KR102154056B1 - 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 A] to [Chemical Formula C] 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 and Excellent luminous efficiency and lifetime characteristics.
[Formula A] [Formula B] [Formula C]

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 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 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 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 so far. 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 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] to [Chemical Formula C] in order to solve the above problems.

[Formula A] [Formula B] [Formula C]

In addition, the present invention comprises a first electrode, a second electrode opposite to the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer is from [Chemical Formula A] to It provides an organic electroluminescent device comprising at least one organic light emitting compound represented by [Chemical Formula C].

Specific substituents of the organic light-emitting compound represented by [Chemical Formula A] to [Chemical Formula C] 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 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 represented by the following [Chemical Formula A] to [Chemical Formula C].

[Formula A] [Formula B] [Formula C]

In the [Chemical Formula A] to [Chemical Formula C],

R ₁ to R ₁₄ 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 alkoxy group having 1 to 30 carbon atoms, 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 arylthioc having 5 to 30 carbon atoms 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 may be selected from the group consisting of 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 ₁₄ may be connected with a substituent adjacent to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S , O may be substituted with one or more heteroatoms selected from.

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

L is a single bond, a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C2 to C60 Alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, 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 may be the same or different from each other.

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

The "-*" 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.

[Chemical Formula A] to [Chemical Formula C] may be any one selected from compounds represented by the following [Chemical Formula D1] to [Chemical Formula D14] depending on the bonding position of Q.

[Formula D1] [Formula D2] [Formula D3]

[Formula D4] [Formula D5]

[Formula D6] [Formula D7]

[Formula D8] [Formula D9]

[Formula D10] [Formula D11]

[Formula D12] [Formula D13] [Formula D14]

In the [Chemical Formula D1] to [Chemical Formula D14], R ₁ to R ₁₄ , Ar ₁ , L, n and Y are the same as defined in [Chemical Formula A] to [Chemical Formula C].

'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 to be substituted with one or more substituents selected from the group consisting of a group and an aryloxy group having 1 to 24 carbon atoms, wherein the substituted R ₁ to R ₄₀ , Ar ₁ and L are each independently further substituted with the above substituent. I can.

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 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.

On the other hand, the aryl group contained in the organic light-emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and 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 an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a C1-C24 group Alkyl group, 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 , It may be substituted with a C2-C24 heteroaryl group or a C2-C24 heteroarylalkyl group.

Meanwhile, the heteroaryl group included in the organic light-emitting compound according to the present invention is a heteroaromatic having 2 to 24 carbon atoms which may include 1 to 4 hetero atoms selected from N, O, P, or S in each ring in the aryl group. It refers to an organic radical, 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.

The heteroaryl group included in the organic light-emitting compound according to 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 ₅₁ ), C (R ₅₂ ) (R ₅₃ ), N, N (R ₅₄ ), O and S .

R ₄₁ to R ₅₄ 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 It may be any one selected from a cycloalkyl group of 3 to 30, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a heteroaryl group having 2 to 50 carbon atoms having O, N or S as a substituted or unsubstituted hetero atom, and , The R ₄₁ to R ₅₄ Any one of the [Chemical Formula A] to [Chemical Formula C] of R ₁ to R ₁₄ , Ar ₁ , L, Y and one of these substituents is connected to form a single bond.

In addition, the [Structural Formula 3] may include a compound represented as [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 ₄₃ and R ₄₄ are the same as defined above.

According to an 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 50 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 An amine group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom having O, N or S as a hetero atom and having 2 to 50 carbon atoms Any one selected from the group consisting of an aryl group, a cyano group, a nitro group, and a halogen group, m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs are the same or different from each other, and any of the one or more X One is connected to any one of R ₁ to R ₁₄ , Ar ₁ , L, Y and their substituents of [Chemical Formula A] to [Chemical Formula C] to form a single bond.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like, and at least one hydrogen atom in the alkyl group is The atom may 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 present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like, and the alkoxy At least one hydrogen atom in the group may be substituted with the same substituent as in the case of the aryl group.

