KR102239027B1 - 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 the following [Chemical Formula 1] and an organic light-emitting device comprising the same, wherein the organic light-emitting device including the organic light-emitting compound according to the present invention has a low driving voltage, luminous efficiency and lifetime characteristics This is excellent.
[Formula 1]

Description

An organoelectro luminescent compound and an organoelectro luminescent device using the same}

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

Recently, organic light emitting devices capable of low voltage driving by self-luminous type have superior viewing angles and contrast ratios compared to liquid crystal displays, which are the mainstream of flat panel display devices, and do not require a backlight, are lightweight and thin, and are advantageous in terms of power consumption and color reproduction. Due to its wide range, it is attracting attention as a next-generation display device.

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

The organic light emitting device can form a device on a transparent substrate that can bend like a plastic, and can be driven at a voltage lower than 10 V compared to a plasma display panel or an inorganic light emitting display, and consumes relatively little power. , It has the advantage of excellent color. In addition, the organic electroluminescent device is capable of displaying three colors of green, blue, and red, and thus is a subject of much interest as a next-generation rich color display device.

The most important factor in determining the luminous efficiency in an organic electroluminescent device is a light-emitting material. Currently, a fluorescent material is widely used as a light emitting material, but the development of a phosphorescent material is one of the methods that can theoretically improve luminous efficiency more due to the light emitting mechanism, and accordingly, various phosphorescent materials have been developed so far. In particular, CBP (4,4'-N,N'-dicarbazolbiphenyl) is the most widely known as a phosphorescent host material, and materials in which various substituents are introduced into carbazole are (Japanese Patent Publication 2008-214244, Japanese Patent Publication). 2003-133075) or an organic electroluminescent device using a BALq derivative as a host is known.

However, organic electroluminescent devices using phosphorescent materials have significantly higher current efficiency compared to devices using fluorescent materials, but when materials such as BAlq and CBP are used as the host of phosphorescent materials, they are driven compared to devices using fluorescent materials. Since the voltage is high, there is no great advantage in terms of power efficiency, and the lifespan of the device is not satisfactory. Therefore, there is a demand for the development of a more stable and high-performance host material in terms of driving voltage and lifespan characteristics.

An object of the present invention is to provide an organic light-emitting compound having superior luminous efficiency and improved power efficiency and long lifespan characteristics than conventional materials.

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

The present invention provides an organic light emitting compound represented by the following [Chemical Formula A] in order to solve the above problems.

[Formula A]

In addition, the present invention comprises 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 is represented by the [Formula A]. It provides an organic light emitting device comprising at least one organic light emitting compound to be displayed.

Specific substituents of the organic light-emitting compound represented by [Chemical Formula A] according to the present invention will be described later.

When the organic light-emitting compound according to the present invention is employed in an organic light-emitting device, low-voltage driving is possible, and luminance, luminous efficiency, and lifespan characteristics are very excellent.

1 is a conceptual diagram showing the structure of an organic light emitting device according to an embodiment of the present invention.

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

The organic light-emitting compound according to the present invention is characterized in that it is represented by the following [Chemical Formula A].

[Formula A]

In the above [Formula A],

R ₁ to R ₂₀ are the same as or different from each other, and each independently 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 2 to 30 alkenyl group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioc Group, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted and heteroatoms It is any one selected from a C2-C50 heteroaryl group, a cyano group, a nitro group, and a halogen group having O, N or S.

In addition, the R ₁ to R ₂₀ are each independently connected with a substituent adjacent to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic carbon atoms are It may be substituted with any one or more heteroatoms selected from N, S, and O.

"-*" of Q _{is connected to any one selected from among 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.

L is a single bond or a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C2 to C60 Alkenylene group, substituted or unsubstituted C2 to C60 alkynylene group, substituted or unsubstituted C3 to C60 It is a linking group selected from a cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms. .

n is an integer of 1 to 3, and when n is 2 or more, a plurality of L is the same as or different from each other.

[Chemical Formula A] may be a compound represented by any one of the following [Chemical Formula A1] to [Chemical Formula A6] depending on the bonding position of Q.

[Formula A1] [Formula A2] [Formula A3]

[Formula A4] [Formula A5] [Formula A6]

In the [Chemical Formula A1] to [Chemical Formula A6], R ₁ to R ₂₀ , L and n are the same as defined in [Chemical Formula A].

In addition, in [Formula A], [Formula A1] to [Formula A6], the L may be a single bond, or may be any one selected from [Structural Formula 1] to [Structural Formula 8] below, and in the case of a plurality of individuals, each of the same or It can be different.

