KR102169446B1 - An organoelectroluminescent compounds and organoelectroluminescent 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 including the same. It can be driven and has improved power efficiency.
[Formula 1]

Description

An organoelectroluminescent compound and an organoelectroluminescent device using the same}

The present invention relates to an organic light emitting compound and an organic electroluminescent device including 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, 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 drawing 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 be formed 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 EL display, and consumes relatively little power. , It has the advantage of excellent color. In addition, the organic electroluminescent device can display three colors of green, blue, and red, and thus has attracted much attention 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 up to now. In particular, CBP (4,4'-N,N'-dicarbazolbiphenyl) is the most widely known phosphorescent host material so far, 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 than 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 lifetime characteristics.

An object of the present invention is to provide an organic light-emitting compound having improved power efficiency by enabling low voltage driving while having superior luminance and luminous efficiency than conventional materials.

In addition, the present invention is to provide an organic electroluminescent device having improved power efficiency, high brightness, and high efficiency by employing the organic light emitting compound as a light emitting material to enable low voltage driving.

The present invention provides an organic light emitting compound represented by the following [Chemical Formula 1] in order to solve the above problems.

[Formula 1]

In [Chemical Formula 1], A is characterized in that it is selected from the following [Chemical Formula I] to [Chemical Formula III].

[Chemical Formula I] [Chemical Formula Ⅱ] [Chemical Formula Ⅲ]

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 above [Formula 1]. It provides an organic electroluminescent device comprising at least one organic light emitting compound to be displayed.

Specific substituents of the organic light emitting compound represented by [Chemical Formula 1] 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, it is possible to implement a device having excellent power efficiency, high luminance, and high-efficiency characteristics because low voltage driving is possible.

1 is a conceptual diagram showing the structure of an organic light emitting diode 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 a compound represented by the following [Chemical Formula 1].

[Formula 1]

In [Chemical Formula 1], A is characterized in that it is selected from the following [Chemical Formula I] to [Chemical Formula III].

[Chemical Formula I] [Chemical Formula Ⅱ] [Chemical Formula Ⅲ]

The X ₁ to X ₈ may be the same as or different from each other, and may each independently be N or CR ₁₂ .

The R ₁ to R ₁₂ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted Alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or Unsubstituted C3-C30 cycloalkenyl group, substituted or unsubstituted C5-C50 aryl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C5-C50 aryloxy Group, substituted or unsubstituted C 1 to C 30 alkylamino group, substituted or unsubstituted C 6 to C 30 arylamino group. It may be selected from the group consisting of a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsilyl group having 5 to 50 carbon atoms.

L is a single bond as a linking group, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted C2 to C30 group Alkenylene group, substituted or unsubstituted C2-C30 alkynylene group, substituted or unsubstituted C3-C30 It may be selected from a cycloalkylene group, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, n is an integer of 0 to 3, wherein n is 2 or more In the case, the plurality of L may be the same or different from each other.

In addition, the R ₁ to R ₁₂ and L may be combined with each other or with adjacent substituents to form an alicyclic, aromatic monocyclic or polycyclic ring, and the carbon atom of the formed ring is selected from N, S, O, and P. It may be substituted with any one or more heteroatoms.

'*' in the [Chemical Formula I] to [Chemical Formula III] refers to a site bonding to the [Chemical Formula 1].

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 1 to 20 carbon atoms, alkynyl group having 1 to 20 carbon atoms, Halogenated alkyl group having 1 to 20 carbon atoms, aryl group having 5 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 5 to 24 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms As meant to be further substituted with one or more substituents selected from an arylsilyl group having 5 to 24 carbon atoms, an alkylamine group having 1 to 20 carbon atoms, and an arylamine group having 6 to 24 carbon atoms, the R ₁ to R ₁₂ and L Each independently may be further substituted by the above substituents.

In addition, the range of carbon number of the alkyl group or aryl group in the'substituted or unsubstituted alkyl group having 1 to 30 carbon atoms' or'substituted or unsubstituted aryl group having 5 to 50 carbon atoms' considers the portion where the substituent is substituted It does not mean the total number of carbon atoms constituting the alkyl moiety or the 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.

According to an embodiment of the present invention, L may be a single bond or any one linking group selected from the following [Structural Formula A1] to [Structure A16].

