KR20140120090A - An organoelectro luminescent compounds and organoelectro luminescent device using the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by chemical formula A, chemical formula B or chemical formula C; and to an organic electroluminescent device including the organic light emitting compound. According to the present invention, the organic electroluminescent device including the organic light emitting compound has a low driving voltage and excellent luminous efficiency and life characteristics.

Description

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

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

In recent years, organic light emitting devices capable of being driven by a low voltage in a self-emission type are superior in viewing angle and contrast ratio compared to a liquid crystal display, which is a mainstream of a flat panel display device, require no backlight and are lightweight and thin, And has been attracting attention as a next generation display device.

An organic electroluminescent device is a device that injects electric charge into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode) to form an electron and a hole.

The organic electroluminescent device can be formed on a transparent substrate that can be made of plastic and can be driven at a voltage as low as 10 V or less as compared with a plasma display panel or an inorganic electroluminescent display and has a relatively low power consumption , And has an advantage of excellent color. In addition, organic electroluminescent devices are capable of displaying three colors of green, blue, and red, and thus are attracting much attention as next-generation rich color display devices.

The most important factor determining the luminous efficiency in an organic electroluminescent device is a light emitting material. However, the development of a phosphorescent material on a light-emitting mechanism is one of the ways that the luminous efficiency can be improved more theoretically. Accordingly, a variety of phosphorescent materials have been developed to date, Particularly, CBP (4,4'-N, N'-dicarbazolbiphenyl) is the most widely known phosphorescent host material, and materials in which various substituents are introduced into carbazole are disclosed in Japanese Patent Laid-Open Publication No. 2008-214244 2003-133075), or an organic electroluminescent device using a BALq derivative as a host.

However, an organic electroluminescent device using a phosphorescent material has a 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 a phosphorescent material, There is no great advantage in terms of power efficiency due to a high voltage and a satisfactory level in terms of lifetime of a device can not be attained. Therefore, development of a high-performance host material with a more stable driving voltage and lifetime characteristics is required.

An object of the present invention is to provide an organic luminescent compound having a luminescent efficiency higher than that of a conventional material, and at the same time having improved power efficiency and longevity.

The present invention also provides an organic electroluminescent device with high efficiency and long life by employing the organic electroluminescent compound as a light emitting material.

In order to solve the above-described problems, the present invention provides organic luminescent compounds represented by the following formulas (A) to (C).

[Chemical Formula B] [Chemical Formula C]

In addition, the present invention is a light emitting device comprising a first electrode, a second electrode facing the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, The organic electroluminescent device includes at least one organic electroluminescent compound represented by Formula (C).

Specific substituents of the organic luminescent compounds represented by the formulas (A) to (C) according to the present invention will be described later.

When the organic electroluminescent compound according to the present invention is employed in an organic electroluminescent device, it can be driven at a low voltage and has excellent luminance, luminescent efficiency, and lifetime.

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

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

The organic luminescent compound according to the present invention is characterized by being represented by the following formulas (A) to (C).

[Chemical Formula B] [Chemical Formula C]

In the above formulas (A) to (C)

R ₁ to R ₁₄ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C1 to 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 aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Substituted and may be selected from two kinds of atoms O, N or the group consisting of carbon number 2 to 50 having an S-heteroaryl group, a cyano group, a nitro group and a halogen group.

R ₁ to R ₁₄ may be connected to adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring, and the carbon atom of the alicyclic or aromatic monocyclic or polycyclic ring may be N, S , And O. The term " heteroaryl "

Ar ₁ may be selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms .

L is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C2-C6 heteroarylene group. . n is an integer of 1 to 3, and when n is 2 or more, a plurality of Ls may be the same or different from each other.

Y is _{CR 31 R 32, NR 33,} O, S, SiR 34 R 35, GeR 36 R 37, PR 38, PR 39 (= O), C = O and selected from BR _40, wherein R ₃₁ to R ₄₀ Are the same as the definitions of R ₁ to R ₁₄ .

The "- *" of Q is connected to any one of R ₅ and R _{6 ,} R ₆ and R _7, and R ₇ and R ₈ by a single bond to form a fused ring.

[Formula (A)] to [Formula (C)] may be any one selected from compounds represented by the following Formulas D1 to D14 according to the bonding position of Q.

[Chemical formula D1] [Chemical formula D2] [Chemical formula D3]

[Chemical formula D4] [Chemical formula D5]

[Chemical formula D6] [Chemical formula D7]

[Chemical formula D8] [Chemical formula D9]

[Chemical formula D10] [Chemical formula D11]

[Chemical formula D12] [Chemical formula D13] [Chemical formula D14]

The Formula D1] to the [formula D14], R ₁ to _{R 14, Ar 1, L,} n , and Y is as defined in the above [Chemical Formula A] to [Chemical Formula C].

The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl 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, 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 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, And an aryloxy group having 1 to 24 carbon atoms, the substituted R ₁ to R ₄₀ , Ar ₁ and L are each independently substituted with a halogen atom, May be further substituted with the above-mentioned substituents.

The carbon number 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 5 to 50 carbon atoms', etc., Quot; means the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when it is regarded as unsubstituted. For example, a phenyl group substituted with a butyl group at the para position means an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

On the other hand, the aryl group contained 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 is a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms And when a substituent is present in the aryl group, it may be fused with an adjacent substituent to further form a ring.

Specific examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, pyranyl group, An aromatic group such as a phenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a pyrenyl group, a perylene group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group.

