KR20150111106A - An organoelectro luminescent compounds and organoelectro luminescent device using the same - Google Patents

Abstract

The present invention relates to an organic luminescent compound represented by chemical formula 1 and an organic electroluminescent element comprising the same. An organic electroluminescent element using an organic luminescent compound according to the present invention can be driven at a lower voltage than an existing element using a phosphorescent host material and has high power efficiency.

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 a pair of electrons and holes, The device can be formed on a substrate and can be driven at a voltage as low as 10 V or less as compared with a plasma display panel or an inorganic electroluminescence display, has a relatively low power consumption, and is excellent in 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 significant advantage in terms of power efficiency due to a high voltage and satisfactory level of life of the device can not be achieved, and development of a more stable and high-performance host material is required.

Accordingly, an object of the present invention is to provide an organic luminescent compound which can be driven at a lower voltage than a conventional material and has improved power efficiency.

The present invention also provides an organic electroluminescent device which can be driven at a low voltage by employing the organic electroluminescent compound as a light emitting material and has higher power efficiency.

In order to solve the above-described problems, the present invention provides an organic luminescent compound represented by the following formula (1).

[Chemical Formula 1]

The structure and the substituents of the above formula (1) will be described later in detail.

Further, the present invention is a liquid crystal display 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.

The organic electroluminescent device employing the organic electroluminescent compound according to the present invention can be driven at a lower voltage than the conventional device using the phosphorescent host material and has high power efficiency.

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

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

One aspect of the present invention relates to a bipolar organic electroluminescent compound represented by the following Chemical Formula 1 and having both a hole transportation unit and an electron transportation unit.

[Chemical Formula 1]

In the above formula (1)

L is a single bond or a divalent group selected from a substituted or unsubstituted alkylene group having 2 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms M is an integer of 0 to 4, and when m is 2 or more, the plural Ls may be the same or different from each other.

The ETU- * of the above-mentioned formula (1) is an electron transporter and is characterized by being represented by [Structural formula 1-1] or [Structural formula 1-2].

[Structural formula 1-1] [Structural formula 1-2]

In the above Structural Formulas 1-1 to 1-2,

A ₁ to A ₇ are the same or different from each other and each independently represent CR ₁ to CR ₇ Or N.

R ₁ to R ₇ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms , A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1- 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 carbon number 5 A substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, A nitro group, a halogen group, a selenium group, a tellurium group, an amide group, an ether group and an ester group, each of which is optionally substituted with one or more groups selected from the group consisting of a halogen atom, .

The above R ₁ to R ₇ And the carbon atoms of the alicyclic or aromatic hydrocarbon ring may be N, S, O, Se, Te, Po, or a combination of two or more of the carbon atoms of the alicyclic or aromatic hydrocarbon ring, May be substituted with any one or more substituted or unsubstituted heteroatoms selected from NR _{14 ,} SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (= O), C═O, S═O and BR ₂₁ . The R ₁₄ To R ₂₁ is as defined the above R ₁ to R _7.

X is the same as defined for R ₁ to R ₇ above except that X is hydrogen.

* -HTU of the above formula (1) is a hole transportation unit, and is characterized by being represented by the following structural formula (1).

[Structural formula 1]

In the above formula 1,

M is either a single _{bond, CR 12 R 13, NR 14} , O, S, Se, Te, Po, SiR 15 R 16, GeR 17 R 18, PR 19, PR 20 (= O), C = O, S = O and BR ₂₁ , and the R ₁₂ To R < ₂₁ > are the same as defined for R &_lt; ₁ > to R &_lt; ₇ >

R ₁₂ and R ₁₃ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ are each independently a substituted or unsubstituted fused cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted fused carbon atom having 2 to 30 carbon atoms, A substituted or unsubstituted aryl group having 5 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

Each of Ar ₁ to Ar ₂ is independently a substituted or unsubstituted aryl group having 5 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom.

According to a preferred embodiment of the present invention, the above-mentioned [formula 1] can be selected from the following formula [2] to [formula 4].

[Structural formula 2]

[Structural Formula 3]

[Structural Formula 4]

In the above Structural Formulas 2 to 4,

R ₈ To R ₁₁ is the above R ₈ as defined for R ₁ to R ₇ in Formula 1, and To R < ₁₁ > may be connected to each other to form a condensed aliphatic, condensed aromatic, condensed heteroaliphatic or fused heteroaromatic ring.

Z is a single _{bond, CR 12 R 13, NR 14} , O, S, Se, Te, Po, SiR 15 R 16, GeR 17 R 18, PR 19, PR 20 (= O), C = O, S = O and BR ₂₁ , and the R ₁₂ To R ₂₁ are the the same as defined in Formula 1 of R ₁ to R _7, wherein R ₁₂ and R _13, R ₁₅ and R _16, R is ₁₇ and R ₁₈ are each connected to each other a substituted or unsubstituted fused A substituted or unsubstituted fused C 2 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 5 -C 30 aryl group or a substituted or unsubstituted C 3 -C 30 heteroaryl group having 3 to 30 carbon atoms, Group can be formed.

Y is the same as defined for R ₁ to R ₇ in the above formula (1), m is an integer of 1 to 5, and when m is 2 or more, plural Ys may be the same as or different from each other.