[Structural Formula A1] [Structural Formula A2] [Structural Formula A3] [Structural Formula A4]

[Structural Formula A5] [Structural Formula A6] [Structural Formula A7] [Structural Formula A8]

[Structural Formula A9] [Structural Formula A10] [Structural Formula A11] [Structural Formula A12]

[Structural Formula A13] [Structural Formula A14] [Structural Formula A15] [Structural Formula A16]

In the [Structural Formulas A1] to [Structural Formulas A16], hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each of the structural formulas.

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

On the other hand, the aryl group as a substituent used in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and includes 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 the aryl group include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 4-methylbiphenyl group, 4 -Ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, And aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

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, in this case referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, Halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms, alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, carbon number It may be substituted with a 2 to 24 heteroaryl group or a C 2 to 24 heteroarylalkyl group.

The heteroaryl group as a substituent used in the present invention may be any one selected from the following [Structural Formula 1] to [Structural Formula 6].

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

[Structural Formula 4] [Structural Formula 5] [Structural Formula 6]

In the [Structural Formula 1] to [Structural Formula 6],

T ₁ to T ₈ are the same as or different from each other, and each independently, may be any one selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O and S, and , Wherein R ₃₁ to R ₄₄ 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 cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted It may be any one selected from a C5 to C30 aryl group and a substituted or unsubstituted C2 to C30 heteroaryl group having O, N, S or P as a hetero atom, and each of [Structural Formula 1] to In [Structural Formula 6], the R ₃₁ to R ₄₄ One may form a single bond with a substituent in [Chemical Formula 1] or [Chemical Formula I] to [Chemical Formula III].

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

[Structural Formula 3-1]

In the [Structural Formula 3-1], T ₁ to T ₅ and R ₃₃ and R ₃₄ are the same as defined above.

In addition, according to a preferred embodiment of the present invention, the [Structural Formula 1] to [Structural Formula 6] may be selected from the following [Structural Formula 7].

[Structural Formula 7]

In [Structural Formula 7],

X is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 to 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 C 1 to C 30 alkoxy group, substituted or unsubstituted A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl having 1 to 30 carbon atoms The group consisting of an amine group, a substituted or unsubstituted aryl group having 5 to carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a hetero atom, a cyano group, a nitro group, a halogen group Any one selected from among, m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs are the same as or different from each other, and any one of the at least one X is [Chemical Formula 1] or [Chemical Formula I] to A single bond may be formed with a substituent in [Formula III].

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

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

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

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

Specific examples of the silyl group as a substituent used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclobutylsilyl And dimethylfurylsilyl.

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

The organic light-emitting compound represented by [Chemical Formula 1] according to the present invention may be more specifically selected from compounds represented by the following [Compound 1] to [Compound 88].

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

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

[Compound 9] [Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15] [Compound 16]

[Compound 17] [Compound 18] [Compound 19] [Compound 20]

[Compound 21] [Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27] [Compound 28]

[Compound 29] [Compound 30] [Compound 31] [Compound 32]

[Compound 33] [Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39] [Compound 40]

[Compound 41] [Compound 42] [Compound 43] [Compound 44]

[Compound 45] [Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51] [Compound 52]

[Compound 53] [Compound 54] [Compound 55] [Compound 56]

[Compound 57] [Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63] [Compound 64]

[Compound 65] [Compound 66] [Compound 67] [Compound 68]

[Compound 69] [Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75] [Compound 76]

[Compound 77] [Compound 78] [Compound 79] [Compound 80]

[Compound 81] [Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87] [Compound 88]

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 1] 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 a 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.

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 electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, and if necessary, 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 conventional 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), etc., 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. Then, the 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. 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 vacuum deposition or spin coating to form a thin film. can do. 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 because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . At this time, the hole blocking material used is not particularly limited, but it must have an electron transport ability and have a higher ionization potential than the 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

Formula 104 Formula 105 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 metal is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

As the material for the electron transport layer, a known electron transport material may be used as it 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, satisfying 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 heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, 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 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 C 5 to 30 carbon atom 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.

The organic electroluminescent device according to the present invention is characterized in that the organic layer includes an emission layer, and the emission layer further includes at least one phosphorescent dopant in addition to the at least one organic emission compound represented by [Chemical Formula 1]. The light emitting dopant applied to the organic electroluminescent device is not particularly limited, but may be one or more compounds selected from compounds represented by the following [General Formula A-1] to [General Formula J-1].