The at least one hydrogen atom of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ' , An alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, 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, , A heteroaryl group having 2 to 24 carbon atoms, or a heteroarylalkyl group having 2 to 24 carbon atoms.

On the other hand, the heteroaryl group contained in the organic light emitting compound according to the present invention is a heteroaromatic group having 2 to 24 carbon atoms which may contain 1 to 4 hetero atoms selected from N, O, P or S in each ring in the aryl group Refers to an organic radical, which rings can be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

The heteroaryl group contained in the organic luminescent compound according to the present invention may be any one selected from the following Structural Formulas 1 to 6:

[Structural formula 1] [Structural formula 2] [Structural formula 3]

[Structural formula 4] [Structural formula 5] [Structural formula 6]

In the above Structural Formulas 1 to 6,

T ₁ to T ₈ may be the same or different and each independently selected from C (R ₅₁ ), C (R ₅₂ ) (R ₅₃ ), N, N (R ₅₄ ) .

R ₄₁ to R ₅₄ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom, , R ₄₁ to R ₅₄ Is bonded to any one of R ₁ to R ₁₄ , Ar ₁ , L, Y and substituents thereof in the above formulas (A) to (C) to form a single bond.

In addition, the above-mentioned [formula 3] may include a compound represented by [formula 3-1] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In the above structural formula 3-1, T ₁ to T ₅ and R ₄₃ and R ₄₄ are the same as defined above.

According to one embodiment of the present invention, the above Structural Formulas 1 to 6 can be selected from the following Structural Formula 7.

[Structural Formula 7]

In the above formula 7,

X is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms A substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom having 2 to 5 carbon atoms having O, N or S, 0, 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, the plural Xs are the same or different from each other, and the one or more X is linked with any one of R ₁ to R ₁₄ , Ar ₁ , L, Y and substituents thereof in the above formulas (A) to (C) to form a single bond.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group used as the substituent in the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy and hexyloxy. At least one hydrogen atom of the group may be substituted with the same substituent as in the case of the aryl group.

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

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclobutylsilyl , And dimethylpurylsilyl. At least one hydrogen atom of the silyl group may be substituted with the same substituent as the aryl group.

The aryloxy group 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, fluorenyloxy, Indenyloxy and the like, and at least one hydrogen atom contained in the aryloxy group may be further substituted.

Specific examples of the alkenyl group used in the present invention include straight or branched chain alkenyl groups, and examples thereof include a 3-pentenyl group, a 4-hexenyl group, a 5-heptenyl group, a 4-methyl- Dimethyl-pentenyl group, 6-methyl-5-heptenyl group and 2,6-dimethyl-5-heptenyl group.

When L is a linking group other than a single bond, it may be independently selected from the following formulas [8] to [15].

[Structural formula 8] [Structural formula 9] [Structural formula 10] [Structural formula 11]

[Structural Formula 12] [Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

In the above Structural Formulas 8 to 15, hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each structural formula.

The present invention also provides a light emitting device comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, ] Can be contained in one or more of these organic luminescent compounds.

The organic layer containing the organic luminescent compound of the present invention may include at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, have. At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, and the light emitting layer may be composed of a host and a dopant, and the organic light emitting compound of the present invention may be used as a host.

In the present invention, a dopant material may be used for the light emitting layer in addition to the host. When the light emitting layer includes a host and a dopant, the dopant content may be selected generally in the range of about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host.

In addition, in the present invention, a known electron transport material can be used as the electron transport layer material, which functions to stably transport electrons injected from an electron injection electrode (cathode). Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, [Compound 201], [Compound 202], oxadiazole derivative PBD, BMD, BND and the like may be used.

TAZ BAlq

[Compound 201] [Compound 202] BCP

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

≪ RTI ID = 0.0 &

In the above formula (C)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond.

M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom.

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

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

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

The Y may be the same or different and independently selected from the following formulas [C1] to [C39].

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

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

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

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

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

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

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

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

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

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

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

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

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

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

Hereinafter, an organic electroluminescent device of the present invention will be described with reference to FIG.

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 emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

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

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

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

The hole injection layer material is not particularly limited as long as it is conventionally used in the art. For example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ] Can be used.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- -Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (? -NPD).

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

Wherein as material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq _2, OXD-7, Liq and [Formula 101] to [Chemical Formula 107] either, but one that can be used is selected from, this limited It is not.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(101)

≪ RTI ID = 0.0 >

Formula 107

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

In addition, the light emitting layer may be made of a host and a dopant. According to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM.

At this time, the dopant used in the light emitting layer may be at least one compound selected from the compounds represented by the following general formulas (A-1) to (J-1).

[General Formula A-1]

In the above 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.

L ₁ , L ₂ and L ₃ may be the same or different from each other as ligands, independently of one another, selected from the following Structural Formula D, and "*" in the following Structural Formula D is coordinated to the metal ion M Represents a site.

[Structural formula D]

In the above structural formula D,

R is different from or the same as each other and is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-50 aryl, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And R is independently selected from the group consisting of 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, Which may be further substituted with one or more substituents selected from a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium, and hydrogen, and R may be linked to each adjacent substituent by alkylene or alkenylene, Aromatic ring and a monocyclic or polycyclic aromatic ring.

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

According to one embodiment of the present invention, the dopant represented by the above-mentioned [formula A-1] may be any one selected from the following compounds.

