene group, A substituted or unsubstituted C 3 to C 60 cycloalkylene group, a substituted or unsubstituted C 2 to C 60 heterocycloalkylene group, a substituted or unsubstituted C 6 to C 60 arylene group, and a substituted or unsubstituted C 2 to C 2 to Any one selected from the heteroarylene group of 60, n ₁ is an integer of 0 to 3, a plurality of L ₁ may be the same as or different from each other.

Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group or heteroalkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted Any one selected from a cyclic heteroaryl group having 2 to 30 carbon atoms.

In addition, the L ₁ , Ar ₁ and Ar ₂ may each independently be further substituted with one or more substituents, and the one or more substituents are deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, and 1 to 24 carbon atoms. Alkyl group, C1-C24 halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C7-C24 arylalkyl group , C2-C24 heteroaryl group or C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C6-C24 arylamino group, C1-C24 heteroaryl It may be selected from the group consisting of an amino group, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms, wherein L ₁ , Ar ₁ , Ar ₂ and substituents thereof are Adjacent substituents may combine with each other to form a saturated or unsaturated ring.

The second compound represented by [Formula 2] according to the present invention may be any one specifically selected from the following [Compound 117] to [Compound 136], whereby the scope of [Formula 2] is not limited .

In addition, according to an embodiment of the present invention, the compound represented by the above [Formula 1] may be included in the hole transport layer or the electron transport layer of the organic light emitting diode according to the present invention.

In addition, according to another embodiment of the present invention, the mixing weight ratio of the first compound, the second compound, and the dopant compound may be 1: 0.01 to 99: 0.01 to 15. When the mixing weight ratio is within the above range, satisfactory energy transfer and light emission can occur.

In addition, the phosphorescent dopant included in the emission layer is not particularly limited, but may be one or more compounds selected from compounds represented by the following [General Formula A-1] to [General Formula J-1].

[General Formula A-1]

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. In addition, the L ₁ , L ₂ , and L ₃ are the same as or different from each other as a ligand, and may each independently be any one selected from the following [Structural Formula D], but are not limited thereto. In addition, * in the following [Structural Formula D] represents a site binding to the metal ion M.

[Structural Formula D]

In the above [Structural Formula D],

Wherein R is different or the same as each other and each independently hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted A heteroaryl group having 5 to 50 carbon atoms, 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, substituted or An unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6-C30 arylsilyl group It may be any one selected from the group.

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. It may be further substituted with one or more substituents.

In addition, R may be connected to each adjacent substituent with 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 an example, the dopant represented by the [General Formula A-1] may be any one selected from the following compounds, but is not limited thereto.

[General Formula B-1]

In the above [General Formula B-1],

M ^A1 represents the same metal ion as defined in [General Formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 each independently represent a carbon atom or a nitrogen atom, Y ^A12 , 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 L ^A11 , L ^A12 , L ^A13 , and L ^A14 are each a linking group as defined above , and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonded to M ^A1 .

An exemplary structure of the compound represented by the [General Formula B-1] is as follows, but is not limited thereto.

[General formula C-1]

In the above [general formula C-1],

M ^B1 represents the same metal ion as defined in [General 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 represents 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 , L ^B14 represents a linking group, Q ^B11 , Q ^B12 are Represents a partial structure containing an atom bonded to M ^B1 .

An exemplary structure of the compound represented by the [General Formula C-1] is as follows, but is not limited thereto.

[General formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1] for the metal ion, R ^C11 , R ^C12 are each independently a hydrogen atom, a substituent that connects to each other and forms a 5-membered ring, Represents a substituent, R ^C13 , R ^C14 each independently represents a hydrogen atom, a substituent connecting to each other to form a 5-membered ring, and a substituent having nothing to connect to each other, G ^C11 , G ^C12 are each independently a nitrogen atom, a substitution or an unsubstituted carbon atom, L ^C11 , L ^C12 represents a linking group, and Q ^C11 , Q ^C12 represents a partial structure containing an atom bonded to M ^C1 .

An exemplary structure of the compound represented by the [General Formula D-1] is as follows, but is not limited thereto.

[General formula E-1]

In the above [general formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], G ^D11 , G ^D12 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11 , J ^D12 , J ^D13 and Each of J ^D14 independently represents a group of atoms necessary to form a 5-membered ring, and L ^D11 and L ^D12 represent a linking group.

An exemplary structure of the compound represented by the [General Formula E-1] is as follows, but is not limited thereto.

[General Formula F-1]

In the above [general formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], J ^E11 , J ^E12 each independently represents an atomic group required to form a 5-membered ring, 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 or a substituted or unsubstituted carbon atom.

An exemplary structure of the compound represented by the [General Formula F-1] is as follows, but is not limited thereto.

[General formula G-1]

In the above [general formula G-1],

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

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 and R ^F13 , R ^F13 and R ^F14 are linked to each other a ring may be formed, wherein the ring formed by R ^F1 and R ^F12 , and R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonding to M ^F1 .

An exemplary structure of the compound represented by the [general formula G-1] is as follows, but is not limited thereto.

