KR102191021B1 - An electroluminescent compound and an electroluminescent device comprising 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 compound according to the present invention has excellent luminous efficiency and lifespan characteristics of a material, thus exhibiting excellent luminous efficiency and at the same time It is possible to manufacture an organic light emitting device having power efficiency and long life characteristics.
[Formula 1]

Description

An electroluminescent compound and an electroluminescent device comprising 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, and do not require a backlight, are lightweight and thin, and are advantageous in terms of power consumption and color reproduction. Due to its wide range, it is 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 not only form the device on a flexible transparent substrate such as plastic, but can be driven at a voltage lower than 10 V compared to a plasma display panel or an inorganic EL display, and consumes relatively little power. , It has the advantage of excellent color. In addition, since organic electroluminescent devices can display three colors of green, blue, and red, they are attracting much attention as a next-generation rich color display device.

The most important factor determining the luminous efficiency in an organic electroluminescent device is a luminescent material. Currently, a fluorescent material is widely used as a light emitting material, but the development of a phosphorescent material is one of the theoretical ways to further improve luminous efficiency 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 is the most widely known until now, and 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, and thus, development of a more stable and high-performance host material is required.

Accordingly, the problem to be solved by the present invention is to solve the above problem, and to provide an organic light-emitting compound having superior luminous efficiency and improved power efficiency and long lifespan 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.

In order to solve the above problems, the present invention provides an organic light-emitting compound represented by the following [Chemical Formula 1], and provides an organic thin film layer for an organic light-emitting device comprising at least one or more of the organic light-emitting compounds. .

[Formula 1]

Specific substituents of the organic light-emitting compound [Chemical Formula 1] according to the present invention will be described later.

In addition, the present invention provides 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 is represented by the [Formula 1]. It is characterized in that it comprises an organic thin film layer containing at least one organic light emitting compound.

The organic layer may include at least one selected from a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer.

The organic light emitting compound is used as a host of the light emitting layer, and the light emitting layer may further include one or more dopant compounds.

In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device that emits white light by including at least one organic light-emitting layer emitting blue, red, or green light.

The organic light-emitting compound according to the present invention has excellent luminous efficiency and lifespan characteristics of a material, so that it is possible to manufacture an organic electroluminescent device having excellent power efficiency and long life characteristics while having excellent luminous efficiency.

1 is a schematic diagram of an organic electroluminescent 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 an organic light emitting compound represented by the following [Chemical Formula 1].

[Formula 1]

In the above [Formula 1],

X and Y are each independently CR ₂ or N, a plurality of X and Y may be the same or different, respectively, Z is CR ₃ R ₄ , SiR ₅ R ₆ , NR ₇ , PR ₈ , BR ₉ , P( =O)R ₁₀ , selected from O and S.

The R ₂ to R ₁₀ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or Unsubstituted C3-C20 heteroaryl group, substituted or unsubstituted C1-C60 alkoxy group, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C1-C20 alkyl Amino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted C 1 To 50 arylalkylamino group, substituted or unsubstituted C2 to C60 alkenyl group, substituted or unsubstituted C2 to C60 alkynyl group, hydroxyl group, nitro group, amino group, amidino group, hydrazine, hydrazone , A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted carbon number 5 It is selected from arylthio groups of to 60, cyano groups, halogen groups, deuterium and hydrogen.

과, 상기 Y 및 Z를 포함하고, 상기 L²에 연결되는

은 하기 [구조식 1]에서 선택될 수 있다.According to a preferred embodiment of the present invention, including the X and Z, and connected to the L ¹

And, including the Y and Z, and connected to the L ²

May be selected from the following [Structural Formula 1].

[Structural Formula 1]

In [Structural Formula 1],

R ₁₁ to R ₁₈ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted It is selected from a cyclic C3-C20 heteroaryl group.

L ¹ and L ² are each independently a chemical bond, a substituted or unsubstituted arylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkyne having 2 to 60 carbon atoms A nylene group, a substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a heterocycloalkylene group having 2 to 60 carbon atoms including at least one selected from N, O and S, a substituted or unsubstituted aryl having 6 to 50 carbon atoms It is selected from a ene group, a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms, and n and m are each independently an integer of 0 to 2.

According to a preferred embodiment of the present invention, L ¹ and L ² may each independently be a substituted or unsubstituted arylene group having 6 to 50 carbon atoms or a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms.

R ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms Of a heteroaryl group, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted Arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, Substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, hydroxyl group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid A group or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, It is selected from cyano group, halogen group, deuterium and hydrogen.

은 하기 [구조식 2] 내지 [구조식 11] 중에서 선택되는 어느 하나일 수 있다.According to a preferred embodiment of the present invention, which is connected to the L ¹

May be any one selected from the following [Structural Formula 2] to [Structure 11].

[Structural Formula 2] [Structural Formula 3] [Structural Formula 4] [Structural Formula 5]

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

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

In the [Structural Formula 2] to [Structural Formula 11],

T ₁ to T ₁₂ are the same as or different from each other, and are each independently selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O and S.

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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number It is selected from 5 to 30 aryl groups and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a hetero atom.

According to a preferred embodiment of the present invention, the [Structural Formula 2] to [Structural Formula 11] may be selected from the following [Structural Formula 12].

[Structural Formula 12]

In [Structural Formula 12],

X is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 to 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl having 1 to 30 carbon atoms Selected from an amine group, a substituted or unsubstituted aryl group having 5 to carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a hetero atom, a cyano group, a nitro group and a halogen group And m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs may be the same or different from each other.

According to a preferred embodiment of the present invention, [Chemical Formula 1] may be selected from the following [Chemical Formula 2] to [Chemical Formula 249].

Another aspect of the present invention relates to an organic thin film layer for an organic light emitting device comprising at least one or more organic light emitting compounds represented by the above [Formula 1].

The organic thin film layer includes an organic light-emitting compound represented by [Chemical Formula 1] as a host, and further includes at least one dopant compound represented by the following [General Formula A-1] to [General Formula J-1] It is characterized.

[General Formula A-1]

ML ₁ L ₂ L ₃

The M is selected from the group consisting of metals of groups 7, 8, 9, 10, 11, 13, 14, 15, and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ and L ₃ may be the same as or different from each other as a ligand, and may each independently include any one selected from the following [Structure 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 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, the 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 a specific 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 5-membered ring, and does not have any Represents a substituent, and R ^C13 and R ^C14 are each independently a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and represents a substituent that does not have anything that connects to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, substituted Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonded to M ^C1 .

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

[General Formula E-1]

In the above [general formula E-1],

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

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

[General Formula F-1]

In the above [general formula F-1],

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

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

[General Formula G-1]

In the above [general formula G-1],

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

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be linked to each other to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonded to M ^F1 .

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

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

In the above [General Formula H-1] 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. ) A ligand, a bipyridyl ligand or a phenanthroline ligand that forms a 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 rings of rings A to D may have a substituent, and the other two rings are an aryl ring or heterocycle 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 two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (term) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. Z ¹ , Z ² , Z ³ and Z ⁴ are any two representing a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

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

[General Formula J-1]

In the above [general formula J-1],

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

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

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

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

In addition, the organic thin film layer according to the present invention may further include various hosts and various dopant materials in addition to the dopant compound and the host compound represented by [Chemical Formula 1].

When the dopant compound is simultaneously included with the host compound as described above, the content of the dopant may be generally selected in the range of about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host.

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 is provided according to the present invention. It includes an organic thin film layer containing a compound represented by [Formula 1].

The organic layer may further include 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, and the hole injection layer, the hole transport layer , One of a functional layer having a hole injection function and a hole transport function at the same time, an emission layer, an electron transport layer, and an electron injection layer may be an organic thin film layer according to the present invention, and preferably, the emission layer may be an organic thin film layer according to the present invention. .

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. Including 80, may further include a hole injection layer 30 and an electron injection layer 70 if necessary, it is also possible to further form an intermediate layer of one or two layers, and 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 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 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 of a hole injection layer material 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 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 vacuum deposition or spin coating to form a thin film. can do. The hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . 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 the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and [Formula 301] to [Formula 307] may be used, but limited thereto It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

[Formula 301] [Formula 302] [Formula 303]

[Chemical Formula 304] [Chemical Formula 305] [Chemical Formula 306]

[Chemical Formula 307]

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

As the material for the electron transport layer, a known electron transport material may be used as it has a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinorate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis(benzoquinolin-10-). olate: Bebq2), ADN, [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, 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, 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 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.

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 is the It refers to a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is a material used as a material for forming each layer. It means 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.

In addition, the organic light-emitting device according to the present invention may include one or more organic light-emitting layers emitting blue, red, or green light to emit white light, and a flat panel display device, a flexible display device, a single color or white flat lighting device And a device selected from 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 Formula 3

Synthesis Example 1-1. <1-a> was synthesized according to the following Scheme 1.