[Formula B-1]

In the above general formula B-1,

M ^A1 represents the same metal ion as defined in the above-mentioned [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 represents a substituted or unsubstituted carbon atoms, a substituted or unsubstituted nitrogen atom, an oxygen atom, a sulfur atom, the L ^A11 , L ^A12 , L ^A13 and L ^A14 each represent a linking group such as L ₁ , L ₂ and L ₃ defined in the above [formula A-1], and Q ^A11 and Q ^A12 represent an atom bonding to M ^A1 . ≪ / RTI >

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula B-1] may be any one selected from the following compounds.

[Formula C-1]

In the above general formula (C-1)

M ^B1 is the represents the same metal ion as defined from the following formula ^{A-1], Y B11,} Y B14, Y B15 and Y ^B18 represents a carbon atom or a nitrogen atom, each independently, Y ^B12, Y ^B13, Y ^B16 and ^YB17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom, L ^B11 , L ^B12 , L ^B13 and L ^B14 represent a linking group, Q ^B11 , Q ^B12 represents a partial structure containing an atom bonding to M ^B1 .

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula C-1] may be any one selected from the following compounds.

[Formula D-1]

In the above general formula (D-1)

M ^C1 represents a metal ion as defined in the above-mentioned [formula A-1], R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent which is mutually connected to form a 5-membered ring, , R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent which is mutually connected to form a 5-membered ring or a substituent which is not connected to each other, R ^C13 and R ^C14 each independently represent a hydrogen atom, G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, Q ^C11 and Q ^C12 Represents a partial structure containing an atom bonding to M ^C1 .

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula D-1] may be any one selected from the following compounds.

[Formula E-1]

In the above general formula E-1,

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

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula E-1] may be any one selected from the following compounds.

[Formula F-1]

In the above general formula F-1,

M ^E1 is above represents the same metal ion as defined from the following formula ^{A-1], J E11,} J E12 represents a group of atoms necessary haneundedo form a 5-membered ring, each ^{independently, G E11, G E12, G} E13 and G ^E14 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom.

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula F-1] may be any one selected from the following compounds.

[Formula G-1]

In the above general formula G-1,

M ^F1 is above represents the same metal ion as defined from the following formula ^{A-1], L F11,} L F12 and L ^F13 represents a linking group, R ^F11, R ^F12, R ^F13 and R ^F14 represents a substituent, R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be connected to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. And Q ^F11 and Q ^F12 represent a partial structure containing an atom bonding to M ^F1 .

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula G-1] may be any one selected from the following compounds.

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

In the above general formula H-1,

R ¹¹ and R ¹² are an alkyl group, an aryl group, or a heteroaryl group, which may form a fused ring with adjacent substituents, and q 11 and q 12 are integers of 0 to 4, preferably 0 to 2. When q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different.

L ¹ is a ligand which binds to platinum and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal ) Ligand forming 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, and preferably 2.

It is preferable that n ¹ and m ¹ are such that the metal complex represented by the above-mentioned [formula H-1] is a neutral complex.

In the above-mentioned general formula H-2,

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

In the above-mentioned general formula H-3,

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

According to one embodiment of the present invention, the compounds represented by the above-mentioned [formula H-1] to [formula H-3] may be any one selected from the following compounds.

[Formula I-1]

In the above general formula I-1,

Ring A, ring B, ring C, and ring D represent a nitrogen-containing heterocyclic ring which may have a substituent, and the remaining two rings are an aryl ring or heteroaryl which may have a substituent A condensed ring can be formed by ring A and ring B, ring A and ring C and / or ring B and ring D, respectively.

X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them coordinate to a platinum atom, and the remaining two represent a carbon atom or a nitrogen atom.

Q ¹ , Q ² and Q ³ each independently represent a divalent atom (or a bond), but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. ^{Two of} Z ¹ , Z ² , Z ³ and Z ⁴ represent coordinate bond, and the remaining two represent a covalent bond, an oxygen atom or a sulfur atom.

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula I-1] may be any one selected from the following compounds.

[Formula J-1]

In the above general formula J-1,

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

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

M is preferably Pt, and Ar1 is preferably selected from a 5-membered ring, a 6-membered ring and condensed ring thereof.

According to one embodiment of the present invention, the compound represented by the above-mentioned [formula J-1] may be any one selected from the following compounds.

In addition, the light emitting layer may further include various dopants and various hosts in addition to the dopant and the host.

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

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

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

Synthesis Example 1. Synthesis of [Compound 1]

(1-1)

Intermediate 1-1

In a nitrogen-purged flask, 61 g (381 mmol) of 1,5-dihydroxynaphthalene, 610 mL of dichloromethane and 75.3 g (952 mmol) of pyridine were added and stirred at 0 ° C. 247.1 g (876 mmol) of trifluoromethanesulfonic anhydride was added dropwise, the temperature was brought to room temperature, and the mixture was stirred for about 8 hours. The reaction mixture was cooled to 0 ° C and water and methanol were sufficiently added thereto, followed by filtration to obtain 156 g (yield 97%).

(1-2)

Intermediates 1-2

To the flask was added 30 g (120 mmol) of 2-nitrophenylboronic acid pinacol ester, 76.6 g (181 mmol) of Intermediate 1-1 synthesized above, 5.6 g (5 mmol) of tetrakis (triphenylphosphine) palladium, 49.9 g (361 mmol) of triethylamine, 300 mL of tetrahydrofuran and 60 mL of distilled water were added and stirred. After the temperature was raised to 40 占 폚, the mixture was stirred for about 8 hours. The organic layer was extracted with ethyl acetate and distilled water. Column chromatography was performed with ethyl acetate and heptane to obtain 27.7 g (yield: 58%).