[General Formula A-1]

ML ₁ L ₂ L ₃

The M is selected from the group consisting of metals of groups 7, 8, 9, 10, 11, 13, 14, 15, and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ and L ₃ may be the same as or different from each other as a ligand, and may each independently include any one selected from the following [Structural Formula D], but is not limited thereto.

In addition, * in the following [Structural Formula D] represents a site coordinated with the metal ion M.

[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 A heteroaryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, 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 may be any one selected from the group.

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

In addition, R may be connected to each of the adjacent substituents 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 with alkylene or alkenylene to form a spiro ring or a fused ring.

As an example, 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 , and L ^A14 each represent a linking group as defined above, and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonded to M ^A1 .

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

[General Formula C-1]

In the above [general formula C-1],

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

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

[General Formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1], and R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent that connects to each other to form a 5-membered ring, and does not have any Represents a substituent, and R ^C13 and R ^C14 are each independently a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and represents a substituent that does not have anything that connects to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, substituted 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 bonded to M ^C1 .

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

[General Formula E-1]

In the above [general formula E-1],

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

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

[General Formula F-1]

In the above [general formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], 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.

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

[General Formula G-1]

In the above [general formula G-1],

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

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be linked to each other to form a ring, wherein the ring formed by R ^F1 and R ^F12 , 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 .

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

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

In the above [General Formula H-1],

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

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

L ¹ is a ligand 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 general formula H-1 become a neutral complex.

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

In the general formula H-3, R ³¹ , n ³ , m ³ , L ³ are the same as R ¹¹ , n ¹ , m ¹ , L ¹ , respectively, and q ³¹ represents an integer of 0 to 8, and 0 to 2 is preferable and 0 is more preferable.

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

[General Formula I-1]

In the above [general formula I-1],

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

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

[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-) bound to the M In this case, 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.

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

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

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

In addition, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process, wherein the deposition method Means a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used as a material for forming each layer It refers to a method of forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, etc., by mixing a 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 monochrome or white flat lighting device, and a single color or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, 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

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

[Intermediate 1-a]

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

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

[Intermediate 1-b]

[Intermediate 1-a] (25.0 g, 149 mmol) obtained in [Scheme 1-1] was added to 200 mL of tetrahydrofuran and stirred. Phenyl magnesium bromide (3.0 M in Et ₂ O) (87.4 mL, 297 mmol) was added dropwise and refluxed at 0° C. for about 1 hour. After adding ethyl chloroformate (19.4 g, 179 mmol) dropwise, it was refluxed for about 1 hour. An aqueous ammonium chloride solution was added until it became slightly acidic, and washed with water and heptane to give 32.4 g (yield 80%) of [Intermediate 1-b].

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

[Intermediate 1-c]

[Intermediate 1-b] (30 g, 110 mmol) obtained in [Scheme 1-2] was added to about 80 mL of phosphorus oxychloride and refluxed overnight. After cooling the temperature to -20 °C, about 400 mL of distilled water was slowly added. Washed with distilled water, methanol, and heptane, and recrystallized from toluene and heptane to give [Intermediate 1-c] 14.1 g (yield 44%).

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

[Intermediate 1-d]

1-bromo-2-methylnaphthalene (10 g, 45.2 mmol) was added to 50 mL of sulfuric acid and stirred. After cooling to 0 °C, nitric acid (2.9 mL, 67.8 mmol) was slowly added dropwise, followed by stirring for about 2 hours. After neutralization, extraction was performed with ethyl acetate, and then separated by column chromatography to obtain 3.5 g (29% yield) of [Intermediate 1-d].

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

[Intermediate 1-e]

[Intermediate 1-d] (3.5 g, 13.1 mmol) obtained in [Scheme 1-4], N-bromosuccinimide (2.3 g, 13.1 mmol), dibenzoyl peroxide (0.32 g, 1.31 mmol) Put in 100 mL of carbon tetrachloride and stirred for about 3 hours. After extraction with ethyl acetate and separation by column chromatography to give [Intermediate 1-e] 2.9 g (65% yield).

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

[Intermediate 1-f]

50 mL of toluene was added to [Intermediate 1-e] (2.8 g, 8.2 mmol) and triphenylphosphine (2.6 g, 9.9 mmol) obtained in [Scheme 1-5] and refluxed at 120° C. for about 12 hours. Washed with methanol to give 4.8 g (yield 97%) of [Intermediate 1-f].