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

Specific examples of the silyl group used in the present invention are trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclobutylsilyl , 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.

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

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.

In addition, when L is a linking group other than a single bond, each may be independently selected from the following [Structural Formula 8] to [Structure 15].

[Structural Formula 8] [Structural Formula 9] [Structural Formula 10] [Structural Formula 11]

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

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

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 comprises the above [Formula A] to [Formula C] It may contain one or more 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.

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, 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.

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, a hole injection layer 30 and An electron injection layer 70 may be further included, and in addition to that, one or two intermediate layers 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), 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, 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. 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 serves to prevent this problem by using a material having a very low level of Highest Occupied Molecular Orbital (HOMO) 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 the light emitting compound, and representatively, BAlq, BCP, TPBI, etc. 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.

In addition, the emission layer may be formed of a host and a dopant. 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, 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 with 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 alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms It may be any one selected from, and wherein R is each 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 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.

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], 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, G ^C11 , G ^C12 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, L ^C11 , L ^C12 represents a linking group, Q ^C11 , 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, 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. Further, 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. Further, 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 rings of the rings A to D may have a substituent, and the other two rings are an aryl ring or heteroaryl which 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 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 cyclic 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 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 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, and the like 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]

(1-1)

Intermediate 1-1

To a flask purged with nitrogen, 61 g (381 mmol) of 1,5-dihydroxynaphthalene, 610 mL of dichloromethane, and 75.3 g (952 mmol) of pyridine were added and stirred, and the temperature was set to 0°C. Trifluoromethanesulfonic acid anhydride 247.1 g (876 mmol) was added dropwise, and the temperature was brought to room temperature, followed by stirring for about 8 hours. Again, the temperature was set to 0°C, water and methanol were sufficiently added, followed by filtration to obtain 156 g (yield 97%).

(1-2)

Intermediate 1-2

In a flask, 2-nitrophenylboronic acid pinacol ester 30 g (120 mmol), the synthesized intermediate 1-1 76.6 g (181 mmol), tetrakis (triphenylphosphine) palladium 5.6 g (5 mmol), potassium carbonate 49.9 g (361 mmol), 300 mL of tetrahydrofuran, and 60 mL of distilled water were added and stirred. After the temperature was set to 40° C., the mixture was stirred for about 8 hours. The organic layer was extracted with ethyl acetate and distilled water. Column chromatography was performed with ethyl acetate and heptane to give 27.7 g (58% yield).

(1-3)

Intermediate 1-3

In a flask, 11.1 g (28 mmol) of the synthesized intermediate 1-2, 2-bromoaniline 5.3 g (31 mmol), tris (dibenzylideneacetone) dipalladium 0.5 g (1 mmol), 2,2'- Bis(diphenylphosphino)-1,1'-binaphthyl 0.3 g (1 mmol), sodium tertiary butoxide 5.4 g (56 mmol), and 115 mL of toluene were added and stirred under reflux. After completion of the reaction, the mixture was concentrated under reduced pressure, and subjected to column chromatography with dichloromethane and heptane to give 5.1 g (yield 43%).

(1-4)

Intermediate 1-4

In a flask, the synthesized intermediate 1-3 5.1 g (12 mmol), tricyclohexylphosphonium tetrafluoroborate 0.1 g (0.24 mmol), palladium (II) acetate 0.028 g (0.12 mmol), potassium carbonate 3.4 g (25 mmol), 67 mL of N,N'-dimethylacetamide was added and stirred under reflux. After completion of the reaction, it was cooled to room temperature. Water was added to the flask and filtered to give 2.5 g (61% yield).

(1-5)

Intermediate 1-5

64 g (0.189 mol) of the synthesized intermediate 1-4, iodobenzene 42.5 g (0.208 mol), copper powder 19.4 g (0.378 mol), 18-crown-6 15 g (0.057 mol), potassium carbonate 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 25 g (yield 32%).