The Y may form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring by bonding to adjacent substituents, and the carbon atom of the alicyclic or aromatic hydrocarbon ring may be N, S, O, Se, Te, Which is substituted with any one or more substituted or unsubstituted heteroatoms selected from the group consisting of Po, NR _{14 ,} SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (= O), C═O, S═O and BR ₂₁ . The R ₁₄ To R ₂₁ is as defined the above R ₁ to R _7.

In the present invention, the substituent X is bonded to a specific position of the structural formulas 1-1 to 1-2, so that the organic electroluminescent device of the present invention has a higher emission efficiency than the organic electroluminescent device of the present invention A device employing a compound can be driven at a lower voltage and has a high power efficiency.

According to a preferred embodiment of the present invention, X is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom .

The 'substituted' in the 'substituted or unsubstituted' signifies the case where R ₁ to R ₂₁ , L and Ar ₁ to Ar ₂ are further substituted by one or more substituents, wherein one or more substituents are selected from the group consisting of R ₁ To R < ₅ >.

More specifically, the one or more substituents may be deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, A halogenated alkyl group having 5 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 5 to 24 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, An arylsilyl group having 24 to 24 carbon atoms, an alkylamine group having 1 to 20 carbon atoms, and an arylamine group having 6 to 24 carbon atoms.

Also, R ₁ to R ₂₁ , L and Ar ₁ to Ar ₂ And the substituents thereof may be connected to each other or adjacent substituents to form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon, and the carbon atom of the alicyclic or aromatic hydrocarbon ring formed may be N, S, O, Se, _{Te, Po, NR 14, SiR} 15 R 16, GeR 17 R 18, PR 19, PR 20 (= O), C = O, S = O and BR ₂₁ least one selected from a substituted or unsubstituted with a hetero atom .

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

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, , Aromatic groups such as a pyrenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a perylene group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group.

The aryl group may be further substituted with at least one substituent selected from the substituents described in the definitions of R ₁ to R _5. More specifically, at least one hydrogen atom of the aryl group may be substituted with a substituent selected from the group consisting of a deuterium atom, a halogen atom, (-NH ₂ , -NH (R), -N (R ') (R "), R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms, 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 alkenyl 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 heteroaryl 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, a heteroarylalkyl group having 2 to 24 carbon atoms, .

The heteroaryl group contained in the organic luminescent compound according to the present invention may be any one selected from the following Structural Formulas 5 to 14:

[Structural Formula 5] [Structural Formula 6] [Structural Formula 7] [Structural formula 8]

[Structural Formula 9] [Structural Formula 10] [Structural Formula 11]

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

In the above Structural Formulas 5 to 14,

T ₁ to T ₁₂ may be the same or different and are each independently any one selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ) and, T ₁ to not is if the T ₁₂ at the same time all the carbon atoms, wherein R ₄₁ to R ₄₄ are the same or different and each independently represent hydrogen, deuterium, an alkyl group, a substituted or unsubstituted 1 to 30 carbon atoms, substituted with each other Or a substituted or unsubstituted aryl group having 5 to 30 carbon atoms and a heteroaryl group having 2 to 30 carbon atoms having a substituted or unsubstituted heteroatom, O, N, S, or P, Is selected.

The above-mentioned [formula 7] may include a compound represented by the following formula [7-1] by a resonance structure according to the movement of electrons.

[Structural formula 7-1]

In the above structural formula 7-1, T ₁ to T ₇ are the same as defined in [Structural formula 5] to [Structural formula 14] above.

According to a preferred embodiment of the present invention, the above [Structural formulas 5] to [Structural formula 14] can be selected from the following [Structural formula 15].

[Structural Formula 15]

In the above structural formula 15,

X is the same as defined for R ₁ to R ₇ in the above formula (1), m is an integer of 1 to 11, and when m is 2 or more, plural Xs are the same as or different from each other, Lt; / RTI >

The formula 1 according to the present invention may be more specifically selected from the following formulas (2) to (162), but the scope of the formula (1) according to the present invention is not limited thereto.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, ] Of at least one organic light emitting compound according to the present invention.

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, and an electron injecting layer .

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 comprises a host and a dopant, the dopant content may be selected in the range of about 0.01 to about 20 parts by weight, based on 100 parts by weight of the host.

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

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

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

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

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

The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. Specific examples thereof include 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 a material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq _2, OXD-7, Liq and [Formula 501] to [Chemical Formula 507] either, but one that can be used is selected from, this limited It is not.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(501) [502] ≪ EMI ID =

≪ EMI ID = ≪ EMI ID = ≪ EMI ID =

≪ EMI ID =

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

As the electron transporting layer material, a known electron transporting material can be used as a material that stably transports 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- materials such as olate: Bebq2), ADN, [Formula 401], [Formula 402], and oxadiazole derivatives PBD, BMD, BND and the like may be used.

TAZ BAlq

[Compound 401] [Compound 402] BCP

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

≪ RTI ID = 0.0 &

In the above formula (C)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted 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.