[Scheme 1-7] Synthesis of [Intermediate 1-g]

[Intermediate 1-g]

[Intermediate 1-f] (4.6 g, 7.6 mmol) and sodium bis(trimethylsilyl) amide (2.8 g, 15.2 mmol) obtained in [Scheme 1-6] were added to 50 mL of tetrahydrofuran and stirred. After cooling to -78 °C, 2-bromo3-nitrobenzaldehyde (1.9 g, 8.4 mmol) was slowly added dropwise, followed by stirring for about 12 hours. After raising the temperature to room temperature, the mixture was stirred for about 72 hours, extracted with ethyl acetate, and separated by column chromatography to give 2.7 g (yield 75%) of [Intermediate 1-g].

[Scheme 1-8] Synthesis of [Intermediate 1-h]

[Intermediate 1-h]

[Intermediate 1-g] (2.7 g, 5.8 mmol) and copper powder (0.4 g, 5.8 mmol) obtained in [Scheme 1-7] were dissolved in 30 mL of dimethylformamide and then refluxed at 120° C. for about 12 hours. . After extraction with ethyl acetate and separation by column chromatography to give 1.5 g (yield 85%) of [Intermediate 1-h].

[Scheme 1-9] Synthesis of [Intermediate 1-i]

[Intermediate 1-i]

[Intermediate 1-h] (1.5 g, 4.9 mmol), iron (0.8 g, 14.8 mmol), and 8.7 mL of hydrochloric acid obtained in [Scheme 1-8] were added to methanol/distilled water 50 mL (9:1, v/v) Dissolved in and stirred at room temperature for 12 hours. Extracted with ethyl acetate and separated by column chromatography to give 0.9 g (yield 80%) of [Intermediate 1-i].

[Scheme 1-10] Synthesis of [Compound 1]

[Compound 1]

60% sodium hydride (1.4 g, 20.5 mmol) and 20 mL of dimethylformamide were added and stirred for about 30 minutes. [Intermediate 1-i] (4.1 g, 17.1 mmol) obtained in [Scheme 1-9] and 50 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. [Intermediate 1-c] (6 g, 20.6 mmol) obtained in [Scheme 1-3] and 50 mL of dimethylformamide were added and stirred overnight. The solid formed by adding 300 mL of distilled water was filtered. Recrystallized from toluene to give [Compound 1] 5.9 g (70% yield).

MS (MALDI-TOF): m/z 495.17 [M ⁺ ]

[ Synthesis example 2] Synthesis of Compound 2

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

[Intermediate 2-a]

[Intermediate 2-a] synthesized in the same manner as in [Scheme 1-1] to [Scheme 1-3], except that heptadeutereo nitronaphthalene was used instead of 1-nitronaphthalene used in [Scheme 1-1] ] (Yield 42%) was obtained.

[Scheme 2-2] Synthesis of [Compound 2]

[Compound 2]

[Compound 2] (yield 70%) was synthesized in the same manner except that [Intermediate 2-a] obtained in [Scheme 2-1] was used instead of [Intermediate 1-c] used in [Scheme 1-10] Got it.

MS (MALDI-TOF): m/z 501.21 [M ⁺ ]

[ Synthesis example 3] Synthesis of compound 13

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

[Intermediate 3-a]

[Intermediate 3-] was synthesized in the same manner as in [Scheme 1-1] to [Scheme 1-3], except that pyridin-4-yl magnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2]. a] (yield 45%) was obtained.

[Scheme 3-2] Synthesis of [Intermediate 3-b]

[Intermediate 3-b]

[Intermediate 3-a] obtained in [Scheme 3-1] (20.4 g, 0.07 mol), 4-iodophenyl boronic acid (20.5 g, 0.08 mol), tetrakis (triphenylphosphine) palladium (4 g, 0.003 mol), potassium carbonate (19 g, 0.14 mol), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 40 mL, and refluxed overnight. After extraction with ethyl acetate and recrystallization with dichloromethane and acetone, 25.7 g (yield 80%) of [Intermediate 3-b] was obtained.

[Scheme 3-3] Synthesis of [Compound 13]

[Compound 13]

[Compound 13] (yield 68%) was synthesized by the same method except that [Intermediate 3-b] obtained in [Scheme 3-2] was used instead of [Intermediate 1-c] used in [Scheme 1-10] Got it.

