KR102249279B1 - An organoelectro luminescent compounds and organoelectro luminescent device using the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by the following [Chemical Formula 1] and an organic light emitting device comprising the same, wherein the organic light emitting device employing the organic light emitting compound according to the present invention is a device employing a conventional phosphorescent host material Compared to that, it can be driven at a lower voltage and has high power efficiency.
[Formula 1]

Description

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

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

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

An organic electroluminescent device is a device that emits light while dissipating after electrons and holes form a pair when electric charges are injected into the organic light emitting layer formed between the electron injection electrode (cathode) and the hole injection electrode (anode). In addition to being able to form a device on a substrate, it is possible to drive at a lower voltage of 10 V or less compared to a plasma display panel or an inorganic electroluminescent display, and has the advantage of relatively low power consumption and excellent color. In addition, the organic electroluminescent device is capable of displaying three colors of green, blue, and red, and thus is a subject of much interest as a next-generation rich color display device.

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

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

Accordingly, the problem to be solved by the present invention is to solve the above problem, and to provide an organic light emitting compound capable of driving at a lower voltage than a conventional material and having improved power efficiency.

In addition, the present invention is to provide an organic light emitting device capable of low voltage driving and having higher power efficiency 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 1] in order to solve the above problems.

[Formula 1]

The structure of [Chemical Formula 1] and specific details of each substituent will be described later.

In addition, the present invention comprises a first electrode, a second electrode opposite to the first electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer is represented by the above [Formula 1]. It provides an organic light-emitting device comprising at least one organic light-emitting compound to be implemented.

The organic light-emitting device employing the organic light-emitting compound according to the present invention can be driven at a lower voltage and has high power efficiency compared to a device employing a conventional phosphorescent light-emitting host material.

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

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

One aspect of the present invention relates to a bipolar organic light-emitting compound represented by the following [Chemical Formula 1] and having a hole transport unit and an electron transport unit at the same time.

[Formula 1]

In the above [Formula 1],

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

ETU-* of the [Chemical Formula 1] is an electron transporter, characterized in that it is represented by the following [Structural Formula 1-1] or [Structural Formula 1-2].

[Structural Formula 1-1] [Structural Formula 1-2]

In the [Structural Formula 1-1] to [Structural Formula 1-2],

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

The R ₁ to R ₇ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms , A substituted or unsubstituted 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 5 to carbon number 30 arylthioxy group, substituted or unsubstituted C1-C30 alkylamine group, substituted or unsubstituted C5-C30 arylamine group, substituted or unsubstituted C5-C50 aryl group, substituted or unsubstituted A heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum having O, N or S as a ring and a hetero atom It is selected from the group consisting of a group, a carbonyl group, a phosphoryl group, an amino group, a thiol group, a cyano group, a hydroxy group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, an ether group and an ester group.

In addition, the R ₁ to R ₇ Two of the adjacent two may be connected to each other to form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring, and the carbon atoms of the formed alicyclic or aromatic hydrocarbon ring are N, S, O, Se, Te, Po, NR _{14 ,} SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (=O), C=O, S=O, and BR ₂₁ may be substituted with one or more substituted or unsubstituted heteroatoms selected from . R _{14 above} To R ₂₁ are the same as those of _{R 1} to R _7.

X is the _{same as the definition of R 1} to R ₇ , except for the case where X is hydrogen.

*-HTU of the [Chemical Formula 1] is a hole transport unit, characterized in that it is represented by the following [Structural Formula 1].

[Structural Formula 1]

In the [Structural Formula 1],

M is a single bond, or CR ₁₂ R ₁₃ , NR ₁₄ , O, S, Se, Te, Po, SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (=O), C=O, S= It is selected from O and BR _{21 , wherein R 12} To R ₂₁ is the same as the definition _{of R 1} to R ₇ in [Chemical Formula 1].

In addition, the R ₁₂ and R ₁₃ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ are each connected to each other to each other, a substituted or unsubstituted fused cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted fused carbon number of 2 to It is possible to form a 30 heterocycloalkyl group, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

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

According to a preferred embodiment of the present invention, the [Structural Formula 1] may be selected from structural formulas represented by the following [Structural Formula 2] to [Structural Formula 4].