(1-6)

Intermediate 1-6

In a flask, 16.6 g (40 mmol) of the synthesized intermediate 1-5, 31.6 g (120 mmol) of triphenylphosphine, and 200 mL of 1,2-dichlorobenzene were added and stirred under reflux. After completion of the reaction, it was concentrated under reduced pressure. After column chromatography with heptane and dichloromethane, recrystallized with methanol to give 6.9 g (yield 45%).

(1-7)

Intermediate 1-7

In a flask, 25.0 g (112 mmol) of 6-bromo-2-naphthol, 25.1 g (146 mmol) of 1-naphthaleneboro acid, 3.2 g (2.8 mmol) of tetrakis (triphenylphosphine) palladium, potassium carbonate 46.5 g (336 mmol), 125 mL of tetrahydrofuran, 125 mL of 1,4-dioxane, and 50 mL of distilled water were added and stirred under reflux. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate and distilled water. Column chromatography with dichloromethane and recrystallized with heptane to give 20 g (yield 66%).

(1-8)

Intermediate 1-8

To a flask purged with nitrogen, 20 g (74 mmol) of the synthesized intermediate 1-7, 200 mL of dichloromethane, and 7.6 g (96 mmol) of pyridine were added and stirred, and the temperature was set to 0°C. Trifluoromethanesulfonic acid anhydride 27.1 g (96 mmol) was added dropwise, and the temperature was brought to room temperature, followed by stirring. After completion of the reaction, 2 N-hydrochloric acid aqueous solution was added, stirred, and extracted with dichloromethane. After concentration under reduced pressure, 24 g was obtained by recrystallization from heptane (yield 81%).

(1-9)

Compound 1

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

MS (MALDI-TOF): m/z 635 [M] ⁺

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

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

(1) Synthesis of Compound 1-1 to Compound 1-2 by the same method using 4-iodo-1,1'-biphenyl substituted in place of Intermediate 1-8 in (1-9) of Synthesis Example 1 I did.

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

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

[Compound 1-3]

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

[Compound 1-4]

(4) Compound 1-5 was synthesized in the same manner using 9-iodophenanthrene substituted for intermediate 1-8 in (1-9) of Synthesis Example 1 above.

[Compound 1-5]

(6) Compound 1-6 was synthesized in the same manner using 2-iodo-9,9'-dimethyl-9H-fluorene substituted for intermediate 1-8 in (1-9) of Synthesis Example 1 above. .

[Compound 1-6]

Synthesis Example 2. Synthesis of [Compound 2]

(2-1)

Intermediate 2-1

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

(2-2)

Intermediate 2-2

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

(2-3)

Intermediate 2-3

In a nitrogen-purged flask, the synthesized intermediate 2-2 (19.8 g, 66 mmol), palladium acetate (7.3 g, 32.6 mmol), sodium carbonate (10 g), dimethylacetamide (200 mL) was added and refluxed for about a day. Stirred. After completion of the reaction, the mixture was brought to room temperature, and water was added thereto and filtered. The filtered solution was extracted with ethyl ether to separate the organic layer. After concentration under reduced pressure, column chromatography was performed to obtain 4.4 g (yield 30%).

(2-4)

Compound 2

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

MS (MALDI-TOF): m/z 560 [M] ⁺

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

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

(1) Compound 2-1 was synthesized in the same manner using 1-chloro-1H-pyrrole substituted for intermediate 1-8 in (2-4) of Synthesis Example 2 above.

[Compound 2-1]

(2) Using the substituted 2-chloro-1-methyl-1H-imidazo[4,5-b]pyridine in place of intermediate 1-8 in Synthesis Example 2 (2-4), compound 2- 2 was synthesized.

[Compound 2-2]

(3) Using 3-bromo-2-methyl-imidazo[2,1-a]isoquinoline substituted in place of intermediate 1-8 in Synthesis Example 2 (2-4), compound 2- 3 was synthesized.

[Compound 2-3]

(4) Compound 2-4 was prepared in the same manner using 6-bromo-2,2':6',2"-terpyridine substituted for intermediate 1-8 in Synthesis Example 2 (2-4). Synthesized.