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

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

In the [Structural Formulas 1] to [Structural Formulas 8], hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each of the structural formulas.

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms , C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group , C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylsilyl It means substituted with one or more substituents selected from the group consisting of a group and an aryloxy group having 1 to 24 carbon atoms.

In addition, the range of carbon atoms of the alkyl group or aryl group in the'substituted or unsubstituted alkyl group having 1 to 30 carbon atoms' and'substituted or unsubstituted aryl group having 5 to 50 carbon atoms' consider the portion where the substituent is substituted It does not mean the total number of carbon atoms constituting the alkyl moiety or aryl moiety when viewed as unsubstituted. For example, a phenyl group in which a butyl group is substituted in the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

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

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

In addition, at least one hydrogen atom in the aryl group is 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')(R") , R'and R" are each independently an alkyl group having 1 to 10 carbon atoms, and in this case, referred to as "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, Alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group , It may be substituted with a C2-C24 heteroaryl group or a C2-C24 heteroarylalkyl group.

The heteroaryl group, which is a substituent used in the compound of the present invention, is a heteroaromatic organic radical having 2 to 24 carbon atoms which may contain 1 to 4 heteroatoms selected from N, O, P or S in each ring in the aryl group. It means, and the rings may be fused to form a ring. And at least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.

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, and at least one hydrogen atom in the alkyl group is The atom can be substituted with the same substituent as in the case of the aryl group.

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

Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclo Butylsilyl, dimethylfurylsilyl, and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.

In addition, the present invention includes a first electrode, a second electrode opposite to the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is the [Chemical Formula A] in the present invention. It may contain one or more kinds of organic light-emitting compounds represented by.

In addition, the organic layer containing the organic light emitting compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. have. In this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer is formed of a host and a dopant, and the organic emission compound of the present invention may be used as a host.

Meanwhile, in the present invention, a dopant material may be used in addition to the host for the emission layer. When the emission layer includes a host and a dopant, the content of the dopant may be generally selected from 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 may be used as the material for the electron transport layer, which has a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinorate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis(benzoquinolin-10-). olate: Bebq2), ADN, [Compound 201], [Compound 202], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 201] [Compound 202] BCP

In addition, as for the electron transport layer used in the present invention, an organometallic compound represented by the following [Chemical Formula C] may be used alone or in combination with the electron transport layer material.

[Formula C]

In [Chemical Formula C],

Y is a portion in which any one selected from C, N, O, and S is directly bonded to the M to form a single bond, and a portion in which any one selected from C, N, O, and S forms a coordination bond to the M. It includes, and is a ligand chelated by the single bond and the coordination bond.

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

OA is a monovalent ligand capable of a single bond or coordination bond with M, wherein O is oxygen, and 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, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms Any one selected from an alkenyl group and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom.

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

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

In addition, each of Y is the same or different, and may be any one selected from the following [Structural Formula C1] to [Structural Formula C39] independently of each other.

[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 [Structural Formula C1] to [Structural Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A C3-C30 heteroaryl group, 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 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It is selected from groups, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

L is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 alkyl group. It is selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein 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, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

Hereinafter, the organic electroluminescent device of the present invention will be described with reference to FIG. 1.

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

Referring to FIG. 1, an organic light emitting device of the present invention and a method of manufacturing the same will be described as follows.

First, an anode 20 is formed by coating a material for an anode electrode on the substrate 10. Here, as the substrate 10, a substrate used in a typical organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness is preferable. In addition, as a 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 have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum thermal evaporation or spin coating on the anode 20 electrode. Thereafter, a hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

The hole injection layer material is not particularly limited as long as it is commonly used in the art, and may be used, for example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ], etc. can be used.

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

Subsequently, an organic light-emitting layer 50 is stacked on the hole transport layer 40 and 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. can do. The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of a light-emitting compound, and representatively, BAlq, BCP, TPBI, and the like may be used.

As a material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and [Formula 101] to [Formula 107] may be used, but limited thereto It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 101 Formula 102 Formula 103

Chemical Formula 104 Chemical Formula 105 Chemical Formula 106

Chemical Formula 107

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode-forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form the cathode 80 electrode. Here, the cathode-forming metals include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like can be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO can be used.

In addition, the emission layer may be formed of a host and a dopant, and according to a specific example of the present invention, the thickness of the emission layer is preferably 50 to 2,000 Å.

In this case, the dopant used in the light emitting layer may be one or more compounds selected from compounds represented by the following [General Formula A-1] to [General Formula J-1].

[General Formula A-1]

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, It is selected from Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag.