[Structural Formula 2]

[Structural Formula 3]

[Structural Formula 4]

In the [Structural Formula 2] to [Structural Formula 4],

R ₈ To R ₁₁ is the same as the definition _{of R 1} to R ₇ in [Chemical Formula 1] _{, and R 8} Two adjacent two of to R ₁₁ may be connected to each other to form a condensed aliphatic, condensed aromatic, condensed heteroaliphatic, or condensed heteroaromatic ring.

Z is a single bond, or CR ₁₂ R ₁₃ , NR ₁₄ , O, S, Se, Te, Po, SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (=O), C=O, S= It is selected from O and BR _{21 , wherein R 12} To R ₂₁ is the same as the definition _{of R 1} to R ₇ of [Formula 1] _{, and R 12} and R ₁₃ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ are each linked to each other to be substituted or unsubstituted fusion A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted fused heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms Can form groups.

_{Y is the same as the definition of R 1} to R ₇ in [Chemical Formula 1], m is an integer of 1 to 5, and when m is 2 or more, a plurality of Ys may be the same or different from each other.

In addition, the Y may be combined with an adjacent substituent to form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring, and the carbon atoms of the formed alicyclic, aromatic hydrocarbon ring are N, S, O, Se, Te, Po, NR _{14 ,} SiR ₁₅ R ₁₆ , GeR ₁₇ R ₁₈ , PR ₁₉ , PR ₂₀ (=O), C=O, S=O and BR ₂₁ to be substituted with one or more substituted or unsubstituted heteroatoms selected from I can. R _{14 above} To R ₂₁ are the same as those of _{R 1} to R _7.

In the present invention, since the substituent X is bonded to a specific position of [Structural Formula 1-1] to [Structural Formula 1-2], organic light-emitting of [Formula 1] according to the present invention is compared to a device employing a conventional phosphorescent host material. A device employing the compound can be driven at a lower voltage and has high power efficiency.

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

'Substituted' in the'substituted or unsubstituted' refers to a case where R ₁ to R ₂₁ , L and Ar ₁ to Ar ₂ are further substituted with one or more substituents, wherein at least one substituent is the R ₁ To R ₅ may be selected from the substituents described in the definition.

The one or more substituents are more specifically 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, 1 to 20 carbon atoms Halogenated alkyl group, C5 to C24 aryl group, C2 to C24 heteroaryl group, C1 to C20 alkoxy group, C5 to C24 aryloxy group, C1 to C20 alkylsilyl group, C5 to C5 It is selected from an arylsilyl group of 24, an alkylamine group having 1 to 20 carbon atoms, an arylamine group having 6 to 24 carbon atoms, and the like.

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

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 the removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, and In addition, when the aryl group has a substituent, it may be fused with neighboring substituents to further form a ring.

As a specific example of the aryl group, a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group And aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, the aryl group may also _{be further substituted with one or more substituents selected from the substituents described in the definition of R 1} to R ₅ , and more specifically, at least one hydrogen atom in the aryl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro Group, cyano group, silyl group, 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 "Alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid 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, carbon number 1 to 24 alkynyl group, C 1 to C 24 heteroalkyl group, C 6 to C 24 aryl group, C 6 to C 24 arylalkyl group, C 2 to C 24 heteroaryl group, C 2 to C 24 heteroarylalkyl group, etc. Can be substituted.

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 5] to [Structural Formula 14].

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

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

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

In the [Structural Formula 5] to [Structural Formula 14],

T ₁ to T ₁₂ 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 T ₁ to T ₁₂ are not all carbon atoms at the same time, and R ₄₁ 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, substituted Or an unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group having O, N, S or P as a hetero atom. Is selected.

In addition, the [Structural Formula 7] may include a compound represented by the following [Structural Formula 7-1] by a resonance structure according to the movement of electrons.

[Structural Formula 7-1]

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

According to a preferred embodiment of the present invention, the [Structural Formula 5] to [Structural Formula 14] may be selected from the following [Structural Formula 15].