[Scheme 1]

<1-a>

In a 5000 mL round-bottom flask under nitrogen, 87 g (0.576 mol) of methyl anthranirate, 135.1 g (0.478 mol) of 1-bromo-4-iodobenzene, and 1.3 g (0.006 of palladium acetate (Pd(OAc) ₂ )) mol), Xantphos 10 g (0.017 mol), cesium carbonate 217.5 g (0.668 mol), and 2500 mL of toluene were added and refluxed for 6 hours. When the reaction was completed, the reaction product was separated into layers to remove an aqueous layer, and the organic layer was separated and concentrated under reduced pressure, and <1-a> 110 g (75%) was obtained through column chromatography.

Synthesis Example 1-2. <1-b> was synthesized according to Scheme 2 below.

[Scheme 2]

<1-b>

To a 5000 mL round-bottom flask, 110 g (0.359 mol) of the compound represented by Formula 1-a obtained from Scheme 1 and 1650 mL of diisopropyl ether obtained from Scheme 1 were added, and after stirring, 419 mL of methylmagnesium 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 an aqueous layer, and the organic layer was separated and concentrated under reduced pressure, and then <1-b> 108g (98.2%) was obtained through column chromatography.

Synthesis Example 1-3. <1-c> was synthesized according to Reaction Scheme 3 below.

[Scheme 3]

<1-c>

To a 1000 mL round-bottom flask, 108 g (0.36 mol) of a compound represented by Formula 1-b obtained from Scheme 2 and 400 mL of phosphoric acid were added, followed by stirring at room temperature. When the reaction was complete, water was added to the reaction product and stirred. After stirring, it was filtered and washed with water and methanol. <1-c> 75 g (75%) was obtained through column chromatography.

Synthesis Example 1-4. <1-d> was synthesized according to Reaction Scheme 4 below.

[Scheme 4]

<1-d>

In a 2000 mL round bottom flask under nitrogen, methylanthranyrate 90 g (0.588 mol), iodobenzene 80 g (0.392 mol), palladium acetate (Pd(OAc) ₂ ) 0.9 g (0.004 mol), xantphos 6.8 g (0.012 mol), cesium carbonate 255.5 g (0.784 mol), and 900 mL of toluene were added and refluxed for 6 hours. When the reaction was completed, the reaction product was separated into layers to remove an aqueous layer, and the organic layer was separated and concentrated under reduced pressure, and then <1-d> 69 g (75%) was obtained through column chromatography.

Synthesis Example 1-5. <1-e> was synthesized according to Scheme 5 below.

[Scheme 5]

<1-e>

In a 2000 mL round-bottom flask, 69 g (0.304 mol) of a compound represented by Formula 1-d obtained from Scheme 4 and 600 mL of diisopropyl ether were added under nitrogen, and after stirring, 390 mL of methylmagnesium 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 an aqueous layer, and the organic layer was separated and concentrated under reduced pressure, and then <1-e> 66g (95%) was obtained through column chromatography.

Synthesis Example 1-6. <1-f> was synthesized according to Scheme 6 below.

[Scheme 6]

<1-f>

To a 1000 mL round-bottom flask, 66 g (0.29 mol) of a compound represented by Formula 1-e obtained from Scheme 5 and 300 mL of phosphoric acid were added, followed by stirring at room temperature. When the reaction was complete, water was added to the reaction product and stirred. After stirring, it was filtered and washed with water and methanol. <1-f> 45g (73%) was obtained through column chromatography.

Synthesis Example 1-7. <1-g> was synthesized according to Scheme 7 below.

[Scheme 7]

<1-g>

In a 2000 mL round bottom flask, 39.5 g (1.7 mol) of magnesium, 10 g of iodine and 100 mL of tetrahydrofuran were added under nitrogen and refluxed for 2 hours. After cooling to room temperature, 212.8 g (1.4 mol) of bromobenzene was dissolved in 200 mL of tetrahydrofuran and slowly added dropwise. After the dropwise addition, it was refluxed for 2 hours and cooled to room temperature. In another 2 L round bottom flask, 100 g (0.54 mol) of cyanuric chloride was dissolved in 200 mL of tetrahydrofuran, and the reaction solution was cooled to 0 °C. Maintain the temperature of the reaction solution above at 0 ℃ and slowly add dropwise. After completion of the reaction, the reaction was terminated with a 4 M aqueous hydrochloric acid solution, extracted, the organic layer was concentrated under reduced pressure, and recrystallized with hexane to obtain <1-g> 100 g (68.9%).