(1-3)

Intermediate 1-3

To the flask, 11.1 g (28 mmol) of the synthesized intermediate 1-2, 5.3 g (31 mmol) of 2-bromoaniline, 0.5 g (1 mmol) of tris (dibenzylideneacetone) dipalladium, 0.3 g (1 mmol) of bis (diphenylphosphino) -1,1'-binaphthyl, 5.4 g (56 mmol) of sodium tertiarybutoxide and 115 mL of toluene were charged and refluxed with stirring. After completion of the reaction, the mixture was concentrated under reduced pressure, and the residue was subjected to column chromatography using dichloromethane and heptane to obtain 5.1 g (yield: 43%).

(1-4)

Intermediates 1-4

To the flask was added 5.1 g (12 mmol) of Intermediate 1-3 synthesized above, 0.1 g (0.24 mmol) of tricyclohexylphosphonium tetrafluoroborate, 0.028 g (0.12 mmol) of palladium (II) acetate and 3.4 g mmol) and N, N'-dimethylacetamide (67 mL), and the mixture was stirred under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature. Water was added to the flask and filtration was conducted to obtain 2.5 g (yield: 61%).

(1-5)

Intermediates 1-5

The flask was charged with 64 g (0.189 mol) of the synthesized Intermediate 1-4, 42.5 g (0.208 mol) of iodobenzene, 19.4 g (0.378 mol) of copper powder, 15 g (0.057 mol) 104.5 g (0.756 mol) were added in this order, 480 mL of 1,2-dichlorobenzene was added thereto, and the mixture was refluxed and stirred at 180 DEG C for 2 days. When the reaction was completed, it was extracted with dichloromethane and distilled water. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 25 g (yield: 32%).

(1-6)

Intermediates 1-6

16.6 g (40 mmol) of Intermediate 1-5 synthesized above, 31.6 g (120 mmol) of triphenylphosphine and 200 mL of 1,2-dichlorobenzene were added and stirred under reflux. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. After column chromatography with heptane and dichloromethane, the residue was recrystallized from methanol to obtain 6.9 g (yield: 45%).

(1-7)

Intermediate 1-7

To the flask was added 25.0 g (112 mmol) of 6-bromo-2-naphthol, 25.1 g (146 mmol) of 1-naphthaleneboronic acid, 3.2 g (2.8 mmol) of tetrakis (triphenylphosphine) palladium, 46.5 g (336 mmol), 125 mL of tetrahydrofuran, 125 mL of 1,4-dioxane, and 50 mL of distilled water were added, and the mixture was stirred under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate and distilled water. The residue was purified by column chromatography with dichloromethane and recrystallized from heptane to obtain 20 g (yield: 66%).

(1-8)

Intermediates 1-8

In a nitrogen-purged flask, 20 g (74 mmol) of the intermediate 1-7 synthesized above, 200 mL of dichloromethane, and 7.6 g (96 mmol) of pyridine were added and stirred at 0 캜. 27.1 g (96 mmol) of trifluoromethanesulfonic anhydride was added dropwise, the temperature was brought to room temperature, and the mixture was stirred. After completion of the reaction, a 2N aqueous hydrochloric acid solution was added thereto, followed by stirring and extraction with dichloromethane. After concentration under reduced pressure, the residue was recrystallized from heptane to obtain 24 g (yield: 81%).

(1-9)

Compound 1

Compound 1 was synthesized in the same manner as in (1-3) with the above synthesized materials. (5.2 g, 55% yield)

MS (MALDI-TOF): m / z 635 [M] ^< ⁺ & gt ^;

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 105.4 109.5 111 111.1 117.6 117.9 118.8 119.6 119.7 119.8 120 121.4 125.1 125.4 125.5 126.1 126.3 126.6 127.2 128.2 128.3 128.7 129.3 129.9 130.9 131.1 131.9 133.1 133.3 134 134.2 135.5 136.7 136.8 137.8 145.4 [48C]

Synthesis Examples 1-1 to 1-6. Synthesis of [Compound 1-1] to [Compound 1-6]

(1) Synthesis of Compounds 1-1 to 1-2 by the same procedure using substituted 4-iodo-1,1'-biphenyl instead of Intermediate 1-8 in (1-9) of Synthesis Example 1 Respectively.

[Compound 1-1] [Compound 1-2]

(2) Compound 1-3 was synthesized in the same manner using the substituted 4-iodo-m-terphenyl in place of Intermediate 1-8 in Synthesis Example 1 (1-9).

[Compound 1-3]

(3) Compound 1-4 was synthesized in the same manner using the substituted 1-iodonaphthalene instead of Intermediate 1-8 in Synthesis Example 1 (1-9).

[Compound 1-4]

(4) Compound 1-5 was synthesized in the same manner as in (1-9) of Synthesis Example 1, using substituted 9-iodophenanthrene instead of Intermediate 1-8.

[Compound 1-5]

(6) Compound 1-6 was synthesized in the same manner as in (1-9) of Synthesis Example 1, except that 2-iodo-9,9'-dimethyl-9H-fluorene substituted for Intermediate 1-8 was used .

[Compound 1-6]

Synthesis Example 2. Synthesis of [Compound 2]

(2-1)

Intermediate 2-1

Intermediate 2-1 was synthesized in the same manner as in (1-1) to (1-2) of Synthesis Example 1.