[Structural Formula 15]

In the above [Structural Formula 15],

_{X is the same as the definition of R 1} to R ₇ in the [Chemical Formula 1], m is an integer of 1 to 11, and when m is 2 or more, a plurality of X are the same or different from each other, and of the [Chemical Formula 1] It may be connected with a substituent.

[Chemical Formula 1] according to the present invention may be more specifically selected from the following [Chemical Formula 2] to [Chemical Formula 162], but the scope of [Chemical Formula 1] according to the present invention is not limited thereto.

In addition, another aspect of the present invention relates to an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer includes the [Formula 1] It may contain at least one or more organic light-emitting compounds according to the present invention 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. .

In this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer is formed of a host and a dopant, and the organic emission compound of the present invention may be used as a host.

Meanwhile, in the present invention, a dopant material may be used in addition to the host for the light emitting layer. When the light emitting 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, an embodiment of an organic light emitting diode according to the present invention will be described in more detail with reference to FIG. 1 below.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode. It includes (80), and may further include a hole injection layer 30 and an electron injection layer 70 if necessary, and in addition to that, it is possible to further form an intermediate layer of one or two layers, and a hole blocking layer Alternatively, an electron blocking layer may be further formed, and an organic layer having various functions may be further included according to the characteristics of the device.

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 electroluminescent device is used, and an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling and waterproofness is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

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

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, and as a specific 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, as long as the material for 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 a vacuum deposition method or a spin coating method. can do. The hole blocking layer plays a role of preventing this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of a light-emitting compound, and representatively, BAlq, BCP, TPBI, and the like may be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and [Formula 501] to [Formula 507] may be used, but limited thereto. It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

[Chemical Formula 501] [Chemical Formula 502] [Chemical Formula 503]

[Chemical Formula 504] [Chemical Formula 505] [Chemical Formula 506]

[Chemical Formula 507]

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

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 transporting substances include quinoline derivatives, in particular tris(8-quinolinorate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis(benzoquinolin-10-). olate: Bebq2), ADN, [Chemical Formula 401], [Chemical Formula 402], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 401] [Compound 402] 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=1 to 3, and n is any one of 0 to 2, which satisfies m+n=3.

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

In addition, the Y may be the same or different, and may be any one selected from the following [Structural Formula C1] to [Structural Formula C39] independently of each other, but is not limited thereto.

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural Formula C4] [Structural Formula C5] [Structural Formula C6]

[Structural Formula C7] [Structural Formula C8] [Structural Formula C9] [Structural Formula C10]

[Structural Formula C11] [Structural Formula C12] [Structural Formula C13]

[Structural Formula C14] [Structural Formula C15] [Structural Formula C16]

[Structural Formula C17] [Structural Formula C18] [Structural Formula C19] [Structural Formula C20]

[Structural Formula C21] [Structural Formula C22] [Structural Formula C23]

[Structural Formula C24] [Structural Formula C25] [Structural Formula C26]

[Structural Formula C27] [Structural Formula C28] [Structural Formula C29] [Structural Formula C30]

[Structural Formula C31] [Structural Formula C32] [Structural Formula C33]

[Structural Formula C34] [Structural Formula C35] [Structural Formula C36]

[Structural Formula C37] [Structural Formula C38] [Structural Formula C39]

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

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

L is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 alkyl group. It is selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

In addition, 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 of the present invention 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]

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 that binds to 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, but is not limited thereto.

[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 are It shows 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 five-membered ring, and does not have any linking to each other. 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 connected to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, substituted Or it represents 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] to [General Formula H-3],

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. It is a ligand, a bipyridyl ligand, or a phenanthroline ligand that forms a )-plated platinum complex.

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 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.

Examples of specific compounds of the [General Formula H-1] to [General Formula 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 of the rings A to D may have a substituent, and the other two rings are an aryl ring or a hetero ring that may have a substituent. Represents and represents an aryl ring, and a condensed ring can 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 bonded to M (-C=N-) 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. Further, the R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl group or an aryl group, and L represents a monodentate ligand.

In the above [general formula J-1], it is preferable that M is Pt. Moreover, 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, 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, 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 monochromatic or white flat lighting device, and a monochromatic or white flexible lighting device.