In addition, the L ₁ , L ₂ and L ₃ may be the same as or different from each other as a ligand, and each independently may be any one selected from the following [Structural Formula D], and “*” in the following Structural Formula D is coordinated to the metal ion M Express the site.

[Structural Formula D]

In the [Structural Formula D],

R is different from each other or the same, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted carbon number 5 to 50 heteroaryl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted A substituted or unsubstituted alkylamino 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 It may be any one selected from, wherein each R is independently 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 may be further substituted with one or more substituents selected from, and the R is connected to each of the adjacent substituents by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring. I can.

L is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 alkyl group. It is selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein 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, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

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

[General Formula B-1]

In the above [general formula B-1],

M ^A1 represents the same metal ion as defined in [General Formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 Each independently represents a carbon atom or a nitrogen atom, Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, L ^A11 , L ^A12 , L ^A13 , L ^A14 each represent a linking group such as _{L 1} , L ₂ and L ₃ defined in [General Formula A-1], ^{and Q A11} and Q ^A12 represent an atom bonded to ^{M A1} It shows the partial structure to contain.

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

[General Formula C-1]

In the above [general formula C-1],

M ^B1 represents the same metal ion as defined in [General Formula A-1], and Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, and 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, and a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represent a linking group, Q ^B11 , Q ^B12 represents a partial structure containing an atom bonded to M ^B1.

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

[General Formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1], and R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent that is connected to each other to form a 5-membered ring, and a substituent that is not connected to each other. , R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent that is connected to each other to form a 5-membered ring, and a substituent that is not connected to each other, and R ^C13 and R ^C14 are each independently a hydrogen atom, each of which is a 5-membered ring Represents a substituent that forms a substituent, a substituent that is not connected to each other, and 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, and Q ^C11 and Q ^C12 Represents a partial structure containing an atom bonded to M ^C1.

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

[General Formula E-1]

In the above [general formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], and 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 required to form a 5-membered ring, and L ^D11 and L ^D12 represent a linking group.

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

[General Formula F-1]

In the above [general formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], and J ^E11 and J ^E12 each independently represent an atomic group required to form 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.

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

[General Formula G-1]

In the above [general formula G-1],

M ^F1 represents the same metal ion as defined in [General Formula A-1], L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be linked to each other to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonded to M ^F1.

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

[General Formula H-1] [General Formula H-2] [General 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, and may form a fused ring with a substituent adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2. In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different, respectively.

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

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

In addition, ^{it is preferable that n 1} and m ¹ make the metal complex represented by the above [general formula H-1] a neutral complex.

In the above [General Formula H-2],

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

In the above [General Formula H-3],

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

According to an embodiment of the present invention, the compound represented by [General Formula H-1] to [General Formula H-3] may be any one selected from the following compounds.

[General Formula I-1]

In the above [general formula I-1],

Ring A, Ring B, Ring C, and Ring D represent a nitrogen-containing heterocycle in which any two of the rings A to D may have a substituent, and the other two rings are an aryl ring or heteroaryl that may have a substituent. Represents a ring, and can form a condensed ring with ring A and ring B, ring A and ring C, and/or ring B and ring D.

X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which any two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom.

Q ¹ , Q ² and Q ³ each independently represent a divalent atom (term) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. Z ¹ , Z ² , Z ³ and Z ⁴ are any two representing a coordination bond, and the other two represent a covalent bond, an oxygen atom, or a sulfur atom.

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

[General Formula J-1]

In the above [general formula J-1],

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

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

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

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

In addition, the emission layer may further include various hosts and various dopant materials in addition to the dopant and host.

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

In addition, the organic electroluminescent device according to the present invention may be used in a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat lighting device, and a monochromatic or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereto.

Synthesis Example 1. Synthesis of [Compound 1]

(1-1)

Intermediate 1-1

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

(1-2)

Intermediate 1-2

At room temperature, the synthesized intermediate 1-1 (20.0 g, 119 mmol) and 120 mL of tetrahydrofuran were added to a flask under a nitrogen stream, followed by stirring. Phenyl magnesium bromide (3.0 M in Et ₂ O) was added dropwise to 79.3 mL (238 mmol). After stirring at reflux for about 1 hour, the temperature was set to 0°C. Ethyl chloroformate (15.5 g, 143 mmol) was added dropwise and stirred under reflux for about 1 hour. An aqueous ammonium chloride solution was added until it became slightly acidic, and the resulting solid was filtered and washed with water and heptane to obtain 30 g (82% yield) of Intermediate 1-2.

