KR102261104B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

[화학식 1-B]

The present invention relates to an organic light emitting compound represented by the following [Formula 1-A] to [Formula 1-B] and an organic electroluminescent device comprising the same, wherein the organic light emitting compound according to the present invention has luminous efficiency and material lifespan characteristics Due to this excellent luminous efficiency, an organic electroluminescent device having power efficiency and long lifespan characteristics can be manufactured at the same time.
[Formula 1-A]

[Formula 1-B]

Description

An electroluminescent compound and an electroluminescent device comprising the same

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

Recently, organic light emitting diodes that are self-luminous and can be driven at a low voltage have superior viewing angle and contrast ratio compared to liquid crystal displays, which are the main types of flat panel display devices, do not require a backlight, are lightweight and thin, and are advantageous in terms of power consumption and color reproduction. It has a wide range and is attracting attention as a next-generation display device.

The organic electroluminescent device is a device that emits light while electrons and holes are paired and then extinguished when electric charges are injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode).

The organic electroluminescent device can be formed on a transparent substrate that can be bent like plastic, and can be driven at a lower voltage of 10 V or less compared to a plasma display panel or an inorganic electroluminescent display, and consumes relatively little power. , the color is excellent. In addition, since the organic electroluminescent device can display three colors of green, blue, and red, it is receiving much attention as a next-generation rich color display device.

The most important factor determining the luminous efficiency in an organic light emitting device is the light emitting material. Fluorescent materials are currently widely used as light-emitting materials, but development of phosphorescent materials is one of the theoretical ways to further improve light-emitting efficiency due to the light-emitting mechanism, and accordingly, various phosphorescent materials have been developed so far. In particular, as a phosphorescent host material, CBP is the most widely known until now, and an organic electroluminescent device using a BAlq derivative as a host is known.

However, an organic electroluminescent device using a phosphorescent material has significantly higher current efficiency than a device using a fluorescent material. However, when a material such as BAlq or CBP is used as a host of the phosphorescent material, it is driven compared to a device using a fluorescent material. Since the voltage is high, there is no great advantage in terms of power efficiency, and also the lifespan of the device does not reach a satisfactory level, so the development of a more stable and high-performance host material is required.

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 improved luminous efficiency and improved power efficiency and long lifespan while at the same time superior in luminous efficiency than conventional materials.

In addition, the present invention is to provide an organic electroluminescent device with high efficiency and long life by employing the organic light emitting compound as a light emitting material.

The present invention provides an organic light emitting compound represented by the following [Formula 1-A] to [Formula 1-B] in order to solve the above problems, and the organic light emitting compound comprises at least one organic light emitting compound It provides an organic thin film layer for an organic light emitting device, characterized in that.

[Formula 1-A]

[Formula 1-B]

Definitions for each substituent or skeletal atom will be described later.

In addition, the present invention provides an organic thin film layer for an organic electroluminescent device comprising at least one organic electroluminescent compound embodied by the above [Formula 1-A] to [Formula 1-B], and an organic electroluminescent device including the same do.

The organic light emitting compound according to the present invention has excellent luminous efficiency and material lifespan characteristics, so that an organic electroluminescent device having excellent luminous efficiency and power efficiency and long lifespan characteristics can be manufactured.

1 is a schematic diagram of an organic electroluminescent device according to an embodiment of the present invention.

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-A] to [Formula 1-B].

[Formula 1-A]

[Formula 1-B]

In the [Formula 1-A] to [Formula 1-B],

L ₁ and L ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted C 2 to C 30 It may be selected from the group consisting of a heteroaryl group, and preferably each independently a substituted or unsubstituted C2-30 heteroaryl group containing at least one nitrogen.

Y _{1 To} Y ₃ are each independently a single bond, a substituted or unsubstituted C 1 to C 30 alkylene group, a substituted or unsubstituted C 2 to C 30 alkenylene group, or a substituted or unsubstituted C 2 to C 30 alkylene group It is a linking group selected from a nylene group, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, and p , q and r are integers from 0 to 5, and when p, q and r are 2 or more, a plurality of Y ₁ to Y ₃ may be the same or different from each other.

Z is a single bond or CR ₁ R ₂ , O, S, SiR ₃ R ₄ and NR ₅ any one selected from, wherein R ₁ to R ₅ are hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted C 2 to 30 heteroaryl groups, and may be combined with each other or adjacent substituents to form a saturated or unsaturated ring.

X ₁ to X ₂₆ are the same as or different from each other and each independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, a nitro group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, Phosphoric acid or a salt thereof, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 5 to C 60 aryl group, a substituted or unsubstituted C 3 to 60 heteroaryl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 5 to C 30 aryloxy group, substituted or unsubstituted C 1 to C 30 alkylamino group, substituted or unsubstituted A substituted or unsubstituted C5 to C30 arylamino group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C5 to C30 arylsilyl group, or a substituted or unsubstituted C1 to C30 arylalkyl group An amino group, a substituted or unsubstituted C5 to C60 arylthio group, a substituted or unsubstituted C2 to C60 alkenyl group, and a substituted or unsubstituted C2 to C60 alkynyl group, wherein X ₁ to X ₁₄ may be combined with each other with adjacent substituents to form a saturated or unsaturated ring, and n is an integer of 1 to 3.

In addition, in the [Formula 1-A] to [Formula 1-B], when L ₁ and L ₂ , Y ₁ , Y ₂ , Y ₃ , R ₁ to R ₅ and X ₁ to X ₂₆ are further substituted An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, a heteroaryl group having 3 to 50 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms. An alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to 50 arylalkylamino group, substituted or unsubstituted C2 to C50 alkenyl group, substituted or unsubstituted C2 to C50 alkynyl group, hydroxyl group, nitro group, amidino group, hydrazine, hydrazone, carboxyl group It may be substituted with one or more substituents selected from a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a cyano group, a halogen group, and deuterium; One or more substituents may combine with adjacent substituents to form saturated or unsaturated rings.

According to a preferred embodiment of the present invention, Y ₁ to Y ₃ may be any one selected from the following [Structural Formula C1] to [Structural Formula C14].

[Formula C1] [Formula C2] [Formula C3] [Formula C4]

[Structural formula C5] [Structural formula C6] [Structural formula C7] [Structural formula C8] [Structural formula C9]

In the [Structural Formula C1] to [Structural Formula C14], hydrogen or deuterium may be bonded to the carbon position of the ring in each structural formula, and R is X _{1 in [Formula 1-A] to [Formula 1-B]} to X ₂₆ .

According to a preferred embodiment of the present invention, _{L 1} and L ₂ connected to _{Y 1} and Y ₂ may be any one selected from the following [Structural Formula 1] to [Structural Formula 10]. In addition, the heteroaryl group included in the organic light emitting compound according to the present invention may be any one selected from the following [Formula 1] to [Formula 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 [Formula 1] to [Formula 10], T ₁ to T ₁₂ are the same as or different from each other, and each independently C(R ₄₁ ), C(R ₄₂ )(R ₄₃ ), N, N(R _{44 )} ), O and S, wherein R ₄₁ to R ₄₄ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 of a cycloalkyl group, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms which is substituted or unsubstituted and has O, N, S or P as a hetero atom.

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

[Structural Formula 11]

In the [Structural Formula 11], X is hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C5-C30 aryl group, or a substituted or unsubstituted C2-C30 alkenyl group , a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C30 of an alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthiooxy group, a substituted or unsubstituted an alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms which is substituted or unsubstituted and has O, N, S or P as a heteroatom, a cyano group , a nitro group and a halogen group, m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs are the same as or different from each other.