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

[Synthesis Example 1] Synthesis of Chemical Formula 23

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

[Intermediate 1-a]

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

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

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

50.0 g (297 mmol) of [Intermediate 1-a] obtained from [Scheme 1-1] and 500 mL of dimethylformamide were stirred. Then, 55.56 g (312 mmol) of N-bromosuccinimide was slowly added to the reactor. After raising to room temperature, the mixture was stirred for 4 hours. Upon completion of the reaction, distilled water was added dropwise at room temperature. When brown crystals were formed, the crystals were filtered and separated by column chromatography, and 68 g of the compound represented by [Intermediate 1-b]. (Yield 92.6%) was obtained.

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

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

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

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

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

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

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

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

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

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

[Intermediate 1-f]

In a dried reactor, 3-bromocarbazole 60 g (244 mmol), phenylboronic acid 38.65 g (317 mmol), tetrakis (triphenylphosphine) palladium 8.45 g (7 mmol), potassium carbonate 101.1 g (731 mmol) , 300 mL of 1,4-dioxane, 300 mL of toluene, and 120 mL of distilled water were added and stirred at 100° C. for 12 hours. When the reaction is complete, extraction is performed using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 45 g (yield 66.9%) of the compound represented by [Intermediate 1-f].

[Scheme 1-7] Synthesis of [Chemical Formula 23]

[Intermediate 1-f] [Intermediate 1-e] [Formula 23]

5.0 g (21 mmol) of the compound represented by [Intermediate 1-f] obtained in [Scheme 1-6], 9.0 g (25 mmol) of [Intermediate 1-e] obtained in [Scheme 1-5], Tris(C) Ibenziridenacetone) dipalladium 0.4 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.6 g (2 mmol), sodium tertiarybutoxide 3.95 g (41 mmol) and xylene 50 mL were added 12 It was refluxed for time. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 5.0 g (yield 42.4%) of a compound represented by [Chemical Formula 23] was obtained by column chromatography.

MS [M] ⁺ : 572

[Synthesis Example 2] Synthesis of Chemical Formula 24

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

[Intermediate 2-a]

Synthesis Example 1 Except that 2-naphthyl boronic acid was used instead of phenyl boronic acid used in [Scheme 1-3] and synthesized in the same manner to obtain 30 g (yield 83.9%) of the compound represented by [Intermediate 2-a] Got it.

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

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

Synthesis Example 1 [Intermediate 1-c] used in [Scheme 1-4] was synthesized in the same manner except that [Intermediate 2-a] was used, and the compound represented by [Intermediate 2-b] 24.3 g (yield 80.2) %).

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

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

Synthesis Example 1 [Intermediate 1-d] used in [Scheme 1-5] was synthesized in the same manner except that [Intermediate 2-b] was used, and the compound represented by [Intermediate 2-c] 29.7 g (yield 80.2 %).

[Scheme 2-4] Synthesis of [Chemical Formula 24]

[Intermediate 1-f] [Intermediate 2-c] [Formula 24]

Synthesis Example 1 Synthesized by the same method except for using [Intermediate 2-c] instead of [Intermediate 1-e] used in [Scheme 1-7], and 5.5 g of the compound represented by [Chemical Formula 24] (yield 35.8%) Got it.

MS [M] ⁺ : 622

[Synthesis Example 3] Synthesis of Chemical Formula 46

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

[Intermediate 3-a]

Synthesis Example 1 Except for using 3-(1-naphthyl)phenyl boronic acid instead of the phenyl boronic acid used in [Reaction Scheme 1-6], it was synthesized in the same manner, and the compound represented by [Intermediate 3-a] 47.5 g (yield 68.4%) was obtained.

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

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

Synthesis Example 1 [Intermediate 1-f] used in [Scheme 1-7] was synthesized by the same method except that [Intermediate 3-a] was used, and 4.5 g of the compound represented by [Chemical Formula 46] (yield 39.6%) Got it.

MS [M] ⁺ : 698

[Synthesis Example 4] Synthesis of Chemical Formula 73

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

[Intermediate 4-a]

Synthesis Example 1 Synthesized by the same method except that 2-aminobenzonitrile was used instead of [Intermediate 1-a] used in [Scheme 1-2], and 54.2 g of the compound represented by [Intermediate 4-a] (yield 92.6% ).