(1-3)

Intermediate 1-3

At room temperature, the synthesized intermediate 1-2 (30.0 g, 135 mmol) and about 80 mL of phosphorus oxychloride were added to a flask under a nitrogen stream, followed by stirring. After reflux stirring overnight, the temperature was cooled to -20 ℃ the next day, and water was slowly added dropwise to about 400 mL. The resulting solid was filtered and washed with water, methanol, and heptane. Recrystallized from toluene and heptane to obtain 17.5 g of Intermediate 1-3. (Yield 45%)

(1-4)

Intermediate 1-4

In a round bottom flask (9-phenyl-9H-carbazol-3-yl) boronic acid 44.8 g (0.156 mol), 2-bromonitrobenzene 26.26 g (0.13 mol), tetrakis (triphenylphosphine) palladium 3.0 g (0.0026 mol), potassium carbonate 45 g (0.325 mol), tetrahydrofuran 130 mL, toluene 130 mL, and water 30 mL were added, followed by refluxing at 80° C. for 12 hours. When the reaction was completed, extraction was performed using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from dichloromethane and hexane to obtain 40.2 g of Intermediate 1-4. (Yield 85%)

(1-5)

Intermediate 1-5

To a round-bottom flask, 26.2 g (0.072 mol) of the synthesized intermediate 1-4, 47.14 g (0.18 mol) of triphenylphosphine, and 200 mL of dichlorobenzene were added, followed by reflux stirring at 160° C. for 12 hours. When the reaction was completed, it was filtered in a hot state, and then extracted using dichloromethane and distilled water. The organic layer was concentrated under reduced pressure and subjected to column chromatography with dichloromethane and hexane to obtain 17.9 g of Intermediate 1-5 (yield 75%).

(1-6)

Compound 1

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a round bottom flask under a nitrogen stream, followed by stirring for about 30 minutes. 13.6 g (41 mmol) of the synthesized intermediate 1-5 and 100 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. 15.4 g (53 mmol) of the synthesized intermediate 1-3 and 100 mL of dimethylformamide were added, followed by stirring overnight. 600 mL of distilled water was added to the flask, and the resulting solid was filtered. Compound 1 was obtained by recrystallization from toluene. (12.1g, yield 50%)

MS (MALDI-TOF): m/z 587 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 118.8 119.8 121.4 121.8 124.9 125.5 126.6 127.2 127.3 127.4 127.5 127.9 128.5 128.7 129.2 129.3 130.1 130.9 131.8 133 133.1 134.4 136.8 144.4 145.4 150 155.8 161 [42C]

Synthesis Example 2. Synthesis of [Compound 2]

(2-1)

Intermediate 2-1

In a round bottom flask, 50 g (0.45 mol) of 1,2-cyclohexanedione, 135 g (0.92 mol) of phenyl hydrazine-hydrochloride, and 1500 mL of ethyl alcohol were added, and after stirring for 30 minutes, 5 mL of concentrated sulfuric acid was added to the reaction solution. Apply. The mixture was stirred at 65° C. for 10 hours. When the reaction was completed, it was lowered to room temperature, filtered, and washed with ethyl alcohol. After drying under reduced pressure at room temperature, the filtrate, 1200 mL of acetic acid, and 120 mL of trifluoroacetic acid were added to a round bottom flask without purification, followed by stirring at 110° C. for 8 hours. When the reaction was completed, it was lowered to room temperature, filtered, and washed with ethyl alcohol and hexane. After drying under reduced pressure at room temperature, 80 g of Intermediate 2-1 was obtained. (Yield 76.8%)

(2-2)

Intermediate 2-2

In a round bottom flask, the synthesized intermediate 2-1 48.5 g (0.189 mol), iodobenzene 42.5 g (0.208 mol), copper powder 19.4 g (0.378 mol), 18-crown-6 15 g (0.057 mol), carbonic acid Potassium 104.5 g (0.756 mol) was added in that order, and 480 mL of 1,2-dichlorobenzene was added, followed by reflux stirring at 180° C. for 2 days. When the reaction was completed, extraction was performed using dichloromethane and distilled water. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography with hexane to obtain 17.9 g of Intermediate 2-2 (yield 28%).

(2-3)

Compound 2

Compound 2 was synthesized from the synthesized intermediate 2-2 in the same manner as in (1-6). (8.5 g, 35% yield)

MS (MALDI-TOF): m/z 587 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 118.8 119.8 120 120.5 121.4 124 124.9 125.5 126.6 127.2 127.3 127.4 127.5 127.9 128.7 129.2 129.3 131.8 133 133.1 134.4 135.5 136.8 144.4 145.4 150 155.8 161 [42C]

Synthesis Example 3. Synthesis of [Compound 3]

(3-1)

Intermediate 3-1

Intermediate 3-1 was synthesized using the synthesis method of (2-1) to (2-3) of Synthesis Example 2.