The organic electroluminescent device according to the present invention is characterized in that the organic layer comprises a light emitting layer and the light emitting layer further comprises at least one phosphorescent dopant in addition to at least one organic light emitting compound represented by the general formula (1) The light emitting dopant to be applied to the organic electroluminescent device of the present invention is not particularly limited, but may be at least one compound selected from compounds represented by the following formulas [A-1] to [J-1].

[General Formula A-1]

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

[Structural formula D]

In the above structural formula D,

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

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

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

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

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

[Formula B-1]

In the above general formula B-1,

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

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

[Formula C-1]

In the above general formula (C-1)

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

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

[Formula D-1]

In the above general formula (D-1)

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

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

[Formula E-1]

In the above general formula E-1,

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

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

[Formula F-1]

In the above general formula F-1,

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

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

[Formula G-1]

In the above general formula G-1,

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

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

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

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

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

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

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

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

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

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

In the above-mentioned general formula H-2,

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

In the above-mentioned general formula H-3,

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

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

[Formula I-1]

In the above general formula I-1,

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

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

[Formula J-1]

In the above general formula J-1,

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

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

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

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

In addition, the light emitting layer may further include various dopants and various hosts as well as 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 (23)

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

[Intermediate 1-a]

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

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

[Intermediate 1-a] [Intermediate 1-b]

50.0 g (297 mmol) of [Intermediate 1-a] obtained from the above Reaction Scheme-1 and 500 mL of dimethylformamide were stirred. 55.56 g (312 mmol) of N-bromosuccinimide was then slowly added to the reactor. The mixture was stirred at room temperature for 4 hours. When the reaction is completed, distilled water is added dropwise at room temperature. When brown crystals are formed, the crystals are separated by filtration and separated by column chromatography to obtain 68 g of a compound represented by [Intermediate 1-b]. (Yield: 92.6%).

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

[Intermediate 1-b] [Intermediate 1-c]

62.8 g (254 mmol) of Intermediate 1-b obtained in the above Scheme 1-2, 40.2 g (330 mmol) of phenylboronic acid, 13.3 g (12 mmol) of tetrakis (triphenylphosphine) palladium, Was added to 70.1 g (508 mmol) of 1,4-dioxane, 250 mL of toluene and 100 mL of distilled water, and the mixture was stirred at 100 DEG C for 12 hours. After the reaction was completed, the temperature was adjusted to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was concentrated and then subjected to column chromatography to obtain 45 g (yield: 91%) of a compound represented by [Intermediate 1-c].

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

[Intermediate 1-c] [Intermediate 1-d]

45.0 g (184 mmol) of Intermediate 1-c obtained in the above Scheme 1-3 and 270 mL of tetrahydrofuran were added thereto, and 129 mL (387 mmol) of 3M-phenylmagnesium bromide was gradually added dropwise thereto at 0 ° C. And the mixture was refluxed and stirred. When the starting material disappeared, the temperature was lowered again, and then 23.99 g (221 mmol) of ethyl chloroformate was dissolved in 225 mL of tetrahydrofuran, and the mixture was slowly added dropwise, followed by stirring under reflux for 2 hours. After the reaction was completed, the reaction was stopped by adding an aqueous solution of ammonium chloride. The reaction was stopped by extraction with ethyl acetate and water. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 40 g of a compound represented by [Intermediate 1-d] (yield 80%).

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

[Intermediate 1-d] [Intermediate 1-e]

40 g (115 mmol) of the intermediate [1-d] obtained in the above Reaction Scheme 1-4 and 200 mL of phosphorus oxychloride were added, and the mixture was refluxed with stirring for 5 hours. When the reaction was complete, it was slowly added dropwise to the lower temperature water. After the dropwise addition was completed, the mixture was filtered, and the mixture was extracted with methylene chloride and water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 30 g (yield 71.2%) of the compound represented by [Intermediate 1-e].

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

[Intermediate 1-f]

60 g (244 mmol) of 3-bromocarbazole, 38.65 g (317 mmol) of phenylboronic acid, 8.45 g (7 mmol) of tetrakis (triphenylphosphine) palladium and 101.1 g , 300 mL of 1,4-dioxane, 300 mL of toluene, and 120 mL of distilled water, and the mixture was stirred at 100 ° C for 12 hours. When the reaction is complete, extract using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 45 g (yield: 66.9%) of a compound represented by [Intermediate 1-f].

[Reaction formula 1-7] Synthesis of [Formula 23]

[Intermediate 1-f] [Intermediate 1-e]

5.0 g (21 mmol) of the compound represented by [Intermediate 1-f] obtained in the above Reaction Scheme 1-6, 9.0 g (25 mmol) of Intermediate 1-e obtained in the Reaction Scheme 1-5, 0.4 g (0.6 mmol) of dipalladium, 0.6 g (2 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 3.95 g (41 mmol) of sodium tertiary butoxide and 50 mL of xylene were charged, The mixture was refluxed over time. When the reaction is completed, the reaction is filtered under reduced pressure in a hot state. After the solution was dried under reduced pressure, 5.0 g (yield: 42.4%) of a compound represented by the formula (23) was obtained by column chromatography.