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

In the [general formula H-1] to [general formula H-3],

R ¹¹ , R ¹² is a substituent of alkyl, aryl or heteroaryl; In addition, a fused ring may be formed with a substituent adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

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

L ¹ is a ligand binding to platinum, preferably a ligand capable of forming an ortho metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal (ortho metal). ) is a ligand that forms a platinum complex, a bipyridyl ligand or a phenanthroline ligand.

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

In addition, n ¹ and m ¹ are preferably such that the metal complex represented by the general formula H-1 becomes a neutral complex.

In the above [general formula H-2],

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

In the above [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 , respectively, and q ³¹ represents an integer of 0 to 8, preferably 0 to 2, and more than 0 desirable.

Examples of specific compounds of the [general formula H-1] to [general formula H-3] are as follows, but are not limited thereto.

[General Formula I-1]

In the above [General Formula I-1],

Ring A, Ring B, Ring C and Ring D represents a nitrogen-containing heterocycle in which any two of the rings A to D may have a substituent, and the other two rings are an aryl ring or heterocyclic ring which may have a substituent. An aryl ring is represented and represented, and a condensed ring may be formed with Ring A and Ring B, Ring A and Ring C and/or Ring B and Ring D. X ¹ , X ² , X ³ and X ⁴ each represents a nitrogen atom coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² , and Q ³ each independently represent a divalent atom (provided) or a bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Any two of Z ¹ , Z ² , Z ³ and Z ⁴ represent a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of specific compounds of the [General Formula I-1] are as follows, but are not limited thereto.

[General formula J-1]

In the [general formula J-1],

M represents the same metal ion as defined in [General Formula A-1], Ar1 represents a substituted or unsubstituted ring structure, and two azomethine bonds bonded to M (-C=N-) In the above, each nitrogen atom (N) is bonded to the M, and forms a tridentate ligand bonded to M as a whole at 3 positions.

Incidentally, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl or aryl group, and L represents a monodentate ligand.

In the [General Formula J-1], M is preferably Pt. Moreover, as said Ar1, it is preferable to select from a 5-membered ring, a 6-membered ring, and these condensed cyclic groups.

Examples of specific compounds of the [General Formula J-1] are as follows, but are not limited thereto.

Hereinafter, the organic light emitting device according to the present invention will be described in more detail.

The organic light emitting device according to the present invention includes an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode, and may further include a hole injection layer and an electron injection layer if necessary, and in addition to that, an intermediate layer of one or two layers It is also possible to further form, a hole blocking layer or an electron blocking layer may be further formed, and may further include an organic layer having various functions according to the characteristics of the device.

Looking at the organic light emitting device and the method for manufacturing the same according to the present invention, first, a material for an anode electrode is coated on a substrate to form an anode. Here, as the substrate, a substrate used in a conventional organic light emitting device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofness is preferable. In addition, as the material for the anode electrode, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc. are used.

A hole injection layer is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode electrode. Next, a hole transport layer is formed by vacuum thermal evaporation or spin coating of a hole transport layer material on the hole injection layer.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, and as a specific example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ] can be used.

In addition, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1 -biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD), etc. can be used.

Subsequently, a thin film may be formed by laminating a light emitting layer on the hole transport layer and selectively depositing a hole blocking layer on the light emitting layer by a vacuum deposition method or a spin coating method. The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because the lifetime and efficiency of the device are reduced when holes are introduced into the cathode through the organic light emitting layer. . In this case, the hole blocking material used is not particularly limited, but has an electron transport ability and has an ionization potential higher than that of a light emitting compound, and typically BAlq, BCP, TPBI, or the like may be used.

After depositing an electron transport layer on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer is formed, and a cathode forming metal is vacuum thermally deposited on the electron injection layer to form a cathode electrode. The small is complete. Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

As the material for the electron transport layer, a known electron transport material may be used as it functions to stably transport electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, especially tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2), ADN, and oxadiazole derivatives PBD, BMD, BND, etc. may be used.

In addition, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process, wherein the deposition method means a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used as a material for forming each layer It refers to a method of mixing a material to be used with a solvent and forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting diode 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 lighting device, and a monochromatic or white flexible lighting device.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereby.

Synthesis example 1. Synthesis of compound 1

Synthesis Example 1-1. Synthesis of <Intermediate 1-a>

<Intermediate 1-a> was synthesized according to Scheme 1 below.

[Scheme 1]

<Intermediate 1-a>

In a dried 1 L round-bottom flask reactor, 2-bromotriphenylene (42 g, 247 mmol) was dissolved in 420 mL of tetrahydrofuran under a nitrogen stream and 1.6 M n-butyllithium (155 mL) while stirring at -78 ° C. , 247 mmol) is slowly added dropwise. When the dropwise addition is completed, the mixture is stirred for an hour and a half while maintaining the temperature below minus 78 °C. Then, trimethylborate (20.8 g, 297 mmol) was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. After completion of the reaction, 200 mL of 2 N aqueous hydrochloric acid solution was added dropwise at room temperature and stirred for 30 minutes. After that, extraction was performed with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized to obtain <Intermediate 1-a>. (32 g, 78.5%)

Synthesis example 1-2. Synthesis of <Intermediate 1-b>

<Intermediate 1-b> was synthesized according to Scheme 2 below.