[Compound 2-4]

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

[Compound 2-5]

(6) 4-chloro-5H-pyrido[4',3':4,5]pyrrolo[3,2-d]pyrid substituted for intermediate 1-8 in Synthesis Example 2 (2-4) Compound 2-6 was synthesized in the same manner using midine.

[Compound 2-6]

Synthesis Example 3. Synthesis of [Compound 3]

(3-1)

Intermediate 3-1

At room temperature, 2-aminobenzonitrile (20.0 g, 169 mmol) and 140 mL of tetrahydrofuran were added to a flask under a nitrogen stream, followed by stirring. 112.9 mL (339 mmol) of phenyl magnesium bromide (3.0M in Et ₂ O) was added dropwise. After stirring at reflux for about 1 hour, the temperature was set to 0°C. Ethyl chloroformate (22.0 g, 203 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 30.1 g. (Yield: 80%)

(3-2)

Intermediate 3-2

At room temperature, the synthesized intermediate 3-1 (30.0g, 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 give 14.6 g. (Yield: 44.9%)

(3-3)

Intermediate 3-3

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a flask under a nitrogen stream, followed by stirring for about 30 minutes. 13.9 g (41 mmol) of the synthesized intermediate 1-4 and 100 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. 12.8 g (53 mmol) of the synthesized intermediate 3-2 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. Recrystallized from toluene to obtain Intermediate 3-3. (15g, 67% yield)

(3-4)

Compound 3

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

MS (MALDI-TOF): m/z 687 [M] ⁺

¹³ C NMR (75MHz, CDCl ₃ ) δ: 103 109.5 111 111.1 117.9 118.8 119.2 119.6 119.8 120 121.4 122.4 125.5 125.8 126.6 127.4 127.5 127.7 128.2 128.3 128.5 128.7 129.2 130.1 130.2 130.9 131.8 132.2 132.3 133.1 134 139.7 144.4 145.4 149.3 155.8 161 [50C ]

Synthesis Example 4. Synthesis of [Compound 4]

(4-1)

Intermediate 4-1

In a flask immersed in water under a stream of nitrogen, 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 reflux stirring 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. Recrystallized from toluene and heptane to give 24.6 g (50.7% yield).

(4-2)

Intermediate 4-2

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, and stirred 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, followed by reflux stirring 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 4-1 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. Then, 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 to obtain 59 g. (Yield 69%)

(4-3)

Compound 4

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

MS (MALDI-TOF): m/z 813 [M] ⁺

¹³ C NMR (75MHz, CDCl ₃ ) δ: 103 109.5 111 111.1 117.9 118.8 119.2 119.6 119.8 120 121.4 122.4 124.9 125.5 125.8 126.6 127.2 127.3 127.4 127.6 127.9 128 128.2 128.3 129.2 130.1 130.2 130.7 130.9 132.2 133 133.1 134 134.4 139.7 140.8 144.4 145.4 150 155.8 161 [60C]

Synthesis Example 5. Synthesis of [Compound 5]

(5-1)

Intermediate 5-1

2,4,6-trichloro-1,3,5-triazine 40.0 g (216.9 mmol), phenylboronic acid 63.5 g (520.6 mmol), tetrakis (triphenylphosphine) palladium 5.0 g (4.4 mmol), Potassium carbonate 72.0 g (520.6 mmol), 200 mL of 1,4-dioxane, 200 mL of toluene, and 80 mL of distilled water were added and stirred at 100 °C for 6 hours. When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and acetone to give 34.8 g. (Yield 60%)

(5-2)

Compound 5

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

MS (MALDI-TOF): m/z 664 [M] ⁺

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

Synthesis Example 6. Synthesis of [Compound 6]

(6-1)

Intermediate 6-1

In (5-1) of Synthesis Example 5, 2,4,6-trichloropyrimidine was added instead of 2,4,6-trichloro-1,3,5-triazine and synthesized in the same manner, and 20g ( Yield 50%).