(3-2)

Compound 3

The synthesized intermediate 3-1 15.6 g (21 mmol), diphenylamine 9.1 g (53.6 mmol), palladium (II) acetate 0.2 g (0.9 mmol), triteributylphosphine (50% in toluene) 0.8 mL (1.7 mmol), 3.3 g (64.3 mmol) of cesium carbonate were dissolved in 500 mL of toluene and stirred under reflux for 8 hours. After completion of the reaction, it was cooled at room temperature, methanol was added, and the resulting solid was filtered under reduced pressure. Again, the solid was washed with distilled water, methanol, and hexane, followed by column chromatography and recrystallized with monochlorobenzene to give 7.5 g (39% yield) of compound 3.

MS (MALDI-TOF): m/z 921 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103.9 107.6 110.8 115.8 119.7 120.3 122.6 124.9 125.5 125.7 126.6 126.8 127.2 127.3 127.4 127.5 127.9 128.5 128.7 129.2 129.3 129.6 129.9 131.8 132.7 133 134.4 136.8 144.4 145.9 146.3 150 155.8 161 [66C]

Synthesis Example 4. Synthesis of [Compound 4]

(4-1)

Intermediate 4-1

3-bromo-9H-carbazole 20.0 g (81.3 mmol), 3-iodopyridine 33.3 g (162.5 mmol), copper powder 10.3 g (162.5 mmol), 18-crown-6 4.3 g (16.3 mmol), carbonic acid Potassium 33.7 g (243.9 mmol) was sequentially added, and 1,2-dichlorobenzene 200 mL was added, followed by refluxing and stirring at 180° C. for 1 day. When the reaction was completed, the solution was concentrated under reduced pressure after high-temperature filtering, and the organic layer solution was subjected to column chromatography with hexane to obtain 22.0 g of Intermediate 4-1. (Yield 84%)

(4-2)

Intermediate 4-2

After dissolving 21.0 g (65.0 mmol) of the synthesized intermediate 4-1 in 210 ml of tetrahydrofuran under a stream of nitrogen, 49 mL (78.0 mmol) of 1.6 M normal-butyllithium was slowly added dropwise while stirring at -78 °C,- It was stirred for 1 hour while maintaining at 78 ℃. Thereafter, 8.1 g (78.0 mmol) of trimethylborate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 2 hours. When the reaction was completed, 100 mL of a 2 M aqueous hydrochloric acid solution was added at room temperature and stirred for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain 12.1 g of Intermediate 4-2. (Yield 65%)

(4-3)

Compound 4

Using the synthesized intermediate 4-2, compound 4 was synthesized in the same manner as in (1-4) to (1-6) of Synthesis Example 1. (11 g, 35% yield)

MS (MALDI-TOF): m/z 588 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 115.3 118.8 119.8 121.4 121.8 124.9 125.5 126.6 127.2 127.3 127.4 127.5 127.9 128.5 128.7 129.2 130.1 131.8 133 133.1 134.4 144.4 147.6 149.9 150 155.8 161 [41C]

Synthesis Example 5. Synthesis of [Compound 5]

(5-1)

Intermediate 5-1

In a round bottom flask, the synthesized intermediate 1-5 13.6 g (0.041 mol), 3-bromoiodobenzene 15.2 g (0.054 mol), copper powder 7.9 g (0.124 mol), 18-crown-6 2.2 g (0.008 mol) ), potassium carbonate 28.6 g (0.207 mol) was sequentially added, and 150 mL of 1,2-dichlorobenzene was added, followed by refluxing at 180° C. for 2 days. When the reaction was completed, extraction was performed using dichloromethane and distilled water, the organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography with hexane to obtain 13.4 g of Intermediate 5-1. (Yield 67%)

(5-2)

Intermediate 5-2

In a round-bottom flask, 25.3 g (0.052 mol) of the synthesized intermediate 5-1, 16.2 g (0.063 mol) of bis (pinacolato) diboron, 1.27 g (0.0016 mol) of PdCl2 (dppf), 11.8 g (0.156 of potassium acetate), potassium acetate mol), 250 mL of dimethyl sulfoxide was added, followed by reflux stirring at 110° C. for 1 day. When the reaction was completed, extraction was performed using dichloromethane and distilled water, and the organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography with dichloromethane and hexane to obtain 21.7 g of Intermediate 5-2. (Yield 78%)

(5-3)