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

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

Synthesis Example 1 [Intermediate 1-b] used in [Scheme 1-3] was synthesized in the same manner except that [Intermediate 4-a] was used, and the compound represented by [Intermediate 4-b] 45.0 g (yield 91 %).

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

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

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

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

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

Synthesis Example 1 The compound represented by [Intermediate 4-d] 46.0 g (yield 80) was synthesized in the same manner except that [Intermediate 4-c] was used instead of [Intermediate 1-d] used in [Scheme 1-5] %).

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

[Intermediate 4-e]

In a 5000 mL round bottom flask under nitrogen, methylanthranylate 73.8 g (0.0.488 mol), 2-bromo-triphenylene 100.0 g (0.326 mol), palladium acetate (Pd(OAc) ₂ ) 0.7 g (0.003) mol), Xantphos 5.7 g (0.010 mol), cesium carbonate 212.1 g (0.651 mol), and 1500 mL of toluene were added and refluxed for 6 hours. When the reaction was completed, the resultant of the reaction was separated into layers to remove an aqueous layer, and the organic layer was separated and concentrated under reduced pressure, followed by column chromatography to obtain 108.6 g (88.4%) of a compound represented by [Intermediate 4-e].

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

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

70 g (0.185 mol) of [Intermediate 4-e] obtained in [Scheme 4-5] and 700 mL of diisopropyl ether were added, stirred, and 205 mL of methyl magnesium bromide was slowly added dropwise. After dropwise addition, the mixture was stirred at 50°C. When the reaction was completed, the reaction product was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure, followed by column chromatography to obtain 58.0 g (82.8%) of a compound represented by [Intermediate 4-f].

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

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

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

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

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

Synthesis Example 1 [Intermediate 4-g] instead of [Intermediate 1-f] used in [Scheme 1-7] was synthesized in the same manner except that [Intermediate 4-d] was used instead of [Intermediate 1-e]. 5.3 g (yield 42.5%) of a compound represented by Chemical Formula 73] was obtained.

MS [M] ⁺ : 638

[Synthesis Example 5] Synthesis of Chemical Formula 84

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

[Intermediate 5-a]

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

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

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

Synthesis Example 1 Except that [intermediate 5-a] was used instead of 3-bromocarbazole used in [Scheme 1-6], and 3-carbazole boronic acid pinacol ester was used instead of phenylboronic acid, synthesized in the same manner [ 19.2 g (yield 65.3%) of the compound represented by Chemical Formula 5-b] was obtained.

[Scheme 5-3] Synthesis of [Chemical Formula 84]

[Intermediate 5-b] [Intermediate 4-d] [Formula 84]

Synthesis Example 1 [Intermediate 5-b] instead of [Intermediate 1-f] used in [Scheme 1-7] was synthesized in the same manner except that [Intermediate 4-d] was used instead of [Intermediate 1-e]. Compound 5.0 g (yield 39.5%) represented by Chemical Formula 84] was obtained.

MS [M] ⁺ : 625

[Synthesis Example 6] Synthesis of Chemical Formula 92

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

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

After filling the dried 2 L reactor with nitrogen, 10.9 g (0.055 mol) of [Intermediate 4-a] obtained in [Scheme 4-1] and 200 mL of tetrahydrofuran were added, and 36.8 mL (0.110) of 3M-phenylmagnesium bromide at 0 °C. mol) was slowly added dropwise and stirred under reflux for 3 hours. When the starting material disappears, the mixture was lowered to a low temperature again, and 14.4 g (0.066 mol) of 4-bromobenzoyl chloride was dissolved in 150 mL of tetrahydrofuran, and then slowly added dropwise, followed by reflux stirring for 2 hours. When the reaction was completed, an aqueous ammonium chloride solution was added to stop the reaction, extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain 17.3 g (yield 71.3%) of the compound represented by [Chemical Formula 6-a].

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

[Intermediate 6-a] [Formula 92]

Synthesis Example 1 [Intermediate 1-f] used in [Scheme 1-7] was synthesized by the same method except that carbazole was used instead of [Intermediate 1-e] and [Intermediate 6-a] was used. 4.8 g (yield 43.1%) of the displayed compound was obtained.