MS (MALDI-TOF): m/z 495.17 [M ⁺ ]

[ Synthesis example 4] Synthesis of Compound 24

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

[Intermediate 4-a]

[Scheme 1], except that heptadeutereo nitronaphthalene was used instead of 1-nitronaphthalene used in [Scheme 1-1], and pentadeutereo phenylmagnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2]. Synthesis was performed in the same manner as in -1] to [Scheme 1-3] to obtain [Intermediate 4-a] (yield 45%).

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

[Intermediate 4-b]

[Intermediate 4-a] obtained from [Scheme 4-1] was used instead of [Intermediate 3-a] used in [Scheme 3-2], and (4-bromo-2,5) was used instead of 4-iodophenyl boronic acid. -[Intermediate 4-b] (75% yield) was obtained by synthesizing in the same manner except that dimethylphenyl)boronic acid was used.

[Scheme 4-3] Synthesis of [Compound 24]

[Compound 24] (yield 70%) was synthesized by the same method except that [Intermediate 4-b] obtained in [Scheme 4-2] was used instead of [Intermediate 1-c] used in [Scheme 1-10] Got it.

MS (MALDI-TOF): m/z 610.31 [M ⁺ ]

[ Synthesis example 5] Synthesis of Compound 31

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

[Intermediate 5-a]

[Scheme 1], except that 5-nitroisoquinoline was used instead of 1-nitronaphthalene used in [Scheme 1-1], and 4-biphenyl magnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2]. Synthesis was performed in the same manner as in -1] to [Scheme 1-3] to obtain [Intermediate 5-a] (yield 48%).

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

[Intermediate 5-b]

[Intermediate 5-a] obtained from [Scheme 5-1] was used instead of [Intermediate 3-a] used in [Scheme 3-2], and 4-bromo-1-naphthalene boron was substituted for 4-iodophenyl boronic acid Except for using an acid, it was synthesized in the same manner to obtain [Intermediate 5-b] (yield 77%).

[Scheme 5-3] Synthesis of [Compound 31]

[Compound 31] (Yield: 72%) Got it.

MS (MALDI-TOF): m/z 698.25 [M ⁺ ]

[ Synthesis example 6] Synthesis of Compound 34

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

[Intermediate 6-a]

[Scheme 1], except that 2-nitronaphthalene was used instead of 1-nitronaphthalene used in [Scheme 1-1], and pentadeutereo phenylmagnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2]. 1] to [Reaction Scheme 1-3] were synthesized in the same manner to obtain [Intermediate 6-a] (yield 44%).

[Scheme 6-2] Synthesis of [Compound 34]

[Compound 34] (yield: 70%) Got it.

MS (MALDI-TOF): m/z 500.20 [M ⁺ ]

[ Synthesis example 7] Synthesis of Compound 54

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

[Intermediate 7-a]

Synthesized in the same manner except that 3-chloro-6-nitroisoquinoline was used instead of [Intermediate 3-a] used in [Scheme 3-2], and phenylboronic acid was used instead of 4-iodophenylboronic acid. [Intermediate 7-a] (yield 82%) was obtained.

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

[Intermediate 7-b]

The same as in [Scheme 1-1] to [Scheme 1-3] except that [Intermediate 7-a] obtained from [Scheme 7-1] was used instead of 1-nitronaphthalene used in [Scheme 1-1] It synthesized by the method to obtain [Intermediate 7-b] (yield 44%).

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

[Intermediate 7-b] obtained from [Scheme 7-2] was used instead of [Intermediate 3-a] used in [Scheme 3-2], and 6-bromopyridine-3-boron was substituted for 4-iodophenyl boronic acid Except for using an acid, it was synthesized in the same manner to obtain [Intermediate 7-c] (74% yield).

[Scheme 7-4] Synthesis of [Compound 54]

[Compound 54] (yield 73%) Got it.

MS (MALDI-TOF): m/z 649.23 [M ⁺ ]

[ Synthesis example 8] Synthesis of Compound 57

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

[Intermediate 8-a]

26.5 g (0.14 mol) of 6-nitro-1-naphthalenol was added to 270 mL of dichloromethane and stirred. After adding 14 g (0.18 mol) of pyridine, the reaction mixture was cooled to 0° C., and then 42.3 g (0.15 mol) of trifluoromethane sulfonic anhydride was slowly added dropwise and stirred at room temperature for 1 hour. Separated by column chromatography to give [Intermediate 8-a] 34.2 g (yield 76%).

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

[Intermediate 8-b]

Except that [Intermediate 8-a] obtained from [Scheme 8-1] was used instead of [Intermediate 3-a] used in [Scheme 3-2], and phenyl boronic acid was used instead of 4-iodophenyl boronic acid. Synthesis was conducted in the same manner to obtain [Intermediate 8-b] (82% yield).