Compound 5

In a round bottom flask, the synthesized intermediate 5-2 15 g (0.028 mol), the synthesized intermediate 1-3 6.4 g (0.022 mol), tetrakis (triphenylphosphine) palladium 1.02 g (0.0008 mol), potassium carbonate 9.2 g (0.066 mol), 40 mL of tetrahydrofuran, 40 mL of 1,4-dioxane, and 15 mL of water were added, followed by reflux stirring at 80° C. for 12 hours. When the reaction was completed, extraction was performed using ethyl acetate and distilled water, the organic layer was concentrated under reduced pressure, and recrystallized with tetrahydrofuran and hexane was repeated to synthesize compound 5. (5.8 g, yield 31%)

MS (MALDI-TOF): m/z 663 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 105.4 109.5 111 118.7 118.8 119.8 121.3 121.4 121.8 124.3 124.9 125.5 126.6 127.2 127.3 127.4 127.5 127.9 128.5 128.7 129.2 129.3 129.8 130.9 131.1 131.2 131.8 133 134.4 135.5 136.8 142.4 145.4 150 155.8 161 [48C ]

Synthesis Example 6. Synthesis of [Compound 6]

(6-1)

Compound 6

In the above synthesis, compound 6 was synthesized in the same manner as in 5, using 1-bromo-4-iodonaphthalene instead of 3-bromoiodobenzene in (5-1). (5.4g, yield 27%)

MS (MALDI-TOF): m/z 713 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 105.4 109.5 111 118.8 119.8 121.4 121.8 123.8 124.9 125.3 125.5 126.3 126.6 126.7 127.2 127.3 127.4 127.5 127.9 128.3 128.5 128.7 129.2 129.3 130.4 130.9 131.1 131.8 132.8 133 133.3 134.4 135.5 135.8 136.8 145.4 150 155.8 161 [52C]

Synthesis Example 7. Synthesis of [Compound 7]

(7-1)

Intermediate 7-1

(7-2)

Compound 7

Using 4-pyridinyl magnesium bromide (0.25M in THF) instead of _{phenyl magnesium bromide (3.0M in Et 2} O) used in Scheme (1-2), the same as in (1-2) to (1-3) Intermediate 7-1 was obtained by the method, and compound 7 was synthesized in the same manner as in Reaction Scheme (1-6) using it. (5.6g, yield 23%)

MS (MALDI-TOF): m/z 588 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 118.8 119.8 121.3 121.4 121.8 124.9 125.5 126.6 127.2 127.3 127.4 127.9 128.5 129.3 130.1 130.9 133 133.1 134.4 136.8 140.3 144.4 145.4 149.8 150 155.8 161 [41C]

Synthesis Example 8. Synthesis of [Compound 8]

(8-1)

Intermediate 8-1

At room temperature, 14.3 g (589 mmol) of magnesium, 3 iodines, and 60 mL of tetrahydrofuran were added to a round-bottom flask A under a nitrogen stream, followed by stirring for about 10 minutes. To a flask immersed in water, 125.9 g (540 mmol) of 4-bromobiphenyl and 240 mL of tetrahydrofuran were added dropwise and stirred under reflux for about 2 hours. After 2 hours, the temperature was set to room temperature. At room temperature, 41.3 g (246 mmol) of the synthesized intermediate 1-1 and 150 mL of tetrahydrofuran were added to another round-bottom flask B under a nitrogen stream, followed by stirring. At room temperature, the reaction solution prepared in flask A was slowly added dropwise to flask B immersed in water. After that, it was stirred under reflux for about 1 hour. The temperature was set to 0° C., and 34.8 g (368 mmol) of methyl chloroformate was added dropwise, followed by reflux stirring for about 1 hour. The temperature was set to 0° C., an aqueous ammonium chloride solution was added until it became slightly acidic, and the resulting solid was filtered and washed with water and heptane. 59 g of intermediates 8-1 were obtained. (Yield 69%)

(8-2)

Compound 8

Using the synthesized intermediate 8-1, compound 8 was synthesized in the same manner as in (1-3) to (1-6) of Synthesis Example 1. (6.5g, yield 40%)

MS (MALDI-TOF): m/z 663 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 118.8 119.8 121.4 121.8 124.9 125.5 126.6 127.2 127.3 127.4 127.6 127.9 128 128.5 129.2 129.3 130.1 130.7 130.9 133 133.1 134.4 136.8 140.8 144.4 145.4 150 155.8 161 [48C]

Synthesis Example 9. Synthesis of [Compound 9]

(9-1)

Intermediate 9-1

(9-2)

Compound 9

Using (2-fluoro[1,1'-biphenyl]-4-) magnesium bromide (0.5M in THF) instead of phenyl magnesium bromide (3.0M in Et _{2 O) used in Scheme (1-2)} Intermediate 9-1 was obtained in the same manner as in (1-2) to (1-3), and compound 9 was synthesized in the same manner as in Reaction Scheme (1-6). (8.5g, yield 37%)