MS [M] ⁺ : 613

[Synthesis Example 7] Synthesis of Chemical Formula 117

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

[Intermediate 7-a]

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

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

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

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

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

[Intermediate 7-c]

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

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

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

In a 2 L reactor, [Intermediate 7-b] 69.0 g (0.197 mol) obtained in [Scheme 7-2], [Intermediate 7-c] 67.1 g (0.256 mol) obtained in [Scheme 7-3], and tetrakis ( Triphenylphosphine) palladium 6.8 g (6 mmol), potassium carbonate 68.1 g (0.493 mol), 1,4-dioxane 345 mL, toluene 345 mL, and distilled water 138 mL were added and stirred at 100° C. for 12 hours. When the reaction was completed, the temperature was adjusted to room temperature, extracted with ethyl acetate, and the organic layer was concentrated, followed by column chromatography to obtain 57.0 g (yield 71.4%) of the compound represented by [Intermediate 7-d].

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

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

[Intermediate 7-d] 57 g (0.141 mol) obtained in [Scheme 7-4] and 570 mL of tetrahydrofuran were added to the dried 2L reactor and stirred. After cooling to 0° C., 164.01 mL (0.492 mol) of 3M-methylmagnesium bromide was added dropwise, followed by refluxing for 3 hours. Saturated aqueous ammonium chloride solution was added, and the organic layer was extracted using ethyl acetate and water. After the organic layer was concentrated under reduced pressure, 171 mL of phosphoric acid was added and stirred at 50° C. for 12 hours. When the reaction was completed, the organic layer was extracted using methylene chloride and distilled water, concentrated under reduced pressure, and separated by column chromatography to obtain 40.0 g (yield 73.4%) of the compound represented by [Intermediate 7-e].

[Scheme 7-6] Synthesis of [Intermediate 7-f]

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

[Intermediate 7-e] 40.0 g (0.103 mol) obtained in [Scheme 7-5], cesium carbonate 100.9 g (0.310 mol), tetrahydrofuran 240 mL, and methanol 120 mL were added to the dried 1 L reactor under nitrogen The mixture was stirred under reflux for 5 hours. When the reaction was completed, the reaction mixture was added to cooled water, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure, and separated by column chromatography to obtain 22.0 g (yield: 91.3%) of the compound represented by [Intermediate 7-f].

[Scheme 7-7] Synthesis of [Chemical Formula 117]

[Intermediate 7-f] [Intermediate 4-d] [Formula 117]

Synthesis Example 1 [Intermediate 7-f] instead of [Intermediate 1-f] used in [Scheme 1-7] was synthesized in the same manner except that [Intermediate 4-d] was used instead of [Intermediate 1-e]. To obtain 3.6 g (yield 38.4%) of a compound represented by Chemical Formula 117].

MS [M] ⁺ : 513

[Synthesis Example 8] Synthesis of Chemical Formula 135

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

[Intermediate 8-a]

After filling the dried 2 L reactor with nitrogen, 100.0 g (999 mmol) of 3-methyl crotonic acid and 500 mL of benzene were added and stirred. Aluminum chloride 399.5 g (2996 mmol) was slowly added and stirred under reflux for 5 hours. When the reaction is complete, the reaction solution is slowly added dropwise to 1500 mL of low-temperature 6N hydrochloric acid, stirred for 30 minutes, extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and distilled under reduced pressure to purify the compound 125.0 represented by [Intermediate 8-a]. g (yield 78%) was obtained.

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

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

To 60 g (375 mmol) of the compound represented by [Intermediate 8-a] obtained from [Scheme 8-1] and 65 g (450 mmol) of phenyl hydrazine hydrochloride, 600 mL of acetic acid and 30 mL of hydrochloric acid were added and stirred under reflux for 12 hours. . When the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 63 g (yield 72%) of the compound represented by [Chemical Formula 8-b].

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

[Intermediate 8-b] [Intermediate 4-d] [Formula 135]

Synthesis Example 1 [Intermediate 8-b] instead of [Intermediate 1-f] used in [Scheme 1-7] was synthesized in the same manner except that [Intermediate 4-d] was used instead of [Intermediate 1-e]. 3.6 g (yield 37.4%) of a compound represented by Chemical Formula 135] was obtained.