On the other hand, the aryl group included in the organic light emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members. In addition, when the aryl group has a substituent, it may be fused with a neighboring substituent to further form a ring.

Specific examples of the aryl group include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 4-methylbiphenyl group, 4 -Ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, and aromatic groups such as pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like.

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"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, A halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 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 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms. It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

Specific examples of the alkyl group as a substituent 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, etc., and at least one hydrogen atom of the alkyl group is a deuterium atom, a halogen atom, a hydroxyl 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), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms 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 as a substituent 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, etc. and may be substituted with the same substituents as in the case of the alkyl group.

Specific examples of the halogen group as a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br), and the like.

The aryloxy group as a substituent used in the present invention means an -O- aryl radical, wherein the aryl group is as defined above, and specific examples thereof include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyl. oxy, 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 as a substituent used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethyl furylsilyl and the like.

Specific examples of the alkenyl group used in the present invention include a linear or branched alkenyl group, 3-pentenyl group, 4-hexenyl group, 5-heptenyl group, 4-methyl-3-pentenyl group, 2,4 -Dimethyl-pentenyl group, 6-methyl-5-heptenyl group, 2,6-dimethyl-5-heptenyl group, etc. are mentioned.

According to a preferred embodiment of the present invention, the [Formula 1-A] to [Formula 1-B] may be selected from compounds represented by the following [Formula 2] to [Formula 169].

[Formula 2] [Formula 3] [Formula 4] [Formula 5]

[Formula 6] [Formula 7] [Formula 8] [Formula 9]

[Formula 10] [Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16] [Formula 17]

[Formula 18] [Formula 19] [Formula 20] [Formula 21]

[Formula 22] [Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28] [Formula 29]

[Formula 30] [Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40] [Formula 41]

[Formula 42] [Formula 43] [Formula 44] [Formula 45]

[Formula 46] [Formula 47] [Formula 48] [Formula 49]

[Formula 50] [Formula 51] [Formula 52] [Formula 53]

[Formula 54] [Formula 55] [Formula 56] [Formula 57]

[Formula 58] [Formula 59] [Formula 60] [Formula 61]

[Formula 62] [Formula 63] [Formula 64] [Formula 65]

[Formula 66] [Formula 67] [Formula 68] [Formula 69]

[Formula 70] [Formula 71] [Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76] [Formula 77]

[Formula 78] [Formula 79] [Formula 80] [Formula 81]

[Formula 82] [Formula 83] [Formula 84] [Formula 85]

[Formula 86] [Formula 87] [Formula 88] [Formula 89]

[Formula 90] [Formula 91] [Formula 92] [Formula 93]

[Formula 94] [Formula 95] [Formula 96] [Formula 97]

[Formula 98] [Formula 99] [Formula 100] [Formula 101]

[Formula 102] [Formula 103] [Formula 104] [Formula 105]

[Formula 106] [Formula 107] [Formula 108] [Formula 109]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

[Formula 114] [Formula 115] [Formula 116] [Formula 117]

[Formula 118] [Formula 119] [Formula 120] [Formula 121]

[Formula 122] [Formula 123] [Formula 124] [Formula 125]

[Formula 126] [Formula 127] [Formula 128] [Formula 129]

[Formula 130] [Formula 131] [Formula 132] [Formula 133]

[Formula 134] [Formula 135] [Formula 136] [Formula 137]

[Formula 138] [Formula 139] [Formula 140] [Formula 141]

[Formula 142] [Formula 143] [Formula 144] [Formula 145]

[Formula 146] [Formula 147] [Formula 148] [Formula 149]

[Formula 150] [Formula 151] [Formula 152] [Formula 153]

[Formula 154] [Formula 155] [Formula 156] [Formula 157]

[Formula 158] [Formula 159] [Formula 160] [Formula 161]

[Formula 162] [Formula 163] [Formula 164] [Formula 165]

[Formula 166] [Formula 167] [Formula 168] [Formula 169]

Another aspect of the present invention relates to an organic thin film layer for an organic light emitting device, characterized in that it contains at least one compound according to [Formula 1-A] to [Formula 1-B] of the present invention.

According to one embodiment of the present invention, the organic thin film layer is characterized in that it further comprises at least one compound represented by the following [Formula A-1] to [Formula J-1].

[General Formula A-1]

ML ₁ L ₂ L ₃

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 include 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 [Structural Formula D],

Wherein R are different or the same as each other and are each independently hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 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 with alkylene or alkenylene to form a spiro ring or a fused ring.

As a specific 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 , Q ^A12 represents 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 A partial structure containing an atom bonded to M ^{B1 is shown.}

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 connected to each other to form a 5-membered ring, and a substituent without anything connecting 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 may be linked to each other to form a ring, 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 from each other.

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 from 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 [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 rings of Rings A to D may have a substituent, and the other two rings are aryl rings or heterocycles 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 represent a nitrogen atom in which any two of them are 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 above [general formula J-1], it is preferable that M is 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.

In addition, the organic thin film layer may further include various host compounds and various dopant compounds in addition to the organic electroluminescent compound and the dopant compound according to the present invention.

Another aspect of the present invention relates to an organic electroluminescent device including the organic thin film layer, wherein at least one organic thin film layer including a light emitting layer is sandwiched between the cathode and the anode of the organic electroluminescent device, and at least one layer of the organic thin film layer The organic light emitting compound of [Formula 1-A] to [Formula 1-B] according to the present invention is included alone or as a component of a mixture, and may further include the dopant compound exemplified above.

The organic electroluminescent device according to the present invention may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer in addition to the light emitting layer, and in the present invention In addition to the light emitting layer, the organic light emitting compound may be used for a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

As a specific example, a hole transport layer (HTL, Hole Transport Layer) is additionally laminated, and an electron transport layer (ETL, Electron Transport Layer) is additionally laminated between the cathode and the organic light emitting layer, the hole transport layer Silver is laminated to facilitate injection of holes from the anode, and electron-donating molecules having a small ionization potential are used as the material of the hole transport layer. Diamine, triamine or tetraamine derivatives having triphenylamine as a basic skeleton are mainly used. It is used a lot.

In the present invention, 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'-diphenyl benzidine (α-NPD), etc. can be used.

A hole injection layer (HIL, Hole Injecting Layer) may be additionally stacked on the lower portion of the hole transport layer, and the hole injection layer material is also not particularly limited as long as it is commonly used in the art, and may be used, for example, For example, CuPc (copper phthalocyanine) or Starburst-type amines TCTA (4,4',4"-tri(N-carbazolyl)triphenyl-amine), m-MTDATA(4,4',4"-tris- (3-methylphenylphenylamino)triphenylamine) and the like can be used.

In addition, the electron transport layer used in the organic light emitting device according to the present invention smoothly transports electrons supplied from the cathode to the organic light emitting layer and suppresses the movement of holes that are not coupled in the organic light emitting layer, thereby recombination in the light emitting layer Opportunity to recombine serves to increase

The electron transport layer material is not particularly limited as long as it is commonly used in the art, and of course, may be used, for example, PBD, BMD, BND or Alq3 which is an oxadiazole derivative may be used.