[Scheme 8-3] Synthesis of [Intermediate 8-c]

[Intermediate 8-c]

The same as in [Scheme 1-1] to [Scheme 1-3] except that [Intermediate 8-b] obtained from [Scheme 8-2] was used instead of 1-nitronaphthalene used in [Scheme 1-1] It synthesized by the method to obtain [Intermediate 8-c] (yield 43%).

[Scheme 8-4] Synthesis of [Compound 57]

[Compound 57] (Yield 73%) Got it.

MS (MALDI-TOF): m/z 571.20 [M ⁺ ]

[ Synthesis example 9] Synthesis of compound 65

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

[Intermediate 9-a]

[Intermediate 9-a] synthesized in the same manner as in [Scheme 1-1] to [Scheme 1-3], except that 9-nitrophenanthrene was used instead of 1-nitronaphthalene used in [Scheme 1-1] (Yield 56%) was obtained.

[Scheme 9-2] Synthesis of [Compound 65]

[Compound 65] (yield: 72%) Got it.

MS (MALDI-TOF): m/z 545.19 [M ⁺ ]

[ Synthesis example 10] Synthesis of Compound 78

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

[Intermediate 10-a]

[Scheme 1-1], except that 9-nitrophenanthrene was used instead of 1-nitronaphthalene used in [Scheme 1-1], and naphthyl magnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2]. ] To [Scheme 1-3] to obtain [Intermediate 10-a] (yield 52%).

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

[Intermediate 10-a] obtained from [Scheme 10-1] was used instead of [Intermediate 3-a] used in [Scheme 3-2], and 5-chloropyrazine-2-boronic acid was substituted for 4-iodophenyl boronic acid. Except for using, it was synthesized in the same manner to obtain [Intermediate 10-b] (70% yield).

[Scheme 10-3] Synthesis of [Compound 78]

[Compound 78] (yield 70%) except that [Intermediate 10-b] obtained from [Scheme 10-2] was used instead of [Intermediate 1-c] used in [Scheme 1-10] Got it.

MS (MALDI-TOF): m/z 673.23 [M ⁺ ]

[ Synthesis example 11] Synthesis of compound 85

[Scheme 11-1] Synthesis of [Intermediate 11-a]

[Intermediate 1-c] obtained from [Scheme 1-3] was used instead of [Intermediate 3-a] used in [Scheme 3-2], and 4-brobiphenyl-4'- instead of 4-iodophenyl boronic acid It was synthesized in the same manner except that boronic acid was used to obtain [Intermediate 11-a] (yield 77%).

[Scheme 11-2] Synthesis of [Compound 85]

[Compound 85] (yield: 72%) Got it.

MS (MALDI-TOF): m/z 647.24 [M ⁺ ]

[ Example 1 to 11] Preparation of organic light emitting diode

The ITO glass was patterned so that the light emitting area was 2 mm × 2 mm in size and washed. After mounting the substrate in the vacuum chamber, the base pressure is 1 × 10 ^-6 torr, and then the organic material is placed on the ITO DNTPD (700Å), α-NPB (300Å), the compound prepared by the present invention + (piq) ₂ Films were formed in the order of Ir(acac) (10%) (300Å), Alq ₃ (350Å), LiF (5Å), and Al (1,000Å), and measured at 0.4 mA.

The structure of DNTPD, α-NPB, (piq) ₂ Ir(acac), Alq ₃ is as follows.

[DNTPD] [α-NPB]

[(piq) ₂ Ir(acac)] [Alq ₃ ]

[ Comparative example One]

The organic light emitting diode device for Comparative Example 1 was the same as in Example 1, except that CBP, which is commonly used as a phosphorescent host material, was used instead of the compound prepared by the present invention in the device structures of Examples 1 to 11 It was produced and the structure of the CBP is as follows.