MS [M] ⁺ : 513

[Synthesis Example 9] Synthesis of Chemical Formula 136

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

[Intermediate 9-a]

Synthesis Example 1 Except that 1-naphthyl boronic acid was used instead of phenyl boronic acid used in [Scheme 1-3] and synthesized by the same method, 27.6 g (yield 81.6%) of the compound represented by [Intermediate 9-a] Got it.

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

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

Synthesis Example 1 [Intermediate 1-c] used in [Scheme 1-4] was synthesized in the same manner except that [Intermediate 9-a] was used, and 23.1 g of the compound represented by [Intermediate 9-b] (yield 79.3 %).

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

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

Synthesis Example 1 [Intermediate 1-d] used in [Scheme 1-5] was synthesized in the same manner, except that [Intermediate 9-b] was used, and the compound represented by [Intermediate 9-c] 18.7 g (yield 80.9) was used. %).

[Scheme 9-4] Synthesis of [Chemical Formula 136]

[Intermediate 8-b] [Intermediate 9-c] [Formula 136]

Synthesis Example 1 [Intermediate 8-b] instead of [Intermediate 1-f] used in [Scheme 1-7] was synthesized in the same manner except that [Intermediate 9-c] was used instead of [Intermediate 1-e]. Compound 4.7 g (yield 41.9%) of the compound represented by Chemical Formula 136] was obtained.

MS [M] ⁺ : 563

[Synthesis Example 10] Synthesis of Chemical Formula 137

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

[Intermediate 10-a]

Synthesis Example 4 Except that 2-naphthyl boronic acid was used instead of phenyl boronic acid used in [Scheme 4-2] and synthesized in the same manner to obtain 30.1 g (yield 83.7%) of the compound represented by [Intermediate 10-a] Got it.

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

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

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

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

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

Synthesis Example 1 [Intermediate 1-d] used in [Scheme 1-5] was synthesized in the same manner except that [Intermediate 10-b] was used, and 25.5 g of the compound represented by [Intermediate 10-c] (yield 80.3) %).

[Scheme 10-4] Synthesis of [Chemical Formula 137]

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

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

MS [M] ⁺ : 563

Example: Preparation of organic light emitting diode

The ITO glass was patterned so that the light emitting area had a size of 2 mm×2 mm, and then washed. After mounting the substrate in the vacuum chamber, the base pressure is 1 × 10 ^-6 torr, and then the organic material is placed on the ITO DNTPD (700 Å), NPD (300 Å), the compound prepared by the present invention + RD-1 ( 10%) (300 Å), Compound E: Liq = 1:1 (250 Å), Liq (10 Å), and Al (1,000 Å) were formed in the order, and the measurement was performed at 0.4 mA.

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

DNTPD NPD

RD-1 Compound E Liq

Comparative example

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

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

For the organic electroluminescent devices manufactured according to Comparative Examples 1 to 4 and Examples 1 to 7, the driving voltage (V), power efficiency (lm/W), and color coordinates (CIEx, CIEy) were measured, and the result Is shown in the following [Table 1].

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

As shown in [Table 1], the organic compounds secured by the present invention are compounds F, G, H, I, that is, compared to compounds that do not have an X substituent at a specific position, as in [Chemical Formula 1] according to the present invention. , It shows the effect of relatively lowering the driving voltage, and thus has higher power efficiency.

Claims (8)

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

In the above [Formula 1],
L may be a single bond, or any one divalent linking group selected from a substituted or unsubstituted arylene group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and m is 0 to It is an integer of 2, and when m is 2, a plurality of L is the same as or different from each other,

ETU-* of the [Chemical Formula 1] is represented by the following [Structural Formula 1-1] or [Structural Formula 1-2],
[Structural Formula 1-1] [Structural Formula 1-2]