[Scheme 2]

<Intermediate 1-a> <Intermediate 1-b>

In a 1 L round bottom flask reactor, 1-bromo-2-iodobenzene (12.5 g, 95 mmol), <Intermediate 1-a> (31.7 g, 105 mmol), potassium carbonate (26.4 g, 191 mmol), tetra Kistriphenylphosphine palladium (2.2 g, 2 mmol), 80 mL of water, 150 mL of toluene and 150 mL of 1,4-dioxane were added and stirred under reflux for 12 hours. After completion of the reaction, the reactants were separated and the organic layer was concentrated under reduced pressure. It was separated by column chromatography to obtain <Intermediate 1-b>. (26 g, 72.1%)

Synthesis example 1-3. Synthesis of <Intermediate 1-c>

<Intermediate 1-c> was synthesized according to Scheme 3 below.

[Scheme 3]

<Intermediate 1-b> <Intermediate 1-c>

In a dried 1 L round-bottom flask reactor, <Intermediate 1-b> (26 g, 107 mmol) was dissolved in 260 mL of tetrahydrofuran under a nitrogen stream, and 1.6 M n-butyllithium (104 mL, 104 mL, 117 mmol) is slowly added dropwise. When the dropwise addition is completed, the mixture is stirred for an hour and a half while maintaining the temperature below minus 78 °C. After that, 2-bromo-9-fluorenone (14.8 g, 107 mmol) was slowly added thereto, and the mixture was raised to room temperature and stirred for 2 hours. After completion of the reaction, 200 mL of water was added dropwise at room temperature and stirred for 30 minutes. Then, extract with ethyl acetate and water, concentrate the organic layer, immediately add 260 mL of acetic acid and 26 mL of hydrochloric acid, and stir under reflux for 2 hours. After completion of the reaction, an excess of water was added, stirred for 30 minutes, filtered, and separated by column chromatography to obtain <Intermediate 1-c>. (28.5 g, 76.6%)

Synthesis example 1-4. Synthesis of <Intermediate 1-d>

<Intermediate 1-d> was synthesized according to Scheme 4 below.

[Scheme 4]

<Intermediate 1-c> <Intermediate 1-d>

<Intermediate 1-d> was obtained by the same method as in Synthesis Example 1-1 except that <Intermediate 1-c> was used instead of 2-bromotriphenylene. (15.7 g, 71%)

Synthesis example 1-5. <compound 1> of synthesis

<Compound 1> was synthesized according to Scheme 5 below.

[Scheme 5]

<Intermediate 1-d> <Compound 1>

In Synthesis Example 1-2, using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-bromo-2-iodobenzene and <Intermediate 1-a> instead of <Intermediate 1-a> <Compound 1> was obtained by synthesizing in the same manner except that d> was used. (4.5 g, 51%)

MS (MALDI-TOF): m/z 697.25 [M ⁺ ]

Synthesis example 2. Synthesis of compound 9

Synthesis Example 2-1. Synthesis of <Intermediate 2-a>

<Intermediate 2-a> was synthesized according to Scheme 6 below.

[Scheme 6]

<Intermediate 2-a>

2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (14 g, 34 mmol), bispinacolato diboron (10.4) in a dried 500 mL round bottom flask reactor g, 41 mmol), palladium (II) chloride-1,1'-bis(diphenylphosphino)ferrocene (1.4 g, 1 mmol), potassium acetate (6.7 g, 68 mmol), and 140 ml of toluene were added for 10 hours while stirring under reflux. After the reaction was completed, the solid was filtered and the filtrate was concentrated under reduced pressure. It was separated by column chromatography to obtain <Intermediate 2-a>. (10.5 g, 61.5%)

Synthesis example 2-2. <compound 9> of synthesis

<Compound 9> was synthesized according to Scheme 7 below.

[Scheme 7]

<Intermediate 1-c> <Intermediate 2-a> <Compound 9>

In Synthesis Example 1-2, <Intermediate 1-c> was used instead of 1-bromo-2-iodobenzene and <Intermediate 2-a> was used instead of <Intermediate 1-a>. <Compound 9> was obtained. (3.8 g, 48.5%)

MS (MALDI-TOF): m/z 773.28 [M ⁺ ]

Synthesis example 3. Synthesis of compound 16

Synthesis Example 3-1. Synthesis of <Intermediate 3-a>

<Intermediate 3-a> was synthesized according to Scheme 8 below.

[Scheme 8]

<Intermediate 1-b> <Intermediate 3-a>

<Intermediate 3-a> was obtained in the same manner as in Synthesis Example 1-3, except that 3-bromo-9-fluorenone was used instead of 2-bromo-9-fluorenone. (12.5 g, 69.5%)

Synthesis example 3-2. Synthesis of <Intermediate 3-b>

<Intermediate 3-b> was synthesized according to Scheme 9 below.

[Scheme 9]

<Intermediate 3-a> <Intermediate 3-b>

<Intermediate 3-b> was obtained by synthesizing in the same manner except that <Intermediate 3-a> was used instead of 2-bromotriphenylene in Synthesis Example 1-1. (20.4 g, 74.2%)

Synthesis example 3-3. <compound 16> of synthesis

<Compound 16> was synthesized according to Scheme 10 below.