On the other hand, an electron injection layer (EIL) that facilitates electron injection from the cathode and ultimately improves power efficiency may be further laminated on the electron transport layer, the electron injection layer material Also, as long as it is conventionally used in the art, it may be used without particular limitation, for example, a material such as LiF, NaCl, CsF, Li2O, BaO, etc. may be used.

The organic electroluminescent device according to the present invention may be used in a display device, a display device, and a device for monochromatic or white lighting.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, a hole injection layer 30 and The electron injection layer 70 may be further included, and in addition to that, it is possible to further form an intermediate layer of one or two layers, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, an organic electroluminescent device and a manufacturing method thereof of the present invention will be described as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10 . Here, as the substrate 10, a substrate used in a conventional organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties is preferable. In addition, as the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

A hole injection layer 30 is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30 .

Subsequently, an organic light emitting layer 50 is laminated on the hole transport layer 40 and a hole blocking layer (not shown) is selectively deposited on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film. can do. 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 it should have an ionization potential higher than that of a light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, etc. may be used.

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a metal for forming a cathode is vacuum-heated on the electron injection layer 70 . By vapor deposition to form the cathode 80 electrode, the organic EL device is completed. 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.

In addition, according to another embodiment of the present invention, 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 is a single molecule deposition method or solution process. The organic light emitting diode according to the present invention may be used in a display device, a display device, and a device for monochromatic or white lighting.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, the scope of the present invention is not limited thereby, and it is common in the art that various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those with knowledge.

<Example 1> Synthesis of the compound represented by [Formula 3]

(1) Synthesis of the compound represented by [Formula 1-a]

The compound represented by [Formula 1-a] was synthesized by the following [Scheme 1].

[Scheme 1]

[Formula 1-a]

20.0 g (102 mmol) of 5-bromoindole and 6.1 g (153 mmol) of 60% sodium hydride were placed in 200 mL of dimethylformamide and stirred at room temperature for 30 minutes. Then, 43.8 g (122.4 mmol) of chlorodiphenyltriazine was dissolved in 300 mL of dimethylformamide and slowly added dropwise, followed by stirring for 1 hour. When the reaction was completed, 250 mL of distilled water was added, filtered and recrystallized to obtain 35.0 g of a compound represented by [Formula 1-a]. (yield 80%)

(2) Synthesis of the compound represented by [Formula 1-b]

The compound represented by [Formula 1-b] was synthesized by the following [Scheme 2].

[Scheme 2]

[Formula 1-b]

Indole 50.0 g (426.8 mmol), 1-bromo-3-iodobenzene 181.1 g (640.2 mmol), copper powder 63.5 g (853.6 mmol), 18-crown-6 22.6 g (83.4 mmol), potassium carbonate 176.9 g (1280.4 mmol) was added in this order, and 500 mL of 1,2-dichlorobenzene was added, followed by refluxing and stirring at 180 °C for 1 day. When the reaction was completed, the solution was concentrated after high-temperature filter and separated by column chromatography with hexane alone to obtain 48 g of a compound represented by [Formula 1-b]. (Yield 41%)

(3) Synthesis of the compound represented by [Formula 1-c]

A compound represented by [Formula 1-c] was synthesized by the following [Scheme 3].

[Scheme 3]

[Formula 1-c]

After dissolving 48.0 g (176.4 mmol) of the compound represented by [Formula 1-b] obtained from [Reaction Scheme 2] in 480 mL of tetrahydrofuran under a nitrogen stream, while stirring at -78 ° C., 132 mL of 1.6 M n-butyllithium ( 211.6 mmol) was slowly added dropwise, and when the addition was completed, the mixture was stirred for 1 hour while maintaining -78 °C. After that, 25.7 g (246.9 mmol) of trimethyl borate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. When the reaction is complete, 200 mL of 1 M aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. After that, extraction was performed with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized from methylene chloride and hexane to obtain 25.2 g of a compound represented by [Formula 1-c]. (yield 60%)

(4) Synthesis of the compound represented by [Formula 3]

A compound represented by [Formula 3] was synthesized by the following [Scheme 4].

[Scheme 4]

[Formula 3]

10.0 g (23.4 mmol) of the compound represented by [Formula 1-a] obtained from [Scheme 1], 8.3 g (35.1 mmol) of the compound represented by [Formula 1-c] obtained from [Scheme 3], tetrakis ( 540 mg (0.5 mmol) of triphenylphosphine) palladium, 6.5 g (46.8 mmol) of potassium carbonate, 50 mL of 1,4-dioxane, 50 mL of toluene, and 20 mL of distilled water, and stirred at 100° C. for 12 hours. When the reaction is completed, extraction is performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and acetone to obtain 6.3 g of a compound represented by [Formula 3]. (Yield 50%)

MS [M] ⁺ : 539.21

<Example 2> Synthesis of the compound represented by [Formula 7]

(1) Synthesis of the compound represented by [Formula 2-a]

The compound represented by [Formula 2-a] was synthesized by the following [Scheme 5].

[Scheme 5]

[Formula 2-a]

Carbazole 20.0 g (119.6 mmol), 1-bromo-3-iodobenzene 50.8 g (179.4 mmol), copper powder 15.2 g (239.2 mmol), 18-crown-6 6.3 g (23.9 mmol), potassium carbonate 49.6 g (358.8 mmol) was added in this order, and 200 mL of 1,2-dichlorobenzene was added thereto, followed by refluxing and stirring at 180° C. for 1 day. After the reaction was completed, the solution was concentrated after high-temperature filter and separated by column chromatography with hexane alone to obtain 25.1 g of a compound represented by [Formula 2-a]. (Yield 65%)

(2) Synthesis of the compound represented by [Formula 2-b]

The compound represented by [Formula 2-b] was synthesized by the following [Scheme 6].

[Scheme 6]

[Formula 2-b]

After dissolving 25.1 g (77.9 mmol) of the compound represented by [Formula 2-a] obtained from [Scheme 5] in 250 mL of tetrahydrofuran under a nitrogen stream, while stirring at -78 ° C., 1.6 M n-butyllithium 58.4 mL ( 93.5 mmol) was slowly added dropwise, and when the addition was completed, the mixture was stirred for 1 hour while maintaining -78 °C. After that, 11.3 g (109.1 mmol) of trimethyl borate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. When the reaction is complete, 100 mL of 1 M aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. After that, extraction was performed with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized from methylene chloride and hexane to obtain 13 g of a compound represented by [Formula 2-b]. (yield 58%)

(3) Synthesis of the compound represented by [Formula 7]

The compound represented by [Formula 7] was synthesized by the following [Scheme 7].

[Scheme 7]

[Formula 7]

10.0 g (23.4 mmol) of the compound represented by [Formula 1-a] obtained from [Scheme 1], 10.1 g (35.1 mmol) of the compound represented by [Formula 2-b] obtained from [Scheme 6], tetrakis ( 540 mg (0.5 mmol) of triphenylphosphine) palladium, 6.5 g (46.8 mmol) of potassium carbonate, 50 mL of 1,4-dioxane, 50 mL of toluene, and 20 mL of distilled water, and stirred at 100° C. for 12 hours. When the reaction is completed, extraction is performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and acetone to obtain 7.2 g of a compound represented by [Formula 7]. (Yield 52%)

MS [M] ⁺ : 589.23

<Example 3> Synthesis of the compound represented by [Formula 12]

(1) Synthesis of the compound represented by [Formula 3-a]

A compound represented by [Formula 3-a] was synthesized by the following [Scheme 8].