MS [M] ^< ⁺ & gt ^; : 572

[Synthesis Example 2] Synthesis of Compound (24)

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

 [Intermediate 2-a]

Synthesis Example 1 30 g (yield: 83.9%) of the compound represented by [Intermediate 2-a] was synthesized, except that 2-naphthylboronic acid was used instead of phenylboronic acid used in [Scheme 1-3] .

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

[Intermediate 2-a] [Intermediate 2-b]

Synthesis Example 1 Synthesis was conducted in the same manner as in [Scheme 1-4], except that [Intermediate 2-a] was used instead of [Intermediate 1-c] to obtain 24.3 g of the compound represented by [Intermediate 2-b] %).

Synthesis of [Reaction 2-3] [Intermediate 2-c]

[Intermediate 2-b] [Intermediate 2-c]

Synthesis Example 1 The procedure of Synthesis Example 1 was repeated except for using [Intermediate 2-b] instead of [Intermediate 1-d] used in [Scheme 1-5] to obtain 29.7 g of the compound represented by [Intermediate 2-c] %).

[Reaction formula 2-4] Synthesis of [Formula 24]

[Intermediate 1-f] [Intermediate 2-c]

Synthesis Example 1 The procedure of Synthesis Example 1 was repeated except that [Intermediate 2-c] was used instead of [Intermediate 1-e] used in Reaction Scheme 1-7 to obtain 5.5 g (yield 35.8% ≪ / RTI >

MS [M] ^< ⁺ & gt ^; : 622

[Synthesis Example 3] Synthesis of Compound (46)

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

[Intermediate 3-a]

Synthesis Example 1 The procedure of Synthesis Example 1 was repeated except that 3- (1-naphthyl) phenylboronic acid was used in place of phenylboronic acid used in [Reaction Scheme 1-6], to thereby yield 47.5 g of the compound represented by [Intermediate 3-a] 68.4%).

[Synthesis 3-2] Synthesis of [Formula 46]

[Intermediate 3-a] [Intermediate 1-g] [Chemical Formula 46]

Synthesis Example 1 4.5 g (the yield: 39.6%) of the compound represented by the formula (46) was synthesized except that [Intermediate 3-a] was used instead of [Intermediate 1-f] used in the scheme [1-7] ≪ / RTI >

MS [M] ^< ⁺ & gt ^; : 698

[Synthesis Example 4] Synthesis of compound of formula (73)

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

[Intermediate 4-a]

Synthesis Example 1 54.2 g (Yield 92.6%) of the compound represented by [Intermediate 4-a] was synthesized except that 2-aminobenzonitrile was used in place of [Intermediate 1-a] used in [Scheme 1-2] ).

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

[Intermediate 4-a] [Intermediate 4-b]

Synthesis Example 1 The same procedure was followed except for using [Intermediate 4-a] instead of [Intermediate 1-b] used in [Scheme 1-3] to obtain 45.0 g of the compound represented by [Intermediate 4-b] %).

Synthesis of [Reaction Scheme 4-3] [Intermediate 4-c]

[Intermediate 4-b] [Intermediate 4-c]

Synthesis Example 1 29.7 g (yield: 80.2%) of the compound represented by [Intermediate 4-c] was synthesized except that [Intermediate 4-b] was used instead of [Intermediate 1-c] used in [Scheme 1-4] %).

Synthesis of [Reaction Scheme 4-4] [Intermediate 4-d]

[Intermediate 4-c] [Intermediate 4-d]

Synthesis Example 1 46.0 g (yield: 80%) of the compound represented by [Intermediate 4-d] was synthesized except that [Intermediate 4-c] was used instead of [Intermediate 1-d] %).

Synthesis of [Reaction Scheme 4-5] [Intermediate 4-e]

[Intermediate 4-e]

5000 mL round bottom flask under nitrogen you methyl anthranilate state rate 73.8 g (0.0.488 mol), 2- bromo-triphenylene 100.0 g (0.326 mol), palladium acetate _{(Pd (OAc) 2) 0.7} g (0.003 5.7 g (0.010 mol) of zincphosphate, 212.1 g (0.651 mol) of cesium carbonate, and 1500 mL of toluene were charged and refluxed for 6 hours. When the reaction was completed, the reaction product was separated into layers and the water layer was removed. The organic layer was separated, concentrated under reduced pressure, and 108.6 g (88.4%) of the compound represented by [Intermediate 4-e] was obtained by column chromatography.

Synthesis of [Reaction Scheme 4-6] [Intermediate 4-f]

[Intermediate 4-e] [Intermediate 4-f]

70 g (0.185 mol) of [Intermediate 4-e] obtained in the above Reaction Scheme 4-5 and 700 mL of diisopropyl ether were added to the solution, and then 205 mL of methylmagnesium bromide was slowly added dropwise thereto. After the dropwise addition, the mixture was stirred at 50 ° C. When the reaction was completed, the reaction product was separated into layers, the water layer was removed, and the organic layer was separated. The organic layer was separated under reduced pressure and subjected to column chromatography to obtain 58.0 g (82.8%) of the compound represented by [Intermediate 4-f].