[Scheme 10]

<Intermediate 3-b> <Compound 16>

In Synthesis Example 1-2, use 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-bromo-2-iodobenzene and <Intermediate 3-a> instead of <Intermediate 1-a> <Compound 16> was obtained by synthesizing in the same manner except that b> was used. (4.1 g, 54.2%)

MS (MALDI-TOF): m/z 697.25 [M ⁺ ]

Synthesis example 4. Synthesis of compound 20

Synthesis Example 4-1. Synthesis of <Intermediate 4-a>

<Intermediate 4-a> was synthesized according to Scheme 11 below.

[Scheme 11]

<Intermediate 4-a>

<Intermediate 4-a> was obtained in the same manner as in Synthesis Example 1-1, except that 1-bromotriphenylene was used instead of 2-bromotriphenylene. (32.2 g, 74.5%)

Synthesis example 4-2. Synthesis of <Intermediate 4-b>

<Intermediate 4-b> was synthesized according to Scheme 12 below.

[Scheme 12]

<Intermediate 4-a> <Intermediate 4-b>

<Intermediate 4-b> was obtained by synthesizing in the same manner except that <Intermediate 4-a> was used instead of <Intermediate 1-a> in Synthesis Example 1-2. (27.2 g, 64.2%)

Synthesis example 4-3. Synthesis of <Intermediate 4-c>

<Intermediate 4-c> was synthesized according to Scheme 13 below.

[Scheme 13]

<Intermediate 4-b> <Intermediate 4-c>

In Synthesis Example 1-3, in the same manner except that <Intermediate 4-b> was used instead of <Intermediate 1-b> and 3-bromo-9-fluorenone was used instead of 2-bromo-9-fluorenone. By synthesis, <Intermediate 4-c> was obtained. (19.5 g, 79.5%)

Synthesis example 4-4. Synthesis of <Intermediate 4-d>

<Intermediate 4-d> was synthesized according to Scheme 14 below.

[Scheme 14]

<Intermediate 4-c> <Intermediate 4-d>

<Intermediate 4-d> was obtained by synthesizing in the same manner except that <Intermediate 4-c> was used instead of 2-bromotriphenylene in Synthesis Example 1-1. (15.4 g, 71.5%)

Synthesis example 4-5. <compound 20> of synthesis

<Compound 20> was synthesized according to Scheme 15 below.

[Scheme 15]

<Intermediate 4-d> <Compound 20>

In Synthesis Example 1-2, using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-bromo-2-iodobenzene and <Intermediate 4-a> instead of <Intermediate 1-a> <Compound 20> was obtained by synthesizing in the same manner except that d> was used. (3.4 g, 44.2%)

MS (MALDI-TOF): m/z 697.25 [M ⁺ ]

Synthesis example 5. Synthesis of compound 32

Synthesis Example 5-1. Synthesis of <Intermediate 5-a>

<Intermediate 5-a> was synthesized according to Scheme 16 below.

[Scheme 16]

<Intermediate 5-a>

Put 2-hydroxymethylphenol (100 g, 806 mmol), sodium cyanide (43.4 g, 886 mmol), and dimethylformamide 1000 mL in a dried 2 L round-bottom flask reactor, and stir at 120 °C for 4 hours. After completion of the reaction, extraction was performed with water and ethyl acetate. After concentration, it was separated by column chromatography to obtain <Intermediate 5-a>. (90 g, 81%)

Synthesis example 5-2. Synthesis of <Intermediate 5-b>

<Intermediate 5-b> was synthesized according to Scheme 17 below.

[Scheme 17]

<Intermediate 5-a> <Intermediate 5-b>

<Intermediate 5-a> (90 g, 676 mmol), 4-dimethylaminopyridine (68.8 g, 338 mmol), triethylamine (137 g, 1352 mmol), and 900 mL of methylene chloride were placed in a dried 2 L reactor Benzyl chloride (82.4 g, 676 mmol) is added dropwise at 0°C. After dropwise addition, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the mixture was concentrated and separated by column chromatography to obtain <Intermediate 5-b>. (40 g, 61%)

Synthesis example 5-3. Synthesis of <Intermediate 5-c>

<Intermediate 5-c> was synthesized according to Scheme 18 below.

[Scheme 18]

<Intermediate 5-b> <Intermediate 5-c>

<Intermediate 5-b> (40 g, 169 mmol), tricyclohexylphosphine (9.5 g, 34 mmol), zinc powder (1.9 g, 17 mmol), palladium acetate (3.8 g, 17 mmol), 400 mL of dimethylformamide, and stirred under reflux for 12 hours under nitrogen. After completion of the reaction, the reactant was added dropwise to excess water at room temperature to form brown crystals, filtered and separated by column chromatography to obtain <Intermediate 5-c>. (20 g, 51.6%)

Synthesis example 5-4. Synthesis of <Intermediate 5-d>

<Intermediate 5-d> was synthesized according to Scheme 19 below.