(2-2)

Intermediate 2-2

15.9 g (60 mmol) of the synthesized intermediate 2-1, 14.1 g (50 mmol) of 1-bromo-2-iodobenzene, CuO nanoparticles (5 mol%) and 4.2 g (75 mmol) of potassium hydroxide were added to the flask, And 50 mL of a mixed solution of DMSO / t-BuOH 1: 3, and the mixture was stirred under reflux at 110 ° C. After completion of the reaction, ethyl acetate and water were added thereto, and the mixture was extracted to separate an organic layer. The organic layer was concentrated under reduced pressure, and then subjected to column chromatography using ethyl acetate and hexane to obtain 23 g. (Yield: 91%)

(2-3)

Intermediate 2-3

Palladium acetate (7.3 g, 32.6 mmol), sodium carbonate (10 g) and dimethylacetamide (200 mL) were added to the above-prepared intermediate 2-2 in a nitrogen-purged flask, Lt; / RTI > After completion of the reaction, the reaction mixture was cooled to room temperature, and water was added thereto, followed by filtration. The filtrate was extracted with ethyl ether and the organic layer was separated. After concentration under reduced pressure, the residue was subjected to column chromatography to obtain 4.4 g (yield: 30%).

(2-4)

Compound 2

Compound 2 was synthesized in the same manner as in (1-6) to (1-9) of Synthesis Example 1, (1.1 g, yield 65%).

MS (MALDI-TOF): m / z 560 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ )?: 106.4 109.5 111.1 111.5 117.6 117.9 119.7 119.8 120 120.9 121.4 122.5 123.3 124.6 124.7 125.1 125.4 126.1 126.3 126.6 127.2 128.2 128.3 128.7 129.9 130.9 131.9 133.1 133.3 134 134.2 136.7 137.8 141.2 145.4 156.5 [42C]

Synthesis Examples 2-1 to 2-6. Synthesis of [Compound 2-1] to [Compound 2-6]

(1) Compound 2-1 was synthesized in the same manner as in (2-4) of Synthesis Example 2, using substituted 1-chloro-1H-pyrrole instead of Intermediate 1-8.

[Compound 2-1]

(2) In the same manner as in (2-4) of Synthesis Example 2, except that 2-chloro-1-methyl-1H-imidazo [4,5- b] 2 were synthesized.

[Compound 2-2]

(3) The same procedure as in (2-4) of Synthesis Example 2 was repeated using 3-bromo-2-methyl-imidazo [2,1-a] isoquinoline instead of Intermediate 1-8, 3 was synthesized.

[Compound 2-3]

(4) Compound 2-4 was synthesized in the same manner as in (2-4) of Synthesis Example 2 except that 6-bromo-2,2 ': 6', 2 "-terpyridine was used instead of Intermediate 1-8. Were synthesized.

[Compound 2-4]

(5) Compound 2-5 was synthesized in the same manner as in (2-4) of Synthesis Example 2, using substituted 2-chlorodibenzo [f, h] quinazoline instead of Intermediate 1-8.

[Compound 2-5]

(6) Synthesis of substituted 4-chloro-5H-pyrido [4 ', 3': 4,5] pyrrolo [3,2-d] Compound 2-6 was synthesized in the same manner.

[Compound 2-6]

Synthesis Example 3. Synthesis of [Compound 3]

(3-1)

Intermediate 3-1

At room temperature, 2-aminobenzonitrile (20.0 g, 169 mmol) and 140 mL of tetrahydrofuran were added to a flask under a nitrogen stream and stirred. 112.9 mL (339 mmol) of phenylmagnesium bromide (3.0 M in Et ₂ O) was added dropwise. After reflux stirring for about 1 hour, the temperature was set to 0 캜. Ethyl chloroformate (22.0 g, 203 mmol) was added dropwise thereto, followed by reflux stirring for about 1 hour. The aqueous ammonium chloride solution was added until it became slightly acidic and the resulting solid was filtered off and washed with water and heptane to give 30.1 g. (Yield: 80%).

(3-2)

Intermediate 3-2

The intermediate 3-1 (30.0 g, 135 mmol) synthesized above and about 80 mL phosphorus oxychloride were added to a flask under a nitrogen atmosphere at room temperature and stirred. After refluxing overnight, the temperature was cooled to -20 ° C on the next day, and then about 400 mL of water was slowly added dropwise. The resulting solid was filtered and washed with water, methanol and heptane. Recrystallization from toluene and heptane yielded 14.6 g. (Yield: 44.9%).

(3-3)

Intermediate 3-3

2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a flask under a nitrogen atmosphere at room temperature, and the mixture was stirred for about 30 minutes. 13.9 g (41 mmol) of Intermediate 1-4 synthesized above and 100 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. 12.8 g (53 mmol) of Intermediate 3-2 synthesized above 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 yielded intermediate 3-3. (15 g, yield 67%).

(3-4)

Compound 3

Compound 3 was synthesized in the same manner as in (1-6) and (1-9) of Synthesis Example 1, (6.2 g, yield 35%).

MS (MALDI-TOF): m / z 687 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 103 109.5 111 111.1 117.9 118.8 119.2 119.6 119.8 120 121.4 122.4 125.5 125.8 126.6 127.4 127.5 127.7 128.2 128.3 128.5 128.7 129.2 130.1 130.2 130.9 131.8 132.2 132.3 133.1 134 139.7 144.4 145.4 149.3 155.8 161 [ ]

Synthesis Example 4. Synthesis of [Compound 4]

(4-1)

Intermediate 4-1

(50.0 g, 289 mmol), ethyl cyanoacetate (98.0 g, 866 mmol), potassium cyanide (20.7 g, 318 mmol) and potassium hydroxide (32.4 g, 577 mmol) in a nitrogen- mmol) were added and stirred. 100 mL of dimethylformamide was added, the temperature was raised to 60 DEG C, and the mixture was stirred overnight. The next day, the change in TLC was checked and the temperature of the flask was brought to room temperature. The reaction solution was concentrated under reduced pressure to remove all possible dimethylformamide. The concentrate was transferred to the reactor with a small amount of dichloromethane, 500 mL of a 5% aqueous solution of sodium hydroxide was added and stirred. After reflux stirring for about 1 hour, the temperature was brought to room temperature. Extracted with ethyl acetate and water. The residue was subjected to column chromatography using ethyl acetate and heptane. Recrystallization from toluene and heptane gave 24.6 g (yield 50.7%).