Synthesis of [Reaction Scheme 4-7] [Intermediate 4-g]

[Intermediate 4-f] [Intermediate 4-g]

58 g (0.154 mol) of the [intermediate 4-f] compound obtained in the above Reaction Scheme 4-6 and 150 mL of phosphoric acid were added and stirred at room temperature. When the reaction was completed, the reaction product was freely stirred with water. After stirring, the mixture was filtered and washed with water and methanol. 44.8 g (81.1%) of the compound represented by [Intermediate 4-g] was obtained by column chromatography.

[Reaction Scheme 4-8] Synthesis of [Formula 73]

[Intermediate 4-g] [Intermediate 4-d] [Compound 73]

Synthesis Example 1 Synthesis was conducted in the same manner as in [Reaction Scheme 1-7] except that [Intermediate 4-g] was used instead of [Intermediate 1-f] instead of [Intermediate 1-e] 5.3 g (yield: 42.5%) of the compound represented by the formula (73) was obtained.

MS [M] ^< ⁺ & gt ^; : 638

[Synthesis Example 5] Synthesis of Compound (84)

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

 [Intermediate 5-a]

The dried 1 L reactor was charged with nitrogen and then 5.85 g (244 mmol) of sodium hydride and 150 mL of N, N-dimethylformamide were stirred. 30 g (122 mmol) of 3-bromocarbazole was dissolved in 250 mL of N, N-dimethylformamide at 0 ° C and slowly added to the reactor. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. 38.05 g (146 mmol) of iodomethane was then dissolved in 50 mL of N, N-dimethylformamide at 0 < 0 > C and slowly added to the reactor. After stirring overnight at room temperature, the reaction solution was added to distilled water. The product was separated by column chromatography to obtain 30 g (yield 97%) of the compound represented by [Intermediate 5-a].

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

[Intermediate 5-a] [Intermediate 5-b]

Synthesis Example 1 Synthesis was conducted in the same manner as in [Scheme 1-6] except that [Intermediate 5-a] was used instead of 3-bromocarbazole and 3-carbazolylboronic acid pinacol ester was used instead of phenylboronic acid [ 19.2 g (yield: 65.3%) of the compound represented by the formula (5-b) was obtained.

[Reaction formula 5-3] Synthesis of [Formula 84]

[Intermediate 5-b] [Intermediate 4-d]

Synthesis Example 1 Synthesis was conducted in the same manner as Intermediate 5-b except that Intermediate 4-d was used instead of Intermediate 1-e in place of Intermediate 1-f used in Reaction Scheme 1-7 [ 5.0 g (yield 39.5%) of the compound represented by the formula (84) was obtained.

MS [M] ^< ⁺ & gt ^; : 625

[Synthesis Example 6] Synthesis of Compound (92)

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

[Intermediate 4-a] [Intermediate 6-a]

After charging the dried 2 L reactor with nitrogen, 10.9 g (0.055 mol) of the intermediate [4-a] obtained in Reaction Scheme 4-1 and 200 mL of tetrahydrofuran were added, and 3M- phenylmagnesium bromide (36.8 mL, 0.110 mol) was slowly added dropwise thereto, followed by reflux stirring for 3 hours. When the starting material disappeared, the temperature was lowered again, and 14.4 g (0.066 mol) of 4-bromobenzoyl chloride was dissolved in 150 mL of tetrahydrofuran, and the mixture was slowly added dropwise, followed by stirring under reflux for 2 hours. After the reaction was completed, the reaction was stopped by adding an aqueous ammonium chloride solution. The reaction mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and then subjected to column chromatography to obtain 17.3 g (yield: 71.3%) of a compound represented by the formula 6-a.

[Reaction Scheme 6-2] Synthesis of [Formula 92]

[Intermediate 6-a]

Synthesis Example 1 Synthesis was conducted in the same manner as in [Formula 92] except that carbazole was used instead of [intermediate 1-f] used in [Reaction Formula 1-7] instead of [intermediate 6-a] To obtain 4.8 g (yield: 43.1%) of the compound to be displayed.

MS [M] ^< ⁺ & gt ^; : 613

[Synthesis Example 7] Synthesis of Compound (117)

Synthesis of [Reaction Scheme 7-1] [Intermediate 7-a]

[Intermediate 7-a]

In a dried 1 L reactor, 35.0 g (0.299 mol) of indole, 60.5 g (0.598 mol) of potassium hydroxide and 250 mL of tetrahydrofuran were dissolved under nitrogen and stirred for 20 minutes. Then, at 0 ° C, 68.4 g (0.359 mol) of 4-toluenesulfonyl chloride was dissolved in 100 mL of tetrahydrofuran, and then slowly added dropwise. After dropwise addition, the mixture was stirred at room temperature for 12 hours. After completion of the reaction, 500 mL of distilled water was added and the mixture was extracted with ethyl acetate. The organic layer was concentrated and then subjected to column chromatography to obtain 62.0 g (yield 76.5%) of the compound represented by [Intermediate 7-a].