MS (MALDI-TOF): m/z 681 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 116.4 118.8 119.8 121.4 121.8 123.6 124.9 125.5 126.6 127.2 127.3 127.4 127.6 127.9 128.5 129 129.2 129.3 130 130.1 130.9 133 133.1 133.5 134.4 136.5 136.8 144.4 145.4 150 155.8 159.2 161 [48C ]

Synthesis Example 10. Synthesis of [Compound 10]

(10-1)

Intermediate 10-1

(10-2)

Compound 10

Using (4-benzylphenyl) magnesium bromide (0.5M in 2-methyltetrahydrofuran) instead of phenyl magnesium bromide (3.0M in Et _{2 O) used in Scheme (1-2) above (1-2) to} Intermediate 10-1 was obtained in the same manner as in (1-3), and compound 10 was synthesized in the same manner as in Reaction Scheme (1-6). (7.5 g, yield 36%)

MS (MALDI-TOF): m/z 677 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 41.3 103 109.5 111 118.8 119.8 121.4 121.8 124.9 125.5 126.2 126.3 126.6 127.2 127.3 127.4 127.9 128.2 128.5 128.7 129.2 129.3 130.1 130.9 133 133.1 134.4 136.8 141.5 144.4 145.4 150 155.8 161 [49C]

Synthesis Example 11. Synthesis of [Compound 11]

(11-1)

Intermediate 11-1

(11-2)

Compound 11

The same method as in (8-1) to (8-2) above using pentadeutereobromobenzene instead of 4-bromobiphenyl used in Scheme (8-1), and dimethyl carbonate instead of methyl chloroformate. Compound 11 was synthesized. (8.5 g, yield 36%)

MS (MALDI-TOF): m/z 592 [M] ⁺

¹³ C NMR (75 MHz, CDCl ₃ ) δ: 103 109.5 111 118.8 119.8 121.4 121.8 124.9 125.5 125.6 126.6 127 127.2 127.3 127.4 127.5 127.9 128.5 129.3 130.1 130.9 133 133.1 134.4 136.8 144.4 145.4 150 155.8 161 [42C]

Examples 1 to 11: Preparation of organic light emitting diode

The ITO glass was patterned so that the light emitting area had a size of 2 mm×2 mm, and then washed. After mounting the substrate in the vacuum chamber, the base pressure was 1×10 ^-6 torr, and then the organic material was placed on the ITO DNTPD (700 Å), α-NPB (300 Å), compounds 1 to 11 prepared by the present invention. As a host (90 wt%), the following (piq) ₂ Ir(acac) (10 wt%) was co-deposited (300 Å) _{as a dopant, and Alq 3} (350 Å), LiF (5 Å), The film was formed in the order of Al (1,000 Å), and the measurement was performed at 0.4 mA.

The structures of the DNTPD, α-NPB, (piq) ₂ Ir(acac), Alq ₃ and [Compound 1] to [Compound 11] are as follows.

[DNTPD] [α-NPB]

[(piq) ₂ Ir(acac)] [Alq ₃ ]

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

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

[Compound 9] [Compound 10] [Compound 11]

Example 12

In the device structures of Examples 1 to 11, the compound used in the light emitting layer was selected as [Compound 1], except that [PTOEP] was used instead of [ _{(piq) 2 Ir(acac)], and [PTOEP]} The structure of] is as follows.

[PTOEP]

Comparative Example 1

The organic light-emitting device for Comparative Example 1 was manufactured in the same manner as the CBP 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 a host of the light-emitting layer in the device structure of the above embodiment. The structure of is as follows.

[CBP]

Comparative Examples 2 to 5

The organic light emitting device for Comparative Examples 2 to 5 is the same except that the following [Compound 12] to [Compound 15] were used as a host instead of the compound prepared by the present invention in the device structures of Examples 1 to 11 It was produced and its structure is as follows.

[Compound 12] [Compound 13] [Compound 14] [Compound 15]

Comparative Example 6

The organic light emitting diode device for Comparative Example 6 was fabricated in the same manner, except that [Compound 12] was used instead of [Compound 1] in the device structure of Example 12.

For the organic electroluminescent devices manufactured according to Examples 1 to 12 and Comparative Examples 1 to 6, voltage, current density, luminance, color coordinates, and lifetime were measured, and the results are shown in Table 1 below.