[Scheme 19]

<Intermediate 5-c> <Intermediate 5-d>

<Intermediate 5-c> (37 g, 156 mmol), urea (16.9 g, 281 mmol), and 185 mL of acetic acid are added to a 500 mL round-bottom flask reactor, and the mixture is stirred under reflux for 12 hours. After completion of the reaction, an excess of water is added to the reactant to precipitate, followed by filtration. After hot slurry with methanol, filtered, hot slurry with toluene, filtered and dried to obtain <Intermediate 5-d>. (24 g, 79%)

Synthesis example 5-5. Synthesis of <Intermediate 5-e>

<Intermediate 5-e> was synthesized according to Scheme 20 below.

[Scheme 20]

<Intermediate 5-d> <Intermediate 5-e>

<Intermediate 5-d> (15 g, 44 mmol) and 150 mL of phosphorus oxychloride were added to a dried 500 mL round-bottom flask reactor, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the reactant is slowly added to excess water at 0° C. to precipitate, followed by filtration. It was separated by column chromatography to obtain <Intermediate 5-e>. (21 g, 81%)

Synthesis example 5-6. <compound 32> of synthesis

<Compound 32> was synthesized according to Scheme 21 below.

[Scheme 21]

<Intermediate 5-e> <Intermediate 1-d> <Compound 32>

In Synthesis Example 1-2, <Intermediate 5-e> was used instead of 1-bromo-2-iodobenzene, and <Intermediate 1-d> was used instead of <Intermediate 1-a>. <Compound 32> was obtained. (2.9 g, 34.2%)

MS (MALDI-TOF): m/z 710.24 [M ⁺ ]

Synthesis example 6. Synthesis of compound 67

Synthesis Example 6-1. Synthesis of <Intermediate 6-a>

<Intermediate 6-a> was synthesized according to Scheme 22 below.

[Scheme 22]

<Intermediate 4-b> <Intermediate 6-a>

<Intermediate 6-a> was obtained by synthesizing in the same manner except that <Intermediate 4-b> was used instead of <Intermediate 1-b> in Synthesis Example 1-3. (20 g, 71.5%)

Synthesis example 6-2. Synthesis of <Intermediate 6-b>

<Intermediate 6-b> was synthesized according to Scheme 23 below.

[Scheme 23]

<Intermediate 6-a> <Intermediate 6-b>

<Intermediate 6-b> was obtained by synthesizing in the same manner except that <Intermediate 6-a> was used instead of 2-bromotriphenylene in Synthesis Example 1-1. (16.4 g, 68.5%)

Synthesis example 6-3. <compound 67> of synthesis

<Compound 67> was synthesized according to Scheme 24 below.

[Scheme 24]

<Intermediate 6-b> <Compound 67>

In Synthesis Example 1-2, 2-chloro-4-phenylquinazoline was used instead of 1-bromo-2-iodobenzene, and <Intermediate 1-a> was used in the same manner except that <Intermediate 6-b> was used. to obtain <Compound 67>. (3.4 g, 45.2%)

MS (MALDI-TOF): m/z 670.24 [M ⁺ ]

Synthesis example 7. Synthesis of compound 69

Synthesis Example 7-1. Synthesis of <Intermediate 7-a>

<Intermediate 7-a> was synthesized according to Scheme 25 below.

[Scheme 25]

<Intermediate 7-a>

In a 2 L reactor, put 2-cyanophenol (24.5 g, 206 mmol), 2-bromoacetophenone (40.9 g, 206 mmol), potassium carbonate (85.3 g, 617 mmol), and acetone 980 mL, and Stir for hours. After completion of the reaction, the reaction solution is cooled to room temperature and filtered with acetone. After concentrating the filtrate, it was recrystallized to obtain <Intermediate 7-a>. (37 g, 76%)

Synthesis example 7-2. Synthesis of <Intermediate 7-b>

<Intermediate 7-b> was synthesized according to Scheme 26 below.

[Scheme 26]

<Intermediate 7-a> <Intermediate 7-b>

<Intermediate 7-b> was obtained by synthesizing in the same manner except that <Intermediate 7-a> was used instead of <Intermediate 5-c> in Synthesis Example 5-4. (17.2 g, 68.1%)

Synthesis example 7-3. Synthesis of <Intermediate 7-c>

<Intermediate 7-c> was synthesized according to Scheme 27 below.

[Scheme 27]

<Intermediate 7-b> <Intermediate 7-c>

<Intermediate 7-c> was obtained by synthesizing in the same manner except that <Intermediate 7-b> was used instead of <Intermediate 5-d> in Synthesis Example 5-5. (12.3 g, 67.1%)

Synthesis example 7-4. <compound 69> of synthesis

<Compound 69> was synthesized according to Scheme 28 below.

[Scheme 28]

<Intermediate 7-c> <Intermediate 1-d> <Compound 69>

In Synthesis Example 1-2, <Intermediate 7-c> was used instead of 1-bromo-2-iodobenzene, and <Intermediate 1-d> was used instead of <Intermediate 1-a>. <Compound 69> was obtained. (2.4 g, 30.4.2%)

MS (MALDI-TOF): m/z 710.24 [M ⁺ ]

Synthesis example 8. Synthesis of compound 89

Synthesis Example 8-1. Synthesis of <Intermediate 8-a>

<Intermediate 8-a> was synthesized according to Scheme 29 below.