Synthesis of [Reaction Scheme 7-2] [Intermediate 7-b]

[Intermediate 7-a] [Intermediate 7-b]

63.0 g (0.232 mol) of [Intermediate 7-a] obtained from the above-mentioned Scheme 7-1 and 630 mL of dichloromethane were stirred under nitrogen in a dried 2 L reactor. Then 29.7 g (0.186 mol) of bromine was dissolved in 315 mL of tetrahydrofuran at 0 ° C, and then slowly added dropwise. After the dropwise addition, the mixture was stirred at 0 ° C for 3 hours. After completion of the reaction, 500 mL of an aqueous solution of sodium bicarbonate was added and the mixture was extracted with methylene chloride. The organic layer was concentrated and then subjected to column chromatography to obtain 69.0 g (yield: 84.9%) of the compound represented by [Intermediate 7-a].

Synthesis of [Reaction Scheme 7-3] [Intermediate 7-c]

   [Intermediate 7-c]

A dried 2 L reactor was charged with 100 g (0.465 mol) of 2-bromoethylacetate, 177.1 g (0.698 mol) bis (pinacolato) diboron, 1,1'-bis (diphenylphosphino) ferrocene ] Dichloropalladium (10.2 g, 14 mmol), potassium acetate (136.9 g, 1.395 mol) and toluene (1000 mL) were added and refluxed for 12 hours. After filtration at a high temperature, the filtrate was concentrated under reduced pressure and then separated by column chromatography to obtain 96 g (yield: 84.9%) of the compound represented by [Intermediate 7-c].

Synthesis of [Reaction Scheme 7-4] [Intermediate 7-d]

[Intermediate 7-b] [Intermediate 7-c] [Intermediate 7-d]

69.1 g (0.197 mol) of Intermediate 7-b obtained in the above Reaction Scheme 7-2, 67.1 g (0.256 mol) of Intermediate 7-c obtained in Reaction Scheme 7-3, tetrakis (6.85 g, 6 mmol), potassium carbonate (68.1 g, 0.493 mol), 1,4-dioxane (345 mL), toluene (345 mL) and distilled water (138 mL), and the mixture was stirred at 100 ° C for 12 hours. After the reaction was completed, the temperature was adjusted to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was concentrated and then subjected to column chromatography to obtain 57.0 g (yield: 71.4%) of the compound represented by [Intermediate 7-d].

Synthesis of [Reaction Scheme 7-5] [Intermediate 7-e]

[Intermediate 7-d] [Intermediate 7-e]

57 g (0.141 mol) of [Intermediate 7-d] obtained in the above Reaction Scheme 7-4 and 570 mL of tetrahydrofuran were added to a dried 2 L reactor under nitrogen and the mixture was stirred. After cooling to 0 占 폚, 164.01 mL (0.492 mol) of 3M-methylmagnesium bromide was added dropwise and the mixture was refluxed for 3 hours. Saturated ammonium chloride aqueous solution was added, and organic layer was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and 171 mL of phosphoric acid was added thereto, followed by stirring at 50 DEG C for 12 hours. After the reaction was completed, the organic layer was extracted with methylene chloride and distilled water, and then concentrated under reduced pressure, followed by separation by column chromatography to obtain 40.0 g (yield: 73.4%) of the compound represented by [Intermediate 7-e].

[Synthesis of Reaction Formula 7-6] [Intermediate 7-f]

[Intermediate 7-e] [Intermediate 7-f]

40.0 g (0.103 mol) of [Intermediate 7-e] obtained in the above Reaction Scheme 7, 100.9 g (0.310 mol) of cesium carbonate, 240 mL of tetrahydrofuran and 120 mL of methanol were added to a dried 1 L reactor under nitrogen, And the mixture was refluxed with stirring for 5 hours. After the completion of the reaction, the reaction mixture was poured into water having a reduced temperature, and the mixture was extracted with methylene chloride and water. The organic layer was concentrated under reduced pressure and the residue was purified by column chromatography to obtain 22.0 g (yield: 91.3%) of a compound represented by [Intermediate 7-f].

[Synthesis of Reaction Formula 7-7] [Formula 117]

[Intermediate 7-f] [Intermediate 4-d]

Synthesis Example 1 Synthesis was conducted in the same manner as Intermediate 7-f except for using Intermediate 4-d instead of Intermediate 1-e instead of Intermediate 1-f used in Reaction Scheme 1-7 [ 3.6 g (yield: 38.4%) of the compound represented by the formula (117) was obtained.

MS [M] ^< ⁺ & gt ^; : 513

[Synthesis Example 8] Synthesis of Compound (135)

Synthesis of [Reaction Scheme 8-1] [Intermediate 8-a]

 [Intermediate 8-a]

Fill the dried 2 L reactor with nitrogen, add 100.0 g (999 mmol) of 3-methylcrotonic acid and 500 mL of benzene and stir. 399.5 g (2996 mmol) of aluminum chloride was slowly added thereto, and the mixture was refluxed with stirring for 5 hours. When the reaction was completed, the reaction solution was slowly added dropwise to 1500 mL of 6 N hydrochloric acid at a low temperature and stirred for 30 minutes. The mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and purified by distillation under reduced pressure to obtain 125.0 g (yield: 78%).