[Scheme 8]

[Formula 3-a]

1-iodobenzene 100.0 g (490.2 mmol), 2-amino-benzoic acid methyl ester 88.9 g (588.2 mmol), tris(dibenzylideneacetone)dipalladium 9.0 g (9.8 mmol), 1,1'-bis(di 5.4 g (9.8 mmol) of phenylphosphino) ferrocene, 70.7 g (735.3 mmol) of sodium tertiary butoxide and 1000 mL of toluene were added, followed by refluxing and stirring for 24 hours. When the reaction is completed, the temperature is adjusted to room temperature and extracted with water and ethyl acetate. The organic layer was dried, concentrated under reduced pressure, and separated by column chromatography to obtain 72.4 g of a compound represented by [Formula 3-a]. (Yield 65%)

(2) Synthesis of the compound represented by [Formula 3-b]

The compound represented by [Formula 3-b] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 3-b]

72.4 g (318.6 mmol) of the compound represented by [Formula 3-a] obtained from [Scheme 8] was dissolved in 550 mL of tetrahydrofuran, and then lowered to 0 °C. 320 mL (955.7 mmol) of 3 M methylmagnesium bromide was slowly added dropwise, and upon completion of the dropwise addition, the mixture was raised to room temperature and stirred for 12 hours. When the reaction is complete, 300 mL of a 2 M aqueous hydrochloric acid solution is 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 from methylene chloride and nucleic acid to obtain 65.2 g of a compound represented by [Formula 3-b]. (yield 90%)

(3) Synthesis of the compound represented by [Formula 3-c]

A compound represented by [Formula 3-c] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 3-c]

65.2 g (286.8 mmol) of the compound represented by [Formula 3-b] obtained from [Scheme 9] was added to 650 mL of phosphoric acid and stirred for 6 hours. When the reaction was completed, the reaction solution was poured into excess water to form a solid and filtered to obtain 35.0 g of a compound represented by [Formula 3-c]. (yield 58%)

(4) Synthesis of the compound represented by [Formula 3-d]

The compound represented by [Formula 3-d] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 3-d]

35.0 g (167.2 mmol) of the compound represented by [Formula 3-c] obtained from [Scheme 10], 71.0 g (250.8 mmol) of 1-bromo-4-iodobenzene, 21.2 g (334.5 mmol) of copper powder, 18-Crown-6 8.8 g (33.5 mmol) and potassium carbonate 69.3 g (501.7 mmol) were added in this order, and 350 mL of 1,2-dichlorobenzene was added, followed by refluxing and stirring at 180° C. for 1 day. When the reaction was completed, the solution was concentrated after high-temperature filter and separated by column chromatography using hexane alone to obtain 36.0 g of a compound represented by [Formula 3-d]. (yield 59%)

(5) Synthesis of the compound represented by [Formula 3-e]

The compound represented by [Formula 3-e] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 3-e]

After dissolving 36.0 g (68.9 mmol) of the compound represented by [Formula 3-d] obtained from [Reaction Scheme 11] in 250 mL of tetrahydrofuran under a nitrogen stream, while stirring at -78 ° C, 51.7 mL of 1.6 M n-butyllithium ( 82.7 mmol) was slowly added dropwise, and when the addition was completed, the mixture was stirred for 1 hour while maintaining -78 °C. After that, 10.0 g (96.5 mmol) of trimethylborate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. When the reaction is complete, 100 mL of 1 M aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. After that, extraction was performed with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized from methylene chloride and hexane to obtain 15 g of a compound represented by [Formula 3-e]. (Yield 66%)

(6) Synthesis of the compound represented by [Formula 12]

The compound represented by [Formula 12] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 12]

10.0 g (23.4 mmol) of the compound represented by [Formula 1-a] obtained from [Scheme 1], 11.6 g (35.1 mmol) of the compound represented by [Formula 3-e] obtained from [Scheme 12], tetrakis ( 540 mg (0.5 mmol) of triphenylphosphine) palladium, 6.5 g (46.8 mmol) of potassium carbonate, 50 mL of 1,4-dioxane, 50 mL of toluene, and 20 mL of distilled water, and stirred at 100° C. for 12 hours. When the reaction is completed, extraction is performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and acetone to obtain 6.8 g of a compound represented by [Formula 12]. (yield 46%)

MS [M] ⁺ : 631.27

<Example 4> Synthesis of the compound represented by [Formula 26]

(1) Synthesis of the compound represented by [Formula 4-a]

A compound represented by [Formula 4-a] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 4-a]

Chlorodiphenyltriazine 20.0 g (74.7 mmol), 4-bromophenylboronic acid 18.0 g (89.7 mmol), tetrakis (triphenylphosphine) palladium 1.7 g (1.5 mmol), potassium carbonate 20.7 g (149.4 mmol) ), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 50 mL, and stirred at 100 °C for 12 hours. When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 23.2 g of a compound represented by [Formula 4-a]. (yield 80%)

(2) Synthesis of the compound represented by [Formula 4-b]

A compound represented by [Formula 4-b] was synthesized by the following [Scheme 15].

[Scheme 15]

[Formula 4-b]

After dissolving 23.2 g (59.8 mmol) of the compound represented by [Formula 4-a] obtained from [Scheme 14] in 230 mL of tetrahydrofuran under a nitrogen stream, while stirring at -78 ° C, 45 mL of 1.6 M n-butyllithium ( 71.76 mmol) was slowly added dropwise, and when the addition was completed, the mixture was stirred for 1 hour while maintaining -78 °C. Then, 18.2 g (71.76 mmol) of iodine was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. When the reaction is complete, 200 mL of sodium thiosulfate aqueous solution is added dropwise and stirred for 30 minutes. Then, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 23.2 g of a compound represented by [Formula 4-b]. (yield 89%)

(3) Synthesis of the compound represented by [Formula 4-c]

A compound represented by [Formula 4-c] was synthesized by the following [Scheme 16].

[Scheme 16]

[Formula 4-c]

23.2 g (53.2 mmol) of the [Formula 4-b] compound obtained from the [Scheme 15], 15.9 g (63.8 mmol) of 5-bromoindole, 6.8 g (106.4 mmol) of copper powder, 1.4 g of 18-crown-6 ( 5.3 mmol), 14.7 g (106.4 mmol) of potassium carbonate were added in this order, and 230 mL of 1,2-dichlorobenzene was added thereto, followed by refluxing and stirring at 180° C. for 1 day. After the reaction was completed, the solution was concentrated under reduced pressure after high-temperature filter, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 22.5 g of a compound represented by [Formula 4-c]. (Yield 84%)

(4) Synthesis of the compound represented by [Formula 26]

The compound represented by [Formula 26] was synthesized by the following [Scheme 17].

[Scheme 17]

[Formula 26]

10.0 g (19.9 mmol) of the compound represented by [Formula 4-c] obtained from [Scheme 16], 4.0 g (23.4 mmol) of carbazole, 0.4 g (0.4 mmol) of tris(dibenzylideneacetone)dipalladium, 1 ,1`-bis(diphenylphosphino)ferrocene 0.2 g (0.4 mmol), sodium tert-butoxide 2.9 g (29.8 mmol) and toluene 100 mL were added, followed by refluxing and stirring for 24 hours. When the reaction is completed, the temperature is adjusted to room temperature and the resulting solid is filtered. The solid was recrystallized from methylene chloride and acetone to obtain 4.7 g of a compound represented by [Formula 26]. (Yield 65%)

MS [M] ⁺ : 589.23

<Example 5> Synthesis of the compound represented by [Formula 64]

(1) Synthesis of the compound represented by [Formula 5-a]

A compound represented by [Formula 5-a] was synthesized by the following [Scheme 18].