(4-2)

Intermediate 4-2

14.3 g (589 mmol) of magnesium, 3 drops of iodine and 60 mL of tetrahydrofuran were added to a round bottom flask A under nitrogen flow at room temperature, and the mixture was stirred for about 10 minutes. 125.9 g (540 mmol) of 4-bromobiphenyl and 240 mL of tetrahydrofuran were added dropwise to a flask containing water, followed by stirring under reflux for about 2 hours. After 2 hours, the temperature was brought to room temperature. 41.3 g (246 mmol) of the above synthesized intermediate 4-1 and 150 mL of tetrahydrofuran were added to another round bottom flask B under nitrogen flow at room temperature and stirred. At the room temperature, the reaction solution prepared in the flask A was slowly added dropwise to the flask B filled with water. Thereafter, the mixture was stirred under reflux for about 1 hour. The temperature was adjusted to 0 占 폚, and methyl chloroformate (34.8 g, 368 mmol) was added dropwise thereto, followed by reflux stirring for about 1 hour. The temperature was adjusted to 0 ° C, and the ammonium chloride aqueous solution was added until it became slightly acidic. The resulting solid was filtered and washed with water and heptane to obtain 59 g. (Yield 69%)

(4-3)

Compound 4

Compound 4 was synthesized in the same manner as in Synthesis Example 3 using the synthesized Intermediate 4-2. (3.1 g, yield 40%)

MS (MALDI-TOF): m / z 813 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 103 109.5 111 111.1 117.9 118.8 119.2 119.6 119.8 120 121.4 122.4 124.9 125.5 125.8 126.6 127.2 127.3 127.4 127.6 127.9 128 128.2 128.3 129.1 130.1 130.2 130.7 130.9 132.2 133 133.1 134 134.4 139.7 140.8 144.4 145.4 150 155.8 161 [60C]

Synthesis Example 5. Synthesis of [Compound 5]

(5-1)

Intermediate 5-1

40.0 g (216.9 mmol) of 2,4,6-trichloro-1,3,5-triazine, 63.5 g (520.6 mmol) of phenylboronic acid, 5.0 g (4.4 mmol) of tetrakis (triphenylphosphine) palladium, (520.0 mmol) of potassium carbonate, 200 mL of 1,4-dioxane, 200 mL of toluene and 80 mL of distilled water, and the mixture was stirred at 100 ° C for 6 hours. When the reaction is complete, extract using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and acetone to obtain 34.8 g. (Yield 60%)

(5-2)

Compound 5

Compound 5 was synthesized in the same manner as in (3-3) of Synthesis Example 1 and Synthesis Example 3, (4.5 g, 34% yield)

MS (MALDI-TOF): m / z 664 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 105.4 109.5 111.1 117.6 117.9 118.8 119.8 120 120.5 121.4 121.7 123.3 125.1 126.3 126.6 126.7 126.9 127.5 128.3 128.5 129.2 129.9 131.1 133 134.3 134.7 135.5 135.8 144.4 145.4 172.1 178.8 [47C]

Synthesis Example 6. Synthesis of [Compound 6]

(6-1)

Intermediate 6-1

In Synthesis Example 5 (5-1), 2,4,6-trichloropyrimidine was added in place of 2,4,6-trichloro-1,3,5-triazine and synthesized by the same method to obtain 20 g Yield: 50%).

(6-2)

Intermediate 6-2

20.0 g (75.0 mmol) of the synthesized Intermediate 6-1, 18.1 g (90.0 mmol) of 4-bromophenylboronic acid, 1.7 g (1.5 mmol) of tetrakis (triphenylphosphine) palladium, 20.7 g (150.0 mmol), 1,4-dioxane (100 mL), toluene (100 mL) and distilled water (50 mL), and the mixture is stirred at 100 ° C for 12 hours. When the reaction is complete, extract 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 22.4 g. (Yield: 77%)

(6-3)

Intermediate 6-3

22.4 g (57.8 mmol) of Intermediate 6-2 synthesized above was dissolved in 230 mL of tetrahydrofuran under nitrogen flow, 44 mL (69.4 mmol) of 1.6 M normal-butyl lithium was slowly added dropwise with stirring at -78 ° C, When complete, the mixture is stirred for 1 hour while maintaining the temperature at -78 ° C. Thereafter, 17.6 g (69.4 mmol) of iodine was slowly added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 230 ml of sodium thiosulfate aqueous solution was added dropwise thereto, followed by stirring for 30 minutes. 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 22.1 g. (Yield: 88%)

(6-4)

Compound 6

Compound 6 was synthesized in the same manner as in (1-5) of Synthesis Example 1. (5.0 g, yield 47%).