In the [Structural Formula 1-1] to [Structural Formula 1-2],
A ₁ to A ₇ are the same as or different from each other, and each independently CR ₁ to CR ₇ or N,
X is 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 aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroatom O, N Or any one selected from a C3-C50 heteroaryl group, a cyano group, and a halogen group having S,
The R ₁ to R ₇ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, 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 A substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, 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 alkylamine having 1 to 30 carbon atoms Group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl having 3 to 50 carbon atoms having O, N or S as a hetero atom It is any one selected from a group, a substituted or unsubstituted silyl group, a cyano group, a nitro group, and a halogen group,
Two adjacent two of R ₁ to R ₇ may be connected to each other to form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring,

*-HTU of the [Chemical Formula 1] is represented by any one selected from the following [Structural Formula 2] to [Structural Formula 4],
[Structural Formula 2]

In the above [Structural Formula 2],
Z is a single bond or any one selected from _{CR 12} R ₁₃ , NR ₁₄ , O, S and SiR ₁₅ R _16,
R ₈ to R ₁₁ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, 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 alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted and hetero atom O, It is any one selected from a C3-C50 heteroaryl group having N or S, a substituted or unsubstituted silyl group, a cyano group, a nitro group, and a halogen group,
Two adjacent two of R ₈ to R ₁₁ are connected to each other to form an additional ring, provided that when Z is a single bond, _{two adjacent two of R 8} to R ₁₁ may be connected to each other to form a condensed aromatic ring. ,
Y is the _{same as the definition of R 1} to R ₇ , m is an integer of 1 to 5, and when m is 2 or more, a plurality of Y may be the same or different from each other,
The Y may be combined with an adjacent substituent to form a monocyclic or polycyclic aromatic hydrocarbon ring,
The R ₁₂ to R ₁₆ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, 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 Any one selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom,
The R ₁₂ and R ₁₃ , R ₁₅ and R ₁₆ are each connected to each other to each other and are a substituted or unsubstituted fused C 3 to C 30 cycloalkyl group, a substituted or unsubstituted fused C 2 to C 30 heterocycloalkyl group, a substituted or Can form an unsubstituted C5 to C30 aryl group or a substituted or unsubstituted C3 to C30 heteroaryl group,

[Structural Formula 3]

[Structural Formula 4]

In the [Structural Formula 3] and [Structural Formula 4],
Z is a single bond or any one selected from _{CR 12} R ₁₃ , NR ₁₄ , O, S and SiR ₁₅ R _16,
R ₈ to R ₁₁ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, and a substituted or unsubstituted It is any one selected from a heteroaryl group having 3 to 50 carbon atoms, which is a ring and has O, N or S as a hetero atom,
Two adjacent two of R ₈ to R ₁₁ may be connected to each other to form a condensed aromatic ring,
Y is the _{same as the definition of R 1} to R ₇ , m is an integer of 1 to 5, and when m is 2 or more, a plurality of Y may be the same or different from each other,
The Y may be combined with an adjacent substituent to form a monocyclic or polycyclic aromatic hydrocarbon ring,
The R ₁₄ to R ₁₆ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, 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 Any one selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom,
The R ₁₅ and R ₁₆ are each connected to each other to each other, a substituted or unsubstituted fused C3 to C30 cycloalkyl group, a substituted or unsubstituted fused C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C5 to C5 30 aryl group or a substituted or unsubstituted C 3 to C 30 heteroaryl group may be formed,
The R ₁₂ and R ₁₃ are the same as or different from each other, and each independently a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C50 Any one selected from an aryl group of and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom,
In the case where Z is CR ₁₂ R ₁₃ , R ₁₂ and R ₁₃ are each linked to each other to form a substituted or unsubstituted fused C 3 to C 30 cycloalkyl group, a substituted or unsubstituted fused C 2 to C 30 heterocycloalkyl group , To form a substituted or unsubstituted aryl group having 5 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. delete The method of claim 1,
X is an organic light-emitting compound, characterized in that selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom. The method of claim 1,
[Chemical Formula 1] is an organic light-emitting compound, characterized in that selected from the following formula:

A first electrode; A second electrode facing the first electrode; And at least one organic layer interposed between the first electrode and the second electrode,
An organic electroluminescent device, wherein the organic layer includes 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 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 6,
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 1]. The method of claim 5,
An organic electroluminescent device, characterized in that the organic layer further includes at least one organic light-emitting layer emitting red, green, or blue light to emit white light.

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