[Scheme 18]

[Formula 5-a]

20.0 g (109.0 mmol) of 2,4,6-trichlorotriazine, 13.2 g (109.0 mmol) of phenylboronic acid and 2.5 g (2.2 mmol) of tetrakis(triphenylphosphine)palladium, 30.1 g (218.0 mmol) of potassium carbonate ) in a mixed solvent of 100 mL of 1,4-dioxane, 100 mL of toluene, and 40 mL of distilled water, stirred for 9 hours, and refluxed. When the reaction is complete, the organic layer after extraction is washed with a saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. After removing the organic solvent by distillation under reduced pressure, it was recrystallized from toluene to obtain 20.7 g of a compound represented by [Formula 5-a]. (Yield 84%)

(2) Synthesis of the compound represented by [Formula 5-b]

A compound represented by [Formula 5-b] was synthesized by the following [Scheme 19].

[Scheme 19]

[Formula 5-b]

20.7 g (91.6 mmol) of the compound represented by [Formula 5-a] obtained from [Scheme 18], (9,9-dimethyl-9H-fluoren-2yl)boronic acid 21.8 g (91.6 mmol) and tetra Kis(triphenylphosphine)palladium 2.1 g (1.8 mmol) and potassium carbonate 25.3 g (183.1 mmol) were placed in a mixed solvent of 100 mL of 1,4-dioxane, 100 mL of toluene, and 40 mL of distilled water, stirred for 12 hours, and refluxed. make it When the reaction is complete, the organic layer after extraction is washed with a saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. After removing the organic solvent by distillation under reduced pressure, it was recrystallized from methylene chloride and hexane to obtain 25.0 g of a compound represented by [Formula 5-b]. (Yield 71%)

(3) Synthesis of the compound represented by [Formula 5-c]

A compound represented by [Formula 5-c] was synthesized by the following [Scheme 20].

[Scheme 20]

[Formula 5-c]

10.7 g (54.6 mmol) of 5-bromoindole and 3.3 g (81.5 mmol) of 60% sodium hydride were placed in 100 mL of dimethylformamide and stirred at room temperature for 30 minutes. After that, 25.0 g (65.5 mmol) of the compound represented by [Formula 5-b] obtained from [Scheme 19] was dissolved in 150 mL of dimethylformamide and slowly added dropwise, followed by stirring for 1 hour. When the reaction was completed, 20 mL of distilled water was added, filtered, and recrystallized to obtain 18.0 g of a compound represented by [Formula 5-c]. (Yield 61%)

(4) Synthesis of the compound represented by [Formula 64]

A compound represented by [Formula 64] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 64]

10.0 g (18.7 mmol) of the compound represented by [Formula 5-c] obtained from [Scheme 20], 4.7 g (22.5 mmol) of the compound represented by [Formula 3-c] obtained from [Scheme 10], Tris ( Dibenzylideneacetone)dipalladium 0.4 g (0.4 mmol), 1,1'-bis(diphenyl phosphino)ferrocene 0.2 g (0.4 mmol), sodium tert-butoxide 2.7 g (28.1 mmol) and 100 mL of toluene After input, reflux and stirring for 24 hours. When the reaction is completed, the temperature is adjusted to room temperature and the resulting solid is filtered. The solid was recrystallized from methylene chloride and acetone to obtain 5.3 g of a compound represented by [Formula 64]. (Yield 42%)

MS [M] ⁺ : 671.30

<Example 6> Synthesis of the compound represented by [Formula 67]

(1) Synthesis of the compound represented by [Formula 6-a]

A compound represented by [Formula 6-a] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 6-a]

20.0 g (88.5 mmol) of the compound represented by [Formula 5-a] obtained from [Scheme 18], 18.8 g (88.5 mmol) of dibenzo[b,d]furan-2-ylboronic acid and tetrakis(triphenyl) Phosphine) palladium 2.1 g (1.8 mmol) and potassium carbonate 24.5 g (177.0 mmol) were put in a mixed solvent of 100 mL of 1,4-dioxane, 100 mL of toluene, and 40 mL of distilled water, stirred for 12 hours, and refluxed. When the reaction is complete, the organic layer after extraction is washed with a saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. After removing the organic solvent by distillation under reduced pressure, it was recrystallized from methylene chloride and hexane to obtain 27.2 g of a compound represented by [Formula 6-a]. (yield 80%)

(2) Synthesis of the compound represented by [Formula 6-b]

The compound represented by [Formula 6-b] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 6-b]

12.4 g (63.3 mmol) of 5-bromoindole and 3.8 g (94.9 mmol) of 60% sodium hydride were placed in 100 mL of dimethylformamide and stirred at room temperature for 30 minutes. After that, 27.2 g (75.9 mmol) of the compound represented by [Formula 6-a] obtained from [Scheme 22] was dissolved in 150 mL of dimethylformamide and slowly added dropwise, followed by stirring for 1 hour. When the reaction was completed, 20 mL of distilled water was added, filtered and recrystallized to obtain 23.5 g of a compound represented by [Formula 6-b]. (yield 72%)

(3) Synthesis of the compound represented by [Formula 67]

The compound represented by [Formula 67] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 67]

10.0 g (19.3 mmol) of the compound represented by [Formula 6-b] obtained from [Scheme 23], 6.6 g (23.2 mmol) of the compound represented by [Formula 2-b] obtained from [Scheme 6], tetrakis 0.5 g (0.4 mmol) of (triphenylphosphine) palladium, 5.3 g (38.7 mmol) of potassium carbonate, 50 mL of 1,4-dioxane, 50 mL of toluene, and 20 mL of distilled water are placed and stirred at 100° C. for 12 hours. When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and acetone to obtain 6.1 g of a compound represented by [Formula 67]. (Yield 46%)

MS [M] ⁺ : 679.24

<Example 7> Synthesis of the compound represented by [Formula 123]

A compound represented by [Formula 123] was synthesized by the following [Scheme 25].

[Scheme 25]

[Formula 123]

Instead of 5-bromobenzene used in [Scheme 1] The compound synthesized by the same method using 6-bromobenzene was synthesized in the same manner using [Formula 1-a] used in [Scheme 7] instead of [Formula 7] to obtain a compound represented by [Formula 123]. (Yield 52%)

MS [M] ⁺ : 589.23

<Example 8> Synthesis of the compound represented by [Formula 134]

(1) Synthesis of the compound represented by [Formula 8-a]

The compound represented by [Formula 8-a] was synthesized by the following [Scheme 26].