MS (MALDI-TOF): m / z 739 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 105.4 108.8 109.5 111 111.1 114.1 117.9 118.8 119.6 119.8 120 121.4 123.3 125.1 126.3 126.6 126.7 126.9 127.5 128.1 128.3 128.7 129.2 129.9 130.9 131.1 131.5 134 134.3 135.5 135.8 136.8 145.4 155 164.6 [54C]

SYNTHESIS EXAMPLE 7 Synthesis of [Compound 7]

(7-1)

Compound 7

Compound (7) was synthesized by the same procedure as in Synthesis Example, but using 2-bromo-4-iodoaniline instead of 2-bromoaniline in Synthesis Example 1 (1-3). (3.0 g, yield 35%).

MS (MALDI-TOF): m / z 713 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 105.4 109.5 111.1 111.6 116.8 117.6 117.9 118.8 119.4 119.8 120 120.5 121.4 121.7 125.1 125.4 125.5 126.3 126.6 127.2 127.4 127.5 127.3 128.3 128.5 129.2 129.3 131.1 131.4 131.8 132.3 133 133.1 134.2 136.7 136.8 143.7 144.3 144.4 149.3 155.8 161 [52C]

Synthesis Example 8. Synthesis of [Compound 8]

(8-1)

Intermediate 8-1-a Intermediate 8-1

Compound 8

The flask was charged with 50.0 g (330 mmol) of biphenyl-4-amine, 43.2 g (276 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 1.2 g (5.6 mmol) of palladium acetate, (11.02 mmol), cesium carbonate (126 g, 386 mmol) and toluene (1000 mL) were added, and the mixture was refluxed with stirring for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the toluene was concentrated under reduced pressure. Separation by column chromatography with ethyl acetate and hexane gave 57 g (yield 91%) of intermediate 8-1-a.

Intermediate 8-1 was synthesized by using the synthesized Intermediate 8-1-a in the same manner as in (1-3) of Synthesis Example 1, and Compound 8 was synthesized in the same manner as Synthesis Example 1. (2.8 g, 30% yield)

MS (MALDI-TOF): m / z 868 [M] ^< ^{+ &}

¹³ C NMR (75 MHz, CDCl ₃ ) ?: 30.9 45.5 105.4 109.5 111 111.1 112 113.7 117.6 117.9 118.8 119.6 119.7 119.8 120 120.7 121 121.4 121.6 122.1 123.2 125.5 126.2 126.6 126.7 127.9 128.1 128.7 128.8 129.2 129.3 129.6 130.6 130.9 131.1 131.8 134 134.4 134.8 135.4 136.8 137.8 138.2 139.8 140.3 140.8 141 144.8 145.4 147.8 148.7 [65C]

Synthesis Examples 8-1 to 8-3. Synthesis of [Compound 8-1] to [Compound 8-3]

(1) In Synthesis Example 8, (9-1-dimethyl-9H-fluoren-2-yl) boronic acid was used instead of Intermediate 8-1-a in (8-1) And Synthesis Example 8, Compound 8-1 was synthesized.

[Compound 8-1]

(2) 1-7 of Synthetic Example 1 and Synthesis Example (1) using the substituted dibenzo [b, d] thiophen-2-ylboronic acid instead of Intermediate 8-1-a in Synthesis Example 8 (8-1) Compound 8-2 was synthesized in the same manner as in 8).

[Compound 8-2]

(3) Synthesis of substituted 5-phenyl-5H-pyrido [2 ', 3': 4,5] pyrrolo [3,2-d ] Pyrimidin-2-ylboronic acid, Compound 8-3 was synthesized in the same manner as in 1-7 and Synthesis Example 8 of Synthesis Example 1.

[Compound 8-3]

Examples 1 to 8: Preparation of organic light emitting diode

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the base pressure was adjusted to 1 x 10 < ^-6 > torr. Then, organic substances were injected onto the ITO using DNTPD (700 ANGSTROM), alpha -NPB (300 ANGSTROM) using as a host (90 wt%) and, to a dopant (piq) ₂ Ir (acac), and co-deposited (300 Å) to _{(10 wt%), Alq 3} (350 Å), LiF (5 Å), Al (1,000 Å) in this order and measured at 0.4 mA.

The structure of the DNTPD, α-NPB, (piq ) 2 Ir (acac), Alq 3 and the [compound 1] to [Compound 8] is:

[DNTPD] [[alpha] -NPB]

_{[(piq) 2 Ir (acac} )] [Alq 3]

[Compound 1] [Compound 2] [Compound 3] [Compound 4]

[Compound 5] [Compound 6] [Compound 7] [Compound 8]

Example 9

PTOEP] was used instead of [(piq) ₂ Ir (acac)], and the compound used in the light emitting layer in the device structures of Examples 1 to 8 was selected as [Compound 3] ] Is as follows.

[PTOEP]

Comparative Example 1

The organic light emitting device for Comparative Example 1 was fabricated in the same manner except that CBP which is widely used as a general phosphorescent host material instead of the organic light emitting compound prepared by the present invention as the host of the light emitting layer in the device structure of the above example was used. The structure of which is as follows.

[CBP]

Comparative Example 2

The organic light emitting diode device for Comparative Example 2 was fabricated in the same manner except that CBP was used instead of [Compound 3] in the device structure of Example 9. [

The voltage, current density, luminance, color coordinates, and lifetime of the organic electroluminescent device manufactured according to Examples 1 to 9 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 1 below.