Synthesis of [Reaction Scheme 8-2] [Intermediate 8-b]

[Intermediate 8-a] [Intermediate 8-b]

600 mL of acetic acid and 30 mL of hydrochloric acid were added to 60 g (375 mmol) of the compound represented by [Intermediate 8-a] obtained in the above Reaction Scheme 8-1 and 65 g (450 mmol) of phenylhydrazine hydrochloride and the mixture was refluxed with stirring for 12 hours . After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography to obtain 63 g (yield 72%) of a compound represented by the following formula 8-b.

[Reaction Scheme 8-3] Synthesis of [Formula 135]

[Intermediate 8-b] [Intermediate 4-d]

Synthesis Example 1 [Intermediate 8-b] was synthesized in the same manner as Intermediate 8-b, except that [Intermediate 4-d] was used instead of [Intermediate 1-e] instead of [Intermediate 1-f] 3.6 g (yield: 37.4%) of the compound represented by the general formula [135] was obtained.

MS [M] ^< ⁺ & gt ^; : 513

[Synthesis Example 9] Synthesis of Compound (136)

Synthesis of [Synthesis 9-1] [Synthesis of Intermediate 9-a]

[Intermediate 9-a]

Synthesis Example 1 27.6 g (yield 81.6%) of the compound represented by [Intermediate 9-a] was synthesized except that 1-naphthylboronic acid was used in place of phenylboronic acid used in [Scheme 1-3] .

Synthesis of [Reaction Scheme 9-2] [Intermediate 9-b]

[Intermediate 9-a] [Intermediate 9-b]

Synthesis Example 1 The procedure of Synthesis Example 1 was repeated except that [Intermediate 9-a] was used instead of [Intermediate 1-c] to obtain 23.1 g of the compound represented by [Intermediate 9-b] %).

Synthesis of [Synthesis 9-3] [Intermediate 9-c]

[Intermediate 9-b] [Intermediate 9-c]

Synthesis Example 1 The procedure of Synthesis Example 1 was repeated except for using Intermediate 9-b instead of Intermediate 1-d to obtain 18.7 g of Intermediate 9-c (yield: 80.9% %).

[Reaction formula 9-4] Synthesis of [Formula 136]

[Intermediate 8-b] [Intermediate 9-c]

Synthesis Example 1 Synthesis was conducted in the same manner as Intermediate 8-b except for using Intermediate 9-c instead of Intermediate 1-e instead of Intermediate 1-f used in Reaction Scheme 1-7 [ To obtain 4.7 g (yield: 41.9%) of the compound represented by the formula (136).

MS [M] ^< ⁺ & gt ^; : 563

[Synthesis Example 10] Synthesis of Compound (137)

Synthesis of [Synthesis 10-1] [Synthesis of Intermediate 10-a]

[Intermediate 10-a]

Synthesis Example 4 The procedure of Synthesis Example 4 was repeated except that 2-naphthylboronic acid was used in place of phenylboronic acid used in Reaction Scheme 4-2 to obtain 30.1 g (yield: 83.7%) of the compound represented by [Intermediate 10-a] .

Synthesis of [Reaction Scheme 10-2] [Intermediate 10-b]

[Intermediate 10-a] [Intermediate 10-b]

Synthesis Example 1 28.3 g (yield 78.5%) of the compound represented by [Intermediate 10-b] was synthesized except that [Intermediate 10-a] was used instead of [Intermediate 1-c] used in [Scheme 1-4] %).

Synthesis of [Reaction Scheme 10-3] [Intermediate 10-c]

[Intermediate 10-b] [Intermediate 10-c]

Synthesis Example 1 Synthesis was conducted in the same manner as in [Scheme 1-5], except that [Intermediate 10-b] was used instead of [Intermediate 1-d], to thereby yield 25.5 g of the compound represented by [Intermediate 10-c] %).

[Synthesis of Reaction Formula 10-4] [Formula 137]

[Intermediate 8-b] [Intermediate 10-c] [Compound 137]

Synthesis Example 1 Synthesis was conducted in the same manner except that [Intermediate 8-b] was used instead of [Intermediate 1-f] used in [Scheme 1-7] instead of [Intermediate 10-c] 5.3 g (yield: 42.8%) of a compound represented by the formula (137) was obtained.

MS [M] ^< ⁺ & gt ^; : 563

Example: Preparation of organic light emitting diode

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was adjusted to have a pressure of 1 × 10 ^-6 torr. Then, organic substances were injected onto the ITO using DNTPD (700 Å), NPD (300 Å) 10 Å) (300 Å), compound E: Liq = 1: 1 (250 Å), Liq (10 Å) and Al (1,000 Å).

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

DNTPD NPD

RD-1 Compound E Liq

Comparative Example

The organic light emitting diode device for the comparative example was fabricated in the same manner except that the following compounds F, G, H and I were used in place of the compound prepared by the invention in the device structure of the embodiment, and the compounds F, G, H, I The structure of which is as follows.