[Scheme 26]

[Formula 8-a]

Chlorodiphenyltriazine 20.0 g (74.7 mmol), 4-bromophenylboronic acid 18.0 g (89.7 mmol), tetrakis (triphenylphosphine) palladium 1.7 g (1.5 mmol), potassium carbonate 20.7 g (149.4 mmol) ), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 50 mL, and stirred at 100 °C for 12 hours. When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 20.3 g of a compound represented by [Formula 8-a]. (yield 70%)

(2) Synthesis of the compound represented by [Formula 8-b]

A compound represented by [Formula 8-b] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 8-b]

After dissolving 20.3 g (52.3 mmol) of [Formula 8-a] obtained from [Scheme 26] in 200 mL of tetrahydrofuran under a nitrogen stream, while stirring at -78 ° C., 39.2 mL (62.7 mmol) of 1.6 M n-butyllithium was added. It is slowly added dropwise, and when the dropwise addition is completed, the mixture is stirred for 1 hour while maintaining -78°C. After slowly adding 15.9 g (62.7 mmol) of iodine dropwise, the mixture was raised to room temperature and stirred for 1 hour. When the reaction is complete, 200 mL of sodium thiosulfate aqueous solution is added dropwise and stirred for 30 minutes. Then, extraction was performed with ethyl acetate and water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 21.0 g of a compound represented by [Formula 8-b]. (yield 92%)

(3) Synthesis of the compound represented by [Formula 8-c]

A compound represented by [Formula 8-c] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 8-c]

21.0 g (48.3 mmol) of the compound [Formula 8-b] obtained from [Scheme 27], 9.5 g (48.3 mmol) of 6-bromoindole, 6.1 g (96.5 mmol) of copper powder, 2.6 g of 18-crown-6 ( 9.7 mmol) and potassium carbonate 20.0 g (144.7 mmol) were added in this order, 210 mL of 1,2-dichlorobenzene was added thereto, refluxed at 180° C. for 1 day, and stirred. After the reaction was completed, the solution was concentrated under reduced pressure after high-temperature filter, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 15.1 g of a compound represented by [Formula 8-c]. (Yield 61%)

(4) Synthesis of the compound represented by [Formula 134]

A compound represented by [Formula 134] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 134]

10.0 g (19.9 mmol) of the compound represented by [Formula 8-c] obtained from [Scheme 27], 4.0 g (23.8 mmol) of carbazole, 0.4 g (0.4 mmol) of tris(dibenzylideneacetone)dipalladium, 1 0.2 g (0.4 mmol) of ,1'-bis(diphenylphosphino)ferrocene, 2.9 g (29.8 mmol) of sodium tert-butoxide and 100 mL of toluene were added, followed by refluxing and stirring for 24 hours. When the reaction is completed, the temperature is adjusted to room temperature and the resulting solid is filtered. The solid was recrystallized from methylene chloride and acetone to obtain 4.9 g of a compound represented by [Formula 134]. (Yield 42%)

MS [M] ⁺ : 589.23

<Example 9> Synthesis of the compound represented by [Formula 131]

A compound represented by [Formula 131] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 131]

10.0 g (19.9 mmol) of the compound represented by [Formula 8-c] obtained from [Scheme 27], 2.8 g (23.8 mmol) of indole, 0.4 g (0.4 mmol) of tris(dibenzylideneacetone)dipalladium, 1, 0.2 g (0.4 mmol) of 1'-bis(diphenylphosphino)ferrocene, 2.9 g (29.8 mmol) of sodium tert-butoxide and 100 mL of toluene were added, followed by refluxing and stirring for 24 hours. When the reaction is completed, the temperature is adjusted to room temperature and the resulting solid is filtered. The solid was recrystallized from methylene chloride and acetone to obtain 4.5 g of a compound represented by [Formula 131]. (Yield 38%)

MS [M] ⁺ : 539.21

<Example 10> Synthesis of a compound represented by Formula 135

The compound represented by [Formula 135] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 135]

10.0 g (19.9 mmol) of the compound represented by [Formula 8-c] obtained from [Scheme 27], 4.8 g (23.8 mmol) of the compound represented by [Formula 2-b] obtained from [Scheme 6], tetrakis (triphenylphosphine) palladium 0.5 g (0.4 mmol), potassium carbonate 5.5 g (39.7 mmol), 1,4-dioxane 50 mL, toluene 50 mL, distilled water 20 mL, put in 20 mL and stirred at 100 ℃ for 12 hours. When the reaction is completed, extraction is performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and acetone to obtain 7.2 g of a compound represented by [Formula 135]. (Yield 54%)

MS [M] ⁺ : 665.26

<Example 11> Synthesis of a compound represented by Formula 158

The compound represented by [Formula 11-a] was synthesized by the following [Scheme 31].

[Scheme 31]

[Formula 11-a]

1-nitronaphthalene 97 g (0.56 mol), methyl cyanoacetate 166.5 g (1.68 mol), potassium cyanide 40.1 g (0.62 mol), potassium hydroxide 62.9 g (1.12 mol) were added and stirred. 970 mL of dimethylformamide was added and stirred at 60 °C overnight. After concentration under reduced pressure at room temperature to remove the solvent, 500 mL of a 10% aqueous sodium hydroxide solution was added and refluxed for about 1 hour. After extraction with ethyl acetate and separation by column chromatography, 50.8 g of a compound represented by [Formula 11-a] was obtained by recrystallization from toluene and heptane. (Yield 54%)

(2) Synthesis of the compound represented by [Formula 11-b]

A compound represented by [Formula 11-b] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 11-b]

25.0 g (149 mmol) of [Formula 11-a] obtained from [Reaction Scheme 31] was placed in 200 mL of tetrahydrofuran and stirred. 87.4 mL (297 mmol) of phenyl magnesium bromide (3.0 M in Et ₂ O) was added dropwise, and the mixture was refluxed at 0° C. for about 1 hour. After 19.4 g (179 mmol) of ethyl chloroformate was added dropwise, the mixture was refluxed for about 1 hour. An aqueous solution of ammonium chloride was added until slightly acidic, and washed with water and heptane to obtain 32.4 g of a compound represented by [Formula 11-b]. (yield 80%)

(3) Synthesis of the compound represented by [Formula 11-c]

A compound represented by [Formula 11-c] was synthesized by the following [Scheme 33].

[Scheme 33]

[Formula 11-c]

30 g (110 mmol) of [Formula 11-b] obtained from [Scheme 32] was placed in about 80 mL of phosphorus oxychloride and refluxed overnight. After cooling the temperature to -20 °C, about 400 mL of distilled water was slowly added. It was washed with water, methanol, and heptane, and recrystallized from toluene and heptane to obtain 14.1 g (yield 44%) of the compound represented by [Formula 11-c].

(4) Synthesis of the compound represented by [Formula 11-d]

The compound represented by [Formula 11-d] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 11-d]

50 mL of dimethylformamide was added to 2.1 g (53 mmol) of 60% sodium hydride, and the mixture was stirred at room temperature for about 30 minutes. 8.0 g (41 mmol) of 5-bromoindole and 100 mL of dimethylformamide were added dropwise, followed by further stirring for about 1 hour. 12.9 g (53 mmol) of [Formula 11-c] obtained from [Scheme 33] and 100 mL of dimethylformamide were added and stirred overnight. 600 mL of distilled water was added to the flask, and the resulting solid was filtered. Recrystallization from toluene gave 13.3 g of a compound represented by [Formula 11-d]. (yield 72%)

(5) Synthesis of the compound represented by [Formula 11-e]

A compound represented by [Formula 11-e] was synthesized by the following [Scheme 35].

[Scheme 35]

[Formula 11-e]

Indole 9.5 g (81.3 mmol), 4-iodophenyl boronic acid 40.3 g (162.5 mmol), copper powder 10.3 g (162.5 mmol), 18-crown-6 4.3 g (16.3 mmol), potassium carbonate 33.7 g (243.9 mmol) ) was added 200 mL of 1,2-dichlorobenzene, and then refluxed at 180 °C for 1 day. After high-temperature filter, it was separated by column chromatography to obtain 16.9 g of a compound represented by [Formula 11-e]. (Yield 88%)

(6) Synthesis of the compound represented by [Formula 158]

A compound represented by [Formula 158] was synthesized by the following [Scheme 36].