T95 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 95%.

division Host
compound Dopant Voltage
(V) Luminance
(Cd / m 2) CIEx CIEy T ₉₅ (Hr) Example 1 One (piq) < / RTI > ₂ Ir (acac) 4.3 1760 0.670 0.329 465 Example 2 2 (piq) < / RTI > ₂ Ir (acac) 4.2 1750 0.674 0.325 415 Example 3 3 (piq) < / RTI > ₂ Ir (acac) 4.1 1800 0.672 0.327 440 Example 4 4 (piq) < / RTI > ₂ Ir (acac) 4.3 1740 0.672 0.327 435 Example 5 5 (piq) < / RTI > ₂ Ir (acac) 4.0 1690 0.674 0.325 395 Example 6 6 (piq) < / RTI > ₂ Ir (acac) 4.2 1710 0.676 0.323 420 Example 7 7 (piq) < / RTI > ₂ Ir (acac) 4.3 1870 0.670 0.329 445 Example 8 8 (piq) < / RTI > ₂ Ir (acac) 4.1 1850 0.671 0.328 425 Example 9 3 PTOEP 4.1 1810 0.652 0.325 430 Comparative Example 1 CBP (piq) < / RTI > ₂ Ir (acac) 7.7 290 0.668 0.331 30 Comparative Example 2 CBP PTOEP 7.5 270 0.652 0.330 30

Claims (10)

Organic light-emitting compounds represented by the following formulas (A) to (C):
[Chemical Formula B] [Chemical Formula C]

In the above formulas (A) to (C)
R ₁ to R ₁₄ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C1 to 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 aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Substituted and is selected from the two kinds of atoms O, N or the group consisting of carbon number 2 to 50 having an S-heteroaryl group, a cyano group, a nitro group and a halogen group,
R ₁ to R ₁₄ may be connected to adjacent substituents to form a monocyclic or polycyclic ring of an alicyclic or aromatic group and the carbon atom of the formed alicyclic or aromatic monocyclic or polycyclic ring may be N, S, O ≪ RTI ID = 0.0 > and / or < / RTI >
The "- *" of Q is connected to any one of R ₅ and R _{6 ,} R ₆ and R _7, and R ₇ and R ₈ by a single bond to form a fused ring,
Ar ₁ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,
L is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C2-C6 heteroarylene group. ,
n is an integer of 1 to 3, and when n is 2 or more, a plurality of L's are the same or different from each other,
Y is _{CR 31 R 32, NR 33,} O, S, SiR 34 R 35, GeR 36 R 37, PR 38, PR 39 (= O), C = O and selected from BR _40, wherein R ₃₁ to R ₄₀ Are the same as the definitions of R ₁ to R ₁₄ . The method according to claim 1,
Each of R ₁ to R ₄₀ , Ar ₁ and L is independently selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl 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, a heteroaryl group having 2 to 24 carbon atoms or a heteroaryl group having 2 to 24 carbon atoms An alkyl group having 1 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 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, A silyl group, and an aryloxy group having 1 to 24 carbon atoms. The method according to claim 1,
The organic electroluminescent compound according to any one of the above [1] to [4], wherein the organic electroluminescent compound is selected from compounds represented by the following formulas [D1] to [D14]
[Chemical formula D1] [Chemical formula D2] [Chemical formula D3]

[Chemical formula D4] [Chemical formula D5]

[Chemical formula D6] [Chemical formula D7]

[Chemical formula D8] [Chemical formula D9]

[Chemical formula D10] [Chemical formula D11]

[Chemical formula D12] [Chemical formula D13] [Chemical formula D14]

In the above formulas (D1) to (D14)
R ₁ to R ₁₄ , Ar ₁ , L, n and Y are the same as defined in [Formula A] to [Formula C]. The method according to claim 1,
The heteroaryl group contained in the above [Formula A] to [Formula C] is any one selected from the following Structural Formulas 1 to 6:
[Structural formula 1] [Structural formula 2] [Structural formula 3]

[Structural formula 4] [Structural formula 5] [Structural formula 6]

In the above Structural Formulas 1 to 6,
T ₁ to T ₈ are the same or different and are each independently selected from C (R ₅₁ ), C (R ₅₂ ) (R ₅₃ ), N, N (R ₅₄ )
R ₄₁ to R ₅₄ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom,
The R ₄₁ to R ₅₄ Is bonded to any one of R ₁ to R ₁₄ , Ar ₁ , L, Y and substituents thereof in the above formulas (A) to (C) to form a single bond. 5. The method of claim 4,
The organic electroluminescent compound according to any one of [1] to [6] is any one selected from the following structural formulas:
[Structural Formula 7]

In the above formula 7,
X is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms A substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom having 2 to 5 carbon atoms having O, N or S, 0, a heteroaryl group, 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, plural Xs are the same or different from each other, and any one of the at least one X is selected from the group consisting of R ₁ to R ₁₄ , Ar ₁ , L, Y, and any of these substituents to form a single bond. The method according to claim 1,
Wherein L is selected from the following Structural Formulas 8 to 15:
[Structural formula 8] [Structural formula 9] [Structural formula 10] [Structural formula 11]

[Structural Formula 12] [Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

In the above Structural Formulas 8 to 15, hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each structural formula. A first electrode; A second electrode facing the first electrode; And at least one organic layer interposed between the first electrode and the second electrode,
Wherein the organic layer comprises at least one organic electroluminescent compound represented by the general formulas (A) to (C) according to claim 1. 8. The method of claim 7,
Wherein the organic layer comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer and an electron injection layer. 9. The method of claim 8,
Wherein the light emitting layer comprises at least one host compound and at least one dopant compound, and the host compound is an organic light emitting compound represented by the above Chemical Formulas A to C, respectively. 8. The method of claim 7,
Wherein the organic layer further comprises one or more organic light emitting layers emitting red, green, or blue light to emit white light.

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