[CBP]

For the organic electroluminescent devices manufactured according to Examples 1 to 11 and Comparative Example 1, voltage, luminance, color coordinates and lifetime were measured, and the results are shown in Table 1 below.

division Host Dopant Voltage(V) Brightness (Cd/㎡) CIEx CIEy Example 1 Compound 1 (piq) ₂ Ir(acac) 4.0 1065 0.671 0.329 Example 2 Compound 2 (piq) ₂ Ir(acac) 4.0 1204 0.676 0.322 Example 3 Compound 13 (piq) ₂ Ir(acac) 3.9 1142 0.670 0.326 Example 4 Compound 24 (piq) ₂ Ir(acac) 3.9 1248 0.676 0.325 Example 5 Compound 31 (piq) ₂ Ir(acac) 4.0 1113 0.669 0.323 Example 6 Compound 34 (piq) ₂ Ir(acac) 4.0 1200 0.674 0.324 Example 7 Compound 54 (piq) ₂ Ir(acac) 3.9 1155 0.676 0.323 Example 8 Compound 57 (piq) ₂ Ir(acac) 4.0 1086 0.674 0.326 Example 9 Compound 65 (piq) ₂ Ir(acac) 4.1 1059 0.674 0.329 Example 10 Compound 78 (piq) ₂ Ir(acac) 4.0 1095 0.667 0.332 Example 11 Compound 85 (piq) ₂ Ir(acac) 3.9 1167 0.674 0.326 Comparative Example 1 CBP (piq) ₂ Ir(acac) 7.9 350 0.667 0.324

As shown in [Table 1], the organic compound secured by the present invention has a much lower driving voltage and luminance than CBP among host materials commonly used as phosphorescent host materials.

Claims (9)

Organic light-emitting compound represented by the following [Formula 1]:
[Formula 1]

In the above [Formula 1],
L is a single bond, or a linking group selected from a substituted or unsubstituted arylene group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, n is an integer of 0 to 3, wherein n is In the case of 2 or more, a plurality of L is the same or different from each other,
R ₁ to R ₁₀ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a substituted Or an unsubstituted C2-C50 heteroaryl group,
A is selected from the following [Formula I] to [Formula III],
[Chemical Formula I] [Chemical Formula Ⅱ] [Chemical Formula Ⅲ]

X ₁ to X ₈ are the same as or different from each other, and each independently N or CR ₁₂ ,
The R ₁₂ is hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, and a substituted or unsubstituted heterocyclic group having 2 to 50 carbon atoms Is selected from aryl groups,
R ₁₁ is selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms,
'*' in the [Chemical Formula I] to [Chemical Formula III] refers to a site bonded to the [Chemical Formula 1]. delete The method of claim 1,
The R ₁ to R ₁₂ and L are each independently deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 1 Halogenated alkyl group of to 20, aryl group of 6 to 24 carbon atoms, heteroaryl group of 2 to 24 carbon atoms, alkoxy group of 1 to 20 carbon atoms, aryloxy group of 6 to 24 carbon atoms, alkylsilyl group of 1 to 20 carbon atoms, carbon number An organic light emitting compound, characterized in that further substituted with one or more substituents selected from 6 to 24 arylsilyl groups, C 1 to C 20 alkylamine groups and C 6 to C 24 arylamine groups. The method of claim 1,
[Chemical Formula 1] is an organic light-emitting compound, characterized in that selected from the compounds represented by the following [Compound 1] to [Compound 88]:
[Compound 1] [Compound 2] [Compound 3] [Compound 4]

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

[Compound 9] [Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15] [Compound 16]

[Compound 17] [Compound 18] [Compound 19] [Compound 20]

[Compound 21] [Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27] [Compound 28]

[Compound 29] [Compound 30] [Compound 31] [Compound 32]

[Compound 33] [Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39] [Compound 40]

[Compound 41] [Compound 42] [Compound 43] [Compound 44]

[Compound 45] [Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51] [Compound 52]

[Compound 53] [Compound 54] [Compound 55] [Compound 56]

[Compound 57] [Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63] [Compound 64]

[Compound 65] [Compound 66] [Compound 67] [Compound 68]

[Compound 69] [Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75] [Compound 76]

[Compound 77] [Compound 78] [Compound 79] [Compound 80]

[Compound 81] [Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87] [Compound 88]

A first electrode; A second 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 1] 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 5,
An organic electroluminescent device, wherein the organic layer interposed between the first electrode and the second electrode includes a light emitting layer. The method of claim 7,
The light-emitting layer is made of a host compound and a dopant compound, the organic light-emitting compound of [Chemical Formula 1] according to claim 1 is used as a host, and the light-emitting layer further includes at least one dopant compound. Electroluminescent device. The method of claim 5,
The organic electroluminescent device according to claim 1, wherein the organic layer further includes at least one organic emission layer emitting red, green, or blue light to emit white light.

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