[Scheme 36]

[Formula 158]

12.6 g of [Formula 11-d] obtained from [Scheme 34], (28 mmol), 8.1 g (34 mmol) of [Formula 11-e] obtained from [Scheme 35], tetrakis (triphenylphosphine) palladium To 0.7 g (0.64 mmol), 8.9 g (64 mmol) of potassium carbonate, 80 mL of 1,4-dioxane, 80 mL of toluene, and 30 mL of distilled water were added and refluxed overnight. After extraction with ethyl acetate and recrystallization with dichloromethane and acetone, 11.8 g of the compound represented by [Compound 158] was obtained. (yield 75%)

MS [M] ⁺ : 562.22

<Example 12> Synthesis of a compound represented by Formula 166

A compound represented by [Formula 12-a] was synthesized by the following [Scheme 37].

[Scheme 37]

[Formula 12-a]

After filling the dried 2 L reactor with nitrogen, 45.0 g (381 mmol) of 2-aminobenzonitrile and 405 mL of tetrahydrofuran were added, and 279 mL (838 mmol) of 3 M phenylmagnesium bromide was slowly added dropwise at 0°C. Stir at reflux for an hour. After lowering to a low temperature, 62 g (0.571 mmol) of ethylchloroformate was dissolved in 200 mL of tetrahydrofuran, slowly added dropwise, and stirred under reflux for 2 hours. It was separated by column chromatography to obtain 50 g of a compound represented by [Formula 12-a]. (yield 58%)

(2) Synthesis of the compound represented by [Formula 12-b]

The compound represented by [Formula 12-b] was synthesized by the following [Scheme 38].

[Scheme 38]

[Formula 12-b]

50 g (225 mmol) of [Formula 12-a] obtained from [Reaction Scheme 37], 500 mL of phosphorus oxychloride, and stirred under reflux for 5 hours. When the reaction is complete, it is slowly added dropwise to the lowered temperature water. After the dropwise addition was completed, the mixture was filtered, extracted with methylene chloride and water, and separated by column chromatography to obtain 41 g of a compound represented by [Formula 12-b]. (yield 75%)

(3) Synthesis of the compound represented by [Formula 12-c]

A compound represented by [Formula 12-c] was synthesized by the following [Scheme 39].

[Scheme 39]

[Formula 12-c]

60.0 g (413 mmol) of 2,3-dimethylindole was dissolved in 400 mL of dimethylformamide and stirred at 0°C. Then, 73.5 g (413 mmol) of N-bromosuccinimide was dissolved in 200 mL of dimethylformamide and slowly added dropwise to the reaction solution while maintaining 0°C for 1 hour. After the reaction solution was added dropwise, the reaction solution was heated to room temperature and stirred for 12 hours. When the reaction was completed, distilled water was added dropwise at room temperature to form brown crystals. The resulting crystals were filtered and recrystallized from toluene and methanol to obtain 50 g of a compound represented by [Formula 12-c]. (Yield 54%)

(4) Synthesis of the compound represented by [Formula 12-d]

A compound represented by [Formula 12-d] was synthesized by the following [Scheme 40].

[Scheme 40]

[Formula 12-d]

Use [Formula 12-c] obtained from [Scheme 39] instead of 5-bromoindole used in [Scheme 34], and use [Formula 12-b] obtained from [Scheme 38] instead of [Formula 11-c] and synthesized in the same manner to obtain a compound represented by [Formula 12-d]. (yield 77%)

(5) Synthesis of the compound represented by [Formula 12-e]

A compound represented by [Formula 12-e] was synthesized by the following [Scheme 41].

[Scheme 41]

[Formula 12-e]

Using 1-amino-4-bromonaphthalene instead of [Formula 11-d] used in [Scheme 36], and using phenyl boronic acid instead of [Formula 11-e], synthesized in the same way [Formula 12-e] ] was obtained. (Yield 73%)

(6) Synthesis of the compound represented by [Formula 12-f]

A compound represented by [Formula 12-f] was synthesized by the following [Scheme 42].

[Scheme 42]

[Formula 12-f]

17.5 g (0.08 mol) of [Formula 12-e] obtained from [Scheme 41], 22.6 g (0.08 mol) of 2-bromoiodobenzene, 1.1 g (0.1 mmol) of tris(dibenzylideneacetone)dipalladium, 1 0.7 g (0.1 mmol) of ,1'-bis(diphenylphosphino)ferrocene and 15.3 g (0.16 mol) of sodium tert-butoxide were added to 250 mL of toluene and refluxed for 24 hours. It was separated by column chromatography to obtain 14 g of a compound represented by [Formula 12-f]. (Yield 47%)

(7) Synthesis of the compound represented by [Formula 12-g]

A compound represented by [Formula 12-g] was synthesized by the following [Scheme 43].

[Scheme 43]

[Formula 12-g]

14 g (0.04 mol) of [Formula 12-f] obtained from [Scheme 42], 4.0 g (0.04 mol) of potassium acetate, and 0.8 g (0.001 mol) of tetrakistriphenylphosphine palladium were placed in 125 mL of dimethylformamide Stirred at 150 °C for 24 h. It was separated by column chromatography and recrystallized from hexane to obtain 4.2 g of a compound represented by [Formula 12-g]. (Yield 36%)

(8) Synthesis of a compound represented by [Formula 166]

A compound represented by [Formula 166] was synthesized by the following [Scheme 44].

[Scheme 44]

[Compound 166]

Use [Formula 12-d] obtained from [Scheme 40] instead of [Formula 4-b] used in [Scheme 16], and use [Formula 12-g] obtained from [Scheme 43] instead of 5-bromoindole and synthesized in the same manner to obtain a compound represented by [Compound 166]. (Yield 66%)

MS [M] ⁺ : 640.26

Examples 1 to 24: Preparation of organic light emitting diodes

After patterning so that the emission 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 the organic material was placed on the ITO, DNTPD (700 Å), NPD (300 Å), the compound prepared by the present invention + Ir (ppy) _A film was formed in the order of 3 (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å), and measurement was performed at 0.4 mA.

Comparative Example 1

The organic light emitting diode device for the comparative example was manufactured in the same manner except that CBP, which is generally used as a phosphorescent host material, was used instead of the compound prepared by the invention in the device structure of the above embodiment, and the structure of the CBP is as follows.