[Scheme 29]

<Intermediate 8-a>

Put 4-dibenzofuranboronic acid (64 g, 302 mmol), bismuth (III) nitrate pentahydrate (102.5 g, 211 mmol), and toluene in a dried 2 L round-bottom flask reactor, and stir under reflux for 6 hours. . After completion of the reaction, after the silica gel filter was heated with toluene, the filtrate was concentrated and separated by column chromatography to obtain <Intermediate 8-a>. (54.2 g, 67.4%)

Synthesis example 8-2. Synthesis of <Intermediate 8-b>

<Intermediate 8-b> was synthesized according to Scheme 30 below.

[Scheme 30]

<Intermediate 8-a> <Intermediate 8-b>

Potassium cyanide (15.8 g, 243 mmol), potassium hydroxide (24.7 g, 441 mmol), ethyl cyanoacetate (74.8 g, 661 mmol), and 380 ml of dimethylformamide were added to a dried 2 L round-bottom flask reactor and stirred. . Dissolve <Intermediate 8-a> (47 g, 220 mmol) in 90 mL of dimethylformamide at 20 °C and add dropwise. Stir at reflux for 12 hours at 60 °C. Add 250 mL of 5% sodium hydroxide and stir under reflux for 2 hours. After completion of the reaction, the reaction solution is slowly added to 1500 mL of water to crystallize and filter. The filtered solid was dissolved in tetrahydrofuran and separated by column chromatography to obtain <Intermediate 8-b>. (11 g, 24%)

Synthesis example 8-3. Synthesis of <Intermediate 8-c>

<Intermediate 8-c> was synthesized according to Scheme 31 below.

[Scheme 31]

<Intermediate 8-b> <Intermediate 8-c>

In a dried 500 mL reactor, <Intermediate 8-b> (11 g, 48 mmol) was added to 55 mL of tetrahydrofuran and stirred. At 0 °C, 3 M phenylmagnesium bromide (37 mL, 101 mmol) and 33 mL of tetrahydrofuran were slowly added dropwise, followed by stirring under reflux for 2 hours. After dropwise addition of 6 N hydrochloric acid at 0° C., the mixture was stirred under reflux for 1 hour. At room temperature, 6 N sodium hydroxide was added to adjust the pH to 8, followed by extraction with water and ethyl acetate. The organic layer was concentrated and recrystallized to obtain <Intermediate 8-c>. (14.5 g, 96%)

Synthesis example 8-4. Synthesis of <Intermediate 8-d>

<Intermediate 8-d> was synthesized according to Scheme 32 below.

[Scheme 32]

<Intermediate 8-c> <Intermediate 8-d>

<Intermediate 8-d> was obtained by synthesizing in the same manner except that <Intermediate 8-c> was used instead of <Intermediate 5-c> in Synthesis Example 5-4. (17.1 g, 68.1%)

Synthesis example 8-5. Synthesis of <Intermediate 8-e>

<Intermediate 8-e> was synthesized according to Scheme 33 below.

[Scheme 33]

<Intermediate 8-d> <Intermediate 8-e>

<Intermediate 8-e> was obtained by synthesizing in the same manner except that <Intermediate 8-d> was used instead of <Intermediate 5-d> in Synthesis Example 5-5. (8.5 g, 65.1%)

Synthesis example 8-6. <compound 89> of synthesis

<Compound 89> was synthesized according to Scheme 34 below.

[Scheme 34]

<Intermediate 8-e> <Intermediate 1-d> <Compound 89>

In Synthesis Example 1-2, <Intermediate 8-e> was used instead of 1-bromo-2-iodobenzene and <Intermediate 1-d> was used instead of <Intermediate 1-a>. <Compound 89> was obtained. (3.5 g, 35.4%)

MS (MALDI-TOF): m/z 760.25 [M ⁺ ]

Example 1: Manufacture of organic light emitting diode

After patterning so that the light emitting area of the ITO glass has a size of 2 mm × 2 mm, it was washed. After mounting the substrate in a vacuum chamber and making the base pressure 1 × 10 ^-6 torr, the organic material was placed on the ITO with HATCN (50 Å), NPD (900 Å), the compound prepared by the present invention, the first host compound 117 The weight ratio of the second host compound 1 and the second host compound 1 was set to 5:5, and a green phosphorescent dopant (GD) was doped with 7% to form an emission layer having a thickness of 400 Å. ET: A film was formed in the order of Liq = 1:1 (300 Å), Liq (10 Å), and Al (1,000 Å), and measurement was performed at 0.4 mA.

Example 2: Manufacture of organic light emitting diode

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 118 and Compound 9 were used instead of Compound 117 and Compound 1 when the emission layer was formed.

Example 3: Manufacture of organic light emitting diode

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 119 and Compound 16 were used instead of Compound 117 and Compound 1 when the emission layer was formed.

Example 4: Manufacture of organic light emitting diode

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 120 and Compound 20 were used instead of Compound 117 and Compound 1 when the emission layer was formed.