T90 refers to the time it takes for the luminance to decrease from the initial luminance (5000nit) to 90%.

division Host
compound Dopant Voltage
(V) Luminance
(Cd/㎡) CIEx CIEy T ₉₀ (Hr) Example 1 One (piq) ₂ Ir(acac) 4.2 1870 0.668 0.331 1455 Example 2 2 (piq) ₂ Ir(acac) 4.4 1830 0.668 0.331 1355 Example 3 3 (piq) ₂ Ir(acac) 4.3 1890 0.669 0.330 1340 Example 4 4 (piq) ₂ Ir(acac) 4.2 1770 0.668 0.331 1350 Example 5 5 (piq) ₂ Ir(acac) 4.0 1930 0.669 0.330 1490 Example 6 6 (piq) ₂ Ir(acac) 4.3 1920 0.668 0.331 1520 Example 7 7 (piq) ₂ Ir(acac) 4.4 1820 0.668 0.331 1370 Example 8 8 (piq) ₂ Ir(acac) 4.0 1900 0.667 0.332 1540 Example 9 9 (piq) ₂ Ir(acac) 4.2 1830 0.668 0.331 1345 Example 10 10 (piq) ₂ Ir(acac) 4.5 1810 0.668 0.331 1310 Example 11 11 (piq) ₂ Ir(acac) 4.2 1900 0.669 0.330 1485 Example 12 One PTOEP 4.3 1710 0.652 0.321 1410 Comparative Example 1 CBP (piq) ₂ Ir(acac) 7.9 350 0.667 0.332 125 Comparative Example 2 12 (piq) ₂ Ir(acac) 4.4 1250 0.668 0.331 275 Comparative Example 3 13 (piq) ₂ Ir(acac) 4.3 1340 0.667 0.332 315 Comparative Example 4 14 (piq) ₂ Ir(acac) 4.2 1210 0.667 0.332 380 Comparative Example 5 15 (piq) ₂ Ir(acac) 4.4 1020 0.669 0.330 290 Comparative Example 6 12 PTOEP 4.3 1240 0.651 0.320 255

Claims (8)

Organic light-emitting compound represented by the following [Formula A]:
[Formula A]

In the above [Formula A],
R ₁ to R ₂₀ are the same as or different from each other, and each independently 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 2 to 30 alkenyl group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioc Group, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted and heteroatoms It is any one selected from a C2-C50 heteroaryl group, a cyano group, a nitro group, and a halogen group having O, N or S,
"-*" of Q _{is connected to any one selected from 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,
L is a single bond or a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C2 to C60 Alkenylene group, substituted or unsubstituted C2 to C60 alkynylene group, substituted or unsubstituted C3 to C60 It is a linking group selected from a cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms ,
n is an integer of 1 to 3, and when n is 2 or more, each L is the same as or different from each other. The method of claim 1,
The R ₁ to R ₂₀ and L are each independently deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, and 1 to 24 alkynyl group, C 1 to C 24 heteroalkyl group, C 6 to C 24 aryl group, C 6 to C 24 arylalkyl group, C 2 to C 24 heteroaryl group or C 2 to C 24 heteroarylalkyl group, carbon number 1 to 24 alkoxy group, C 1 to C 24 alkylamino group, C 1 to C 24 arylamino group, C 1 to C 24 hetero arylamino group, C 1 to C 24 alkylsilyl group, C 1 to C 24 arylsilyl group and An organic light-emitting compound, characterized in that it is further substituted with one or more substituents selected from the group consisting of an aryloxy group having 1 to 24 carbon atoms. The method of claim 1,
[Chemical Formula A] is an organic light-emitting compound, characterized in that any one selected from compounds represented by the following [Chemical Formula A1] to [Chemical Formula A6]:
[Formula A1] [Formula A2] [Formula A3]

[Formula A4] [Formula A5] [Formula A6]

In the [Chemical Formula A1] to [Chemical Formula A6], R ₁ to R ₂₀ , L and n are the same as defined in [Chemical Formula A]. The method of claim 1,
The L is an organic light-emitting compound, characterized in that selected from the following [Structural Formula 1] to [Structure 8]
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

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

In the [Structural Formulas 1] to [Structural Formulas 8], hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each of the structural formulas. 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, characterized in that the organic layer comprises at least one organic light-emitting compound represented by [Chemical Formula A] according to claim 1. The method of claim 5,
The organic layer comprises at least one layer selected from 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 of claim 6,
The emission layer includes at least one host compound and at least one dopant compound, and the host compound is an organic electroluminescent device, wherein the host compound is a carbazole derivative represented by [Chemical Formula A]. The method of claim 5,
An organic electroluminescent device, characterized in that the organic layer further includes at least one organic light-emitting layer emitting red, green, or blue light to emit white light.

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