division host dopant Doping Concentration% V Cd/m2 CIEx CIEy T ₈₀ (Hr) Comparative Example 1 CBP Ir(ppy) ₃ 10 7.9 3800 0.297 0.624 68 Example 1 3 Ir(ppy) ₃ 10 3.9 5120 0.312 0.621 207 Example 2 7 Ir(ppy) ₃ 10 4.0 5110 0.311 0.622 203 Example 3 12 Ir(ppy) ₃ 10 4.1 5290 0.310 0.625 189 Example 4 26 Ir(ppy) ₃ 10 3.8 5180 0.309 0.621 180 Example 5 64 Ir(ppy) ₃ 10 3.9 5310 0.312 0.620 239 Example 6 67 Ir(ppy) ₃ 10 4.1 5200 0.309 0.622 241 Example 7 123 Ir(ppy) ₃ 10 4.3 5230 0.314 0.623 197 Example 8 131 Ir(ppy) ₃ 10 3.8 4900 0.308 0.623 235 Example 9 134 Ir(ppy) ₃ 10 3.5 5210 0.309 0.622 267 Example 10 135 Ir(ppy) ₃ 10 4.2 5270 0.313 0.621 253 Example 11 4 Ir(ppy) ₃ 10 4.1 5130 0.314 0.626 188 Example 12 8 Ir(ppy) ₃ 10 3.7 4820 0.308 0.624 199 Example 13 11 Ir(ppy) ₃ 10 3.6 5200 0.315 0.623 203 Example 14 15 Ir(ppy) ₃ 10 4.0 5120 0.312 0.621 198 Example 15 22 Ir(ppy) ₃ 10 4.2 5230 0.322 0.620 189 Example 16 47 Ir(ppy) ₃ 10 3.8 5020 0.311 0.621 201 Example 17 77 Ir(ppy) ₃ 10 4.0 5130 0.315 0.620 182 Example 18 96 Ir(ppy) ₃ 10 4.3 5090 0.313 0.624 193 Example 19 106 Ir(ppy) ₃ 10 4.1 5050 0.307 0.623 179 Example 20 126 Ir(ppy) ₃ 10 3.7 5100 0.309 0.614 173 Example 21 137 Ir(ppy) ₃ 10 3.9 4870 0.313 0.621 216 Example 22 138 Ir(ppy) ₃ 10 4.4 5120 0.309 0.621 203 Example 23 146 Ir(ppy) ₃ 10 4.1 4970 0.312 0.623 194 Example 24 154 Ir(ppy) ₃ 10 4.3 5030 0.311 0.622 197

Examples 25 to 27: Preparation 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, the base pressure was 1 × 10 ^-6 torr, and the organic material was placed on the ITO with DNTPD (700 Å), α-NPB (300 Å), the compound prepared by the present invention + (piq ) ₂ Ir(acac) (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed into a film in the order, and the measurement was performed at 0.4 mA.

Comparative Example 2

In the organic light emitting diode device for Comparative Example 2, CBP, which is commonly used as a phosphorescent host material, was used instead of the compound prepared by the invention in the device structures of Examples 25 to 28.

division host dopant Voltage (V) Cd/m2 CIEx CIEy T ₉₀ (Hr) Comparative Example 2 CBP (piq) ₂ Ir(acac) 7.5 410 0.667 0.328 410 Example 25 158 (piq) ₂ Ir(acac) 4.1 1320 0.671 0.325 1080 Example 26 159 (piq) ₂ Ir(acac) 4.4 1300 0.674 0.327 1115 Example 27 166 (piq) ₂ Ir(acac) 4.1 1280 0.671 0.327 1075

In [Table 1] and [Table 2], T ₈₀ means the time required for the luminance to be reduced to 80% compared to the initial luminance.

As shown in [Table 1] and [Table 2], when the organic light emitting compound implemented according to the present invention is employed as the host compound for the light emitting layer of the organic light emitting device, the lifespan characteristics are remarkably improved and the light emitting properties are excellent. In addition, by lowering the driving voltage, power consumption can be improved by inducing an increase in power efficiency.

10: substrate 20: anode
30: hole injection layer 40: hole transport layer
50: organic light emitting layer 60: electron transport layer
70: electron injection layer 80: cathode

Claims (13)

An organic light-emitting compound represented by any one of the following [Formula 1-A] to [Formula 1-B]:
[Formula 1-A]

[Formula 1-B]

In the [Formula 1-A] to [Formula 1-B],
L ₁ and L ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted C 2 to C 30 It is selected from the group consisting of a heteroaryl group,
Y _{1 To} Y ₃ are each independently a single bond, a linking group selected from a substituted or unsubstituted C5 to C50 arylene group and a substituted or unsubstituted C2 to C50 heteroarylene group (p, q and r is an integer of 0 to 5, and when p, q and r are 2 or more, a plurality of Y ₁ to Y ₃ are the same or different from each other),
However, in [Formula 1-A], Y ₃ is connected to any one selected from _{X 3} , X ₅ and X _6,
Z is CR ₁ R ₂ or SiR ₃ R ₄ , wherein R ₁ to R ₄ are hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and substituted or an unsubstituted heteroaryl group having 2 to 30 carbon atoms, wherein R ₁ to R ₄ may combine with each other or an adjacent substituent to form a saturated or unsaturated ring,
X ₁ to X ₂₆ are the same as or different from each other and each independently represent hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or an unsubstituted C 5 to C 60 aryl group and a substituted or unsubstituted C 3 to C 60 heteroaryl group,
n is an integer from 1 to 3. According to claim 1,
When L ₁ and L ₂ , Y ₁ , Y ₂ , Y ₃ , R ₁ to R ₄ and X ₁ to X ₂₆ are further substituted, deuterium, a cyano group, a halogen group, an alkyl group having 1 to 30 carbon atoms, 3 to carbon atoms A cycloalkyl group having 30, an aryl group having 6 to 50 carbon atoms, a heteroaryl group having 3 to 50 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, 6 to carbon atoms An organic light emitting compound, characterized in that it is substituted with one or more selected from an arylamino group of 30, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms. delete delete delete delete According to claim 1,
The [Formula 1-A] to [Formula 1-B] are organic light emitting compounds, characterized in that any one selected from compounds represented by the following formula:

[Formula 10] [Formula 11] [Formula 12]

[Formula 14] [Formula 15] [Formula 16]

[Formula 34] [Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40] [Formula 41]

[Formula 42] [Formula 43] [Formula 44] [Formula 45]

[Formula 48] [Formula 49]

[Formula 52] [Formula 53]

[Formula 56] [Formula 57]

[Formula 60] [Formula 61]

[Formula 64] [Formula 65]

[Formula 68] [Formula 69]

[Formula 72] [Formula 73]

[Formula 76] [Formula 77]

[Formula 99]

[Formula 104]

[Formula 118] [Formula 119] [Formula 120] [Formula 121]

[Formula 126] [Formula 127] [Formula 128] [Formula 129]

[Formula 131] [Formula 132] [Formula 133]

[Formula 137]

[Formula 138] [Formula 139] [Formula 141]

[Formula 142] [Formula 144] [Formula 145]

[Formula 147] [Formula 148] [Formula 149]

[Formula 153]

[Formula 161]

[Formula 163]

[Formula 166] [Formula 167] [Chemical Formula 1-A] to [Formula 1-B] according to claim 1, characterized in that it comprises at least one organic light emitting compound represented by any one of the organic thin film layer for an organic light emitting device. 9. The method of claim 8,
The organic thin film layer has an organic light emitting compound represented by any one of [Formula 1-A] to [Formula 1-B] as a host, and further comprises at least one dopant compound. anode; a cathode opposite the anode; and the organic thin film layer according to claim 8 interposed between the anode and the cathode. 11. The method of claim 10,
The organic electroluminescent device further comprises one or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron blocking layer between the anode and the cathode,
An organic electroluminescent device, characterized in that one of the light emitting layer, the hole injection layer, the hole transport layer, the hole blocking layer, the electron transport layer, the electron injection layer and the electron blocking layer is the organic thin film layer according to claim 8. 12. The method of claim 11,
The organic electroluminescent device, characterized in that the light emitting layer is the organic thin film layer according to claim 8. 12. The method of claim 11,
The organic light emitting device comprises at least one organic light emitting layer emitting blue, red, or green light to emit white light.

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