Example 5: Manufacture of organic light emitting diode

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 121 and Compound 32 were used instead of Compound 117 and Compound 1 when the emission layer was formed.

comparative example 1 to 5

The organic light emitting diode device for Comparative Example 1 was prepared in the same manner except that compounds 117 to 121 prepared by the invention were used alone as a host in the device structure of the above example.

For the organic electroluminescent devices manufactured according to Examples 1 to 5 and Comparative Examples 1 to 5, voltage, current density, luminance, color coordinates and lifetime were measured, and the results are shown in Table 1 below. T ₉₅ means the time required for the luminance to decrease to 95% from the initial luminance (6000 cd/m 2 ).

division first host second host wt:wt V Cd/A CIEx CIEy T ₉₅ (Hrs) Example 1 compound 117 compound 1 5:5 4.0 57 0.337 0.628 170 Example 2 compound 118 compound 9 5:5 3.9 55 0.322 0.629 160 Example 3 compound 119 compound 16 5:5 3.9 56 0.330 0.626 190 Example 4 compound 120 compound 20 5:5 3.8 57 0.333 0.609 180 Example 5 compound 121 compound 32 5:5 3.9 55 0.325 0.620 195 Comparative Example 1 compound 117 One 6.2 10.1 0.333 0.609 8 Comparative Example 2 compound 118 One 6.0 11.2 0.325 0.620 7 Comparative Example 3 compound 119 One 6.5 9.2 0.326 0.621 5 Comparative Example 4 compound 120 One 6.3 7.9 0.347 0.621 7 Comparative Example 5 compound 121 One 6.4 7.9 0.347 0.621 8

As shown in [Table 1], it can be seen that the organic light emitting devices of Examples 1 to 5 have superior driving voltage, efficiency, and lifespan characteristics compared to the organic light emitting devices of Comparative Examples 1 to 5.

Example 6 to 8: Preparation of organic light emitting diodes

After patterning so that the light emitting area of the ITO glass has a size of 2 mm × 2 mm, it was washed. After mounting the substrate in a vacuum chamber and making the base pressure 1 × 10 ^-6 torr, the organic material was placed on the ITO with HATCN (50Å), NPD (650Å), Blue (Blue) Host (BH) + Blue (Blue) plate A light emitting layer having a thickness of 200 Å was formed by doping with 5% of BD (BD). Compounds 67-89 according to the present invention: Liq = 1:1 (300 Å), Liq (10 Å), Al (1,000 Å) was formed into a film in the order, and the measurement was performed at 0.4 mA. The structures of [HATCN], [NPD], [BD], [BH], and [Liq] are as follows.

[HATCN] [NPD] [BD]

[BH] [Liq]

comparative example 6

The organic light emitting diode device for Comparative Example 6 was manufactured in the same way except that ET, which is generally used as an electron transport layer material, was used instead of the compound prepared by the invention in the device structure of the above embodiment, and the structure of the ET is as follows .

[ET]

For the organic electroluminescent devices manufactured according to Examples 6 to 8 and Comparative Example 6, voltage, current, luminance, color coordinates and lifetime were measured, and the results are shown in Table 2 below. T95 means the time it takes for the luminance to decrease to 95% compared to the initial luminance (2000 cd/m 2 ).

division ETL V Cd/A CIEx CIEy T ₉₅ (Hrs) Comparative Example 6 ET 4.3 6.5 0.133 0.129 10 Example 6 compound 67 3.6 8.1 0.132 0.130 34 Example 7 compound 69 3.8 8.3 0.133 0.128 33 Example 8 compound 89 3.7 8.4 0.132 0.126 29

As shown in [Table 2], the organic compound secured by the present invention has higher efficiency, lower driving voltage and longer life than ET, which is widely used as an electron transport layer material.

Example 9 to 11: Organic Manufacturing of light emitting diodes

After patterning so that the light emitting area of the ITO glass has a size of 2 mm × 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was 1 × 10 ^-6 torr, and then the organic material was placed on the ITO with HATCN (50 Å), the compounds 105 to 107 (650 Å) according to the present invention, blue (Blue) host (BH) + blue dopant (GD) 5% doping to form a 200 Å thick light emitting layer. ET: Liq = 1:1 (300 Å), Liq (10 Å), Al (1,000 Å) was formed in the order of the film was formed, and the measurement was performed at 0.4 mA. The structures of [HATCN], [NPD], [BD], [BH], and [Liq] are as follows.

[HATCN] [ET] [BD]

[BH] [Liq]

comparative example 7

The organic light emitting diode device for Comparative Example 7 was manufactured in the same manner except that NPD, which is generally used as a hole transport layer material, was used instead of the compound prepared by the invention in the device structure of the above embodiment, and the structure of the NPD is as follows. .