<Compound F><CompoundG><CompoundH><CompoundI>

The driving voltage V, the power efficiency (lm / W) and the color coordinates (CIEx, CIEy) were measured for the organic electroluminescent devices manufactured according to the comparative examples 1 to 4 and the embodiments 1 to 7, Are shown in Table 1 below.

division Host Doping concentration% V lm / W CIEx CIEy Comparative Example 1 Compound F 10 4.5 14.0 0.665 0.334 Comparative Example 2 Compound G 10 4.7   17.0 0.664 0.335 Comparative Example 3 Compound H 10 4.7 14.5 0.664 0.335 Comparative Example 4 Compound I 10 5.2 15.0 0.664 0.335 Example 1 Compound 23 10 3.6 17.0 0.664 0.335 Example 2 Compound 24 10 3.5 17.5 0.664 0.335 Example 3 Compound 92 10 3.3 22.5 0.665 0.334 Example 4 Compound 136 10 4.2 18.5 0.665 0.334 Example 5 Compound 138 10 4.2 17.9 0.664 0.335 Example 6 Compound 117 10 4.0 15.0 0.665 0.334 Example 7 Compound 153 10 3.9 16.4 0.665 0.334

As shown in the above Table 1, the organic compounds obtained according to the present invention can be used as the compounds F, G, H and I, that is, as compared with the compounds having no X substituent at specific positions, , The driving voltage is relatively lowered, and thus the power efficiency is higher.

Claims (8)

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

In the above formula (1)
L is a single bond or a divalent group selected from a substituted or unsubstituted alkylene group having 2 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms And m is an integer of 0 to 4, and when m is 2 or more, a plurality of Ls may be the same or different from each other,
ETU- * in the above formula (1) is represented by the following formula [1-1] or [1-2]
[Structural formula 1-1] [Structural formula 1-2]

In the above Structural Formulas 1-1 to 1-2,
A ₁ to A ₇ are the same or different from each other and each independently represent CR ₁ to CR ₇ Or N,
X and R ₁ to R ₇ are the same or different and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted Or a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 alkyl group A substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having hetero atoms such as O, N or S, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, (Except when X is hydrogen), &lt; RTI ID = 0.0 &gt;
Wherein R ₁ to R of two adjacent ones of ₇ are connected to each other alicyclic hydrocarbon ring, or a monocyclic or polycyclic, and may form an aromatic hydrocarbon ring, the carbon atom of the formed alicyclic, aromatic hydrocarbon ring N, S, O, At least one selected from the group consisting of Se, Te, Po, NR _{14 ,} SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (═O), C═O, S═O and BR ₂₁ Lt; / RTI &gt; and R &lt; ₁₄ &gt; To R ₂₁ are the same as defined the above R ₁ to R _7,
* -HTU of the above formula (1) is represented by the following formula 1,
[Structural formula 1]

In the above formula 1,
M is either a single _{bond, CR 12 R 13, NR 14} , O, S, Se, Te, Po, SiR 15 R 16, GeR 17 R 18, PR 19, PR 20 (= O), C = O, S = O and BR ₂₁ , and the R ₁₂ To R &lt; ₂₁ &gt; are the same as defined for R &_lt; ₁ &gt; to R &_lt; ₇ &
R ₁₂ and R ₁₃ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ are each connected to form a substituted or unsubstituted fused C 3 -C 30 cycloalkyl group, a substituted or unsubstituted fused C 2 -C 30 A substituted or unsubstituted aryl group having 5 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
Each of Ar ₁ to Ar ₂ is independently a substituted or unsubstituted aryl group having 5 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom. The method according to claim 1,
[Formula 1] is an organic light-emitting compound represented by the following Structural Formula 2 to Structural Formula 4:
[Structural formula 2]

[Structural Formula 3]

[Structural Formula 4]

In the above Structural Formulas 2 to 4,
R ₈ To R ₁₁ is the above R ₈ as defined for R ₁ to R ₇ in Formula 1, and To R &lt; ₁₁ &gt; may be connected to each other to form a condensed aliphatic, condensed aromatic, condensed heteroaliphatic or fused heteroaromatic ring,
Z is a single _{bond, CR 12 R 13, NR 14} , O, S, Se, Te, Po, SiR 15 R 16, GeR 17 R 18, PR 19, PR 20 (= O), C = O, S = O and BR ₂₁ , and the R ₁₂ To R ₂₁ are the the same as defined in Formula 1 of R ₁ to R _7, wherein R ₁₂ and R _13, R ₁₅ and R _16, R is ₁₇ and R ₁₈ are each connected to each other a substituted or unsubstituted fused A substituted or unsubstituted fused C 2 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 5 -C 30 aryl group or a substituted or unsubstituted C 3 -C 30 heteroaryl group having 3 to 30 carbon atoms, Group,
Y is the same as defined for R ₁ to R ₇ in the above formula (1), m is an integer of 1 to 5, and when m is 2 or more, plural Ys may be the same or different,
The Y may form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring by bonding to adjacent substituents, and the carbon atom of the alicyclic or aromatic hydrocarbon ring may be N, S, O, Se, Te, Po, May be substituted with any one or more substituted or unsubstituted heteroatoms selected from NR _{14 ,} SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (= O), C═O, S═O and BR ₂₁ . The R ₁₄ To R ₂₁ is as defined the above R ₁ to R _7. The method according to claim 1,
Wherein X is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom. The method according to claim 1,
The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is selected from the following formulas (2) to (162):

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 Formula 1 according to Claim 1. 6. The method of claim 5,
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. The method according to claim 6,
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 following formula (1). 6. The method of claim 5,
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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