(6-2)

Intermediate 6-2

20.0 g (75.0 mmol) of the synthesized intermediate 6-1, 4-bromophenylboronic acid 18.1 g (90.0 mmol), tetrakis (triphenylphosphine) palladium 1.7 g (1.5 mmol), potassium carbonate 20.7 g (150.0 mmol), 100 mL of 1,4-dioxane, 100 mL of toluene, and 50 mL of distilled water were added and stirred at 100° C. for 12 hours. When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 22.4 g. (Yield 77%)

(6-3)

Intermediate 6-3

After dissolving 22.4 g (57.8 mmol) of the synthesized intermediate 6-2 in 230 mL of tetrahydrofuran under a nitrogen stream, 1.6 M normal-butyllithium 44 mL (69.4 mmol) was slowly added dropwise while stirring at -78 °C, and added dropwise. Upon completion, the mixture was stirred for 1 hour while maintaining -78°C. After that, 17.6 g (69.4 mmol) of iodine was slowly added dropwise, and then heated to room temperature and stirred for 1 hour. Upon completion of the reaction, 230 ml of an aqueous sodium thiosulfate solution was added dropwise and stirred for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 22.1 g. (Yield 88%)

(6-4)

Compound 6

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

MS (MALDI-TOF): m/z 739 [M] ⁺

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

Synthesis Example 7. Synthesis of [Compound 7]

(7-1)

Compound 7

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

MS (MALDI-TOF): m/z 713 [M] ⁺

¹³ C NMR (75MHz, CDCl ₃ ) δ: 105.4 109.5 111.1 111.6 116.8 117.6 117.9 118.8 119.4 119.8 120 120.5 121.4 121.7 125.1 125.4 125.5 126.3 126.6 127.2 127.4 127.5 127.7 128.3 128.5 128.7 129.2 129.3 131.1 131.4 131.8 132.3 133 133.1 134.2 136.7 136.8 143.7 144.3 144.4 149.3 155.8 161 [52C]

Synthesis Example 8. Synthesis of [Compound 8]

(8-1)

Intermediate 8-1-a Intermediate 8-1

Compound 8

In a flask, biphenyl-4-amine 50.0 g (330 mmol), 2-bromo-9,9-dimethyl-9H-fluorene 43.2 g (276 mmol), palladium acetate 1.2 g (5.6 mmol), Xantphos 6.4 g (11.02 mmol), 126 g (386 mmol) of cesium carbonate, and 1000 mL of toluene were added, followed by reflux stirring for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and toluene was concentrated under reduced pressure. Separated by column chromatography with ethyl acetate and hexane to give 57 g (91% yield) of intermediate 8-1-a.

Using the synthesized intermediate 8-1-a, intermediate 8-1 was synthesized in the same manner as in Synthesis Example 1 (1-3), and compound 8 was synthesized in the same manner as in Synthesis Example 1. (2.8g, yield 30%)

MS (MALDI-TOF): m/z 868 [M] ⁺

¹³ C NMR (75MHz, CDCl ₃ ) δ: 30.9 45.5 105.4 109.5 111 111.1 112 113.7 117.6 117.9 118.8 119.6 119.7 119.8 120 120.7 121 121.4 121.6 122.1 123.2 125.5 126.2 126.6 126.7 127.6 127.9 128.1 128.7 128.8 129.2 129.3 129.6 130.6 130.9 131.1 131.8 134 134.4 134.8 135.4 136.8 137.8 138.2 139.8 140.3 140.8 141 144.8 145.4 147.8 148.7 [65C]

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

(1) 1-7 of Synthesis Example 1 using (9,9-dimethyl-9H-fluoren-2yl) boronic acid substituted for intermediate 8-1-a in (8-1) of Synthesis Example 8 And Compound 8-1 was synthesized in the same manner as in Synthesis Example 8.