[NPD]

For the organic electroluminescent devices manufactured according to Examples 9 to 11 and Comparative Example 7, voltage, current, luminance, color coordinates and lifetime were measured, and the results are shown in Table 3 below. T95 means the time it takes for the luminance to decrease to 95% compared to the initial luminance (2000 cd/m 2 ).

division HTL V Cd/A CIEx CIEy T ₉₅ (Hrs) Comparative Example 7 NPD 4.3 6.5 0.133 0.129 10 Example 9 compound 105 3.7 8.2 0.132 0.129 31 Example 10 compound 106 3.7 8.2 0.133 0.128 30 Example 11 compound 107 3.9 8.1 0.131 0.127 32

As shown in [Table 3], the organic compound secured by the present invention has higher efficiency, lower driving voltage, and longer lifespan than NPD, which is widely used as a hole transport layer material.

Claims (17)

The organic light emitting compound represented by the following [Formula 1]:
[Formula 1]

In the above [Formula 1],
X is CR', at least one of a plurality of R' is represented by A,
L is a linking group, a single bond or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, a substituted or unsubstituted C 2 to C 60 alkynylene group, substituted or an unsubstituted C 3 to C 60 cycloalkylene group, a substituted or unsubstituted C 2 to C 60 heterocycloalkylene group, a substituted or unsubstituted C 6 to C 60 arylene group, and a substituted or unsubstituted C 2 to C 60 Any one selected from the heteroarylene group of
n is an integer from 0 to 3, a plurality of L may be the same or different from each other,
Ar is hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl or heteroalkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted C 2 to C 30 heteroaryl group selected from which one,
R′ and R ₁ to R ₉ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms , a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C5 to 30 arylamine group, substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, substituted or unsubstituted silyl group , substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group, phosphoryl group, amino group, nitrile group, hydroxyl group, nitro group, halogen group, selenium group, tellurium group, Any one selected from the group consisting of an amide group and an ester group,
m is an integer from 0 to 2. According to claim 1,
The L, Ar, R' and R ₁ to R ₉ may each independently be further substituted with one or more substituents, and the one or more substituents may be deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, and 1 to carbon atoms. 24 alkyl group, C1-C24 halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C7-C24 Arylalkyl group, C2-C24 heteroaryl group or C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C6-C24 arylamino group, C1-C24 An organic light emitting compound, characterized in that it is selected from the group consisting of a heteroarylamino group, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms. The method of claim 1,
The organic light emitting compound represented by the [Formula 1] is an organic light emitting compound, characterized in that any one selected from the group represented by the following compounds:

a first electrode; a second electrode opposite the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by [Formula 1] according to claim 1 . 5. The method of claim 4,
The organic layer includes a light emitting layer, a hole transport layer between the light emitting layer and the first electrode, and an electron transport layer between the light emitting layer and the second electrode,
An organic light emitting device comprising a compound represented by the [Formula 1] in the electron transport layer or the hole transport layer. 5. The method of claim 4,
The organic light emitting device further comprises one or more light emitting layers emitting blue, red, or green light to emit white light. Illumination comprising the organic light emitting device according to claim 4. A display device comprising the organic light emitting device according to claim 4 . a first electrode; a second electrode opposite the first electrode; and an organic layer interposed between the first electrode and the second electrode,
The organic layer includes an emission layer, a hole transport layer between the emission layer and the first electrode, and an electron transport layer between the emission layer and the second electrode,
The organic layer is an organic light emitting device comprising (a) a first compound represented by [Formula 1] according to claim 1 and (b) a second compound represented by the following [Formula 2]:
[Formula 2]

In the above [Formula 2],
L ₁ is a linking group, a single bond or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, a substituted or unsubstituted C 2 to C 60 alkynylene group, A substituted or unsubstituted C 3 to C 60 cycloalkylene group, a substituted or unsubstituted C 2 to C 60 heterocycloalkylene group, a substituted or unsubstituted C 6 to C 60 arylene group, and a substituted or unsubstituted C 2 to C 2 to Any one selected from the heteroarylene group of 60,
n ₁ is an integer of 0 to 3, a plurality of L ₁ may be the same or different from each other,
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group or heteroalkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted Any one selected from a cyclic heteroaryl group having 2 to 30 carbon atoms. 10. The method of claim 9,
The L ₁ , Ar ₁ and Ar ₂ may each independently be further substituted with one or more substituents, wherein the one or more substituents are deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, A halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms. A heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, An organic light emitting device, characterized in that it is selected from the group consisting of an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms. 11. The method of claim 10,
The L ₁ , Ar ₁ , Ar ₂ and substituents thereof combine with adjacent substituents to form a saturated or unsaturated ring. 10. The method of claim 9,
The light emitting layer is an organic light emitting device, characterized in that it comprises a phosphorescent dopant compound. 13. The method of claim 12,
The mixing weight ratio of the first compound, the second compound, and the phosphorescent dopant compound is 1: 0.01 to 99: an organic light emitting device, characterized in that 0.01 to 15. 10. The method of claim 9,
The organic light emitting compound represented by the [Formula 2] is an organic light emitting device, characterized in that any one selected from the group represented by the following [Compound 117] to [Compound 136]:

10. The method of claim 9,
The organic light emitting device further comprises one or more light emitting layers emitting blue, red, or green light to emit white light. 10. Illumination comprising the organic light emitting device according to claim 9. A display device comprising the organic light emitting diode according to claim 9 .