[Compound 8-1]

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

[Compound 8-2]

(3) 5-phenyl-5H-pyrido[2',3':4,5]pyrrolo[3,2-d substituted for intermediate 8-1-a in Synthesis Example 8 (8-1) ] Using pyrimidine-2-ylboronic acid, compound 8-3 was synthesized in the same manner as in Synthesis Example 1 1-7 and Synthesis Example 8.

[Compound 8-3]

Examples 1 to 8: 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 (700 Å), α-NPB (300 Å), compounds 1 to 8 prepared by the present invention. Is used as a host (90 wt%), and the following (piq) ₂ Ir(acac) (10 wt%) is co-deposited (300 Å) as a dopant, 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 8] 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]

Example 9

In the device structures of Examples 1 to 8, the compound used for the light emitting layer was selected as [Compound 3], 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, was used 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 Example 2

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

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

T95 refers to the time it takes for the luminance to decrease from initial luminance (5000 nits) to 95%.

division Host
compound Dopant Voltage
(V) Luminance
(Cd/㎡) CIEx CIEy T ₉₅ (Hr) Example 1 One (piq) ₂ Ir(acac) 4.3 1760 0.670 0.329 465 Example 2 2 (piq) ₂ Ir(acac) 4.2 1750 0.674 0.325 415 Example 3 3 (piq) ₂ Ir(acac) 4.1 1800 0.672 0.327 440 Example 4 4 (piq) ₂ Ir(acac) 4.3 1740 0.672 0.327 435 Example 5 5 (piq) ₂ Ir(acac) 4.0 1690 0.674 0.325 395 Example 6 6 (piq) ₂ Ir(acac) 4.2 1710 0.676 0.323 420 Example 7 7 (piq) ₂ Ir(acac) 4.3 1870 0.670 0.329 445 Example 8 8 (piq) ₂ Ir(acac) 4.1 1850 0.671 0.328 425 Example 9 3 PTOEP 4.1 1810 0.652 0.325 430 Comparative Example 1 CBP (piq) ₂ Ir(acac) 7.7 290 0.668 0.331 30 Comparative Example 2 CBP PTOEP 7.5 270 0.652 0.330 30

Claims (10)

Organic light-emitting compound represented by the following [Chemical Formula D11]:
[Formula D11]

In [Chemical Formula D11],
R ₁ to R ₁₄ 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 3 to 30 cycloalkyl group, substituted or unsubstituted C 1 to C 30 alkylamine group, substituted or unsubstituted C 5 to C 30 arylamine group, substituted or unsubstituted C 5 to C 50 aryl group, substituted or It is selected from the group consisting of a C2-C50 heteroaryl group, a cyano group, a nitro group, and a halogen group, which is unsubstituted and has O, N or S as a hetero atom,
The R ₁ to R ₁₄ may be connected with a substituent adjacent to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S, O It may be substituted with any one or more heteroatoms selected from,
Ar ₁ is selected from the group consisting of a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,
L is a single bond or a linking group selected from 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, wherein n is In the case of 2 or more, a plurality of L is the same or different from each other),
Y is NR ₃₃ , O or S, and R ₃₃ is the same as the definition of R ₁ to R ₁₄ . The method of claim 1,
The R ₁ to R ₁₄ , R ₃₃ , Ar ₁ and L are each independently at least one selected from the group consisting of deuterium, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and a heteroaryl group having 2 to 24 carbon atoms Organic light-emitting compound, characterized in that further substituted with a substituent. The method of claim 1,
The [Chemical Formula D11] is an organic light-emitting compound selected from compounds represented by the following formula:

delete delete delete A first electrode; A second electrode facing the first electrode; And one or more organic layers interposed between the first electrode and the second electrode,
An organic electroluminescent device, wherein the organic layer includes at least one organic light-emitting compound represented by [Chemical Formula D11] according to claim 1. The method of claim 7,
The organic layer comprises at least one layer selected from 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. The method of claim 8,
The emission layer includes at least one host compound and at least one dopant compound, and the host compound is an organic light emitting compound represented by [Chemical Formula D11]. The method of claim 7,
An organic electroluminescent device, characterized in that 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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