Synthesis Example 1-8. <1-h> was synthesized according to Scheme 8 below.

[Scheme 8]

<1-h>

In a 500 mL round-bottom flask, 0.7 g of sodium hydride was dissolved in 30 mL of N,N-diethylamide under nitrogen and cooled to 0°C. 6.0 g (0.021 mol) of the compound represented by Formula 1-c obtained from Scheme 3 at 0° C. was dissolved in 30 mL of N,N-diethylamide and slowly added dropwise. After dropwise addition, the mixture was stirred for 1 hour. 8.4 g (0.031 mol) of the compound represented by Formula 1-g obtained from Scheme 8 at 0° C. was dissolved in 60 mL of N,N-diethylamide, and then slowly added dropwise. After dropwise addition, it was stirred at room temperature. When the reaction was completed, the reaction product was poured into water, stirred, filtered, and washed with water and methanol to obtain 8.0 g (80%) of <1-h>.

Synthesis Example 1-9. <3> was synthesized according to Scheme 9 below.

[Scheme 9]

<Formula 3>

In a 100 mL round-bottom flask, 8.0 g (15.0 mmol) of the compound represented by formula 1-h obtained from Scheme 8, 6.8 g (32.0 mmol) of the formula 1-f obtained from Scheme 6, and tris(dibenzylideneacetone)dipalladium 0.6 g (1.0 mmol), 1,1`-bis (diphenylphosphino) ferrocene 0.4 g (1.0 mmol), sodium tertiary butoxide 6.2 g (65.0 mmol) and toluene 120 mL were added, followed by refluxing and stirring for 24 hours. . When the reaction is finished, the temperature is adjusted to room temperature and the crystal is filtered. The crystal was recrystallized from methylene chloride and acetone to obtain 5.3 g (53%) of a compound represented by <Chemical Formula 3>.

MS(MALDI-TOF): m/z 647.30[M] ⁺

Anal. Calc. for C ₄₈ H ₃₇ N ₅ : C, 83.43; H, 5.76; N, 10.81. Found C, 83.46; H, 5.75; N, 10.82.

Synthesis Example 2. Synthesis of Formula 6

Synthesis Example 2-1. <2-a> was synthesized according to Scheme 10 below.

[Scheme 10]

<2-a>

Compound represented by formula 1-g obtained from Scheme 8 100.0 g (373.5 mmol), 3-bromophenylboronic acid 75.0 g (373.5 mmol), tetrakis (triphenylphosphine) palladium 8.6 mg (7.5 mmol) , Potassium carbonate 103.0 g (747.0 mmol), 1,4-dioxane 500 mL, toluene 500 mL, distilled water 200 mL, and stirred at 100 °C for 24 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 63.0 g (43%) of the compound represented by <2-a>.

Synthesis Example 2-2. <2-b> was synthesized according to Scheme 11 below.

[Scheme 11]

<2-b>

In a 1000 mL round bottom flask, 100 g (0.478 mol) of the compound represented by 1-f obtained from Scheme 8, 202.8 g (0.717 mol) of 1-bromo-4-iodobenzene, 198.1 g (0.433 mol) of potassium carbonate, Copper chloride 14.2 g (0.143 mol) and dimethyl sulfoxide 800 mL were added and refluxed for 6 hours. When the reaction was completed, the reaction product was extracted, the organic layer was separated, concentrated under reduced pressure, and <2-b> 140 g (78%) was obtained through column chromatography.

Synthesis Example 2-3. <2-c> was synthesized according to Scheme 12 below.

[Scheme 12]

<2-c>

<2-c> 20 g (62%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Formula 1-a.

Synthesis Example 2-4. <2-d> was synthesized according to Scheme 13 below.

[Scheme 13]

<2-d>

<2-d> 18g (75%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Formula 1-b.

Synthesis Example 2-5. <2-f> was synthesized according to Scheme 14 below.

[Scheme 14]

<2-f>

<2-f> 15g (86%) was obtained by synthesizing in the same manner as the synthesis method for the compound represented by Formula 1-c above.

Synthesis Example 2-6. <Chemical Formula 6> was synthesized by the following Scheme 15.

[Scheme 15]

<Formula 6>

Synthesis was performed in the same manner as for the synthesis of the compound represented by Chemical Formula 2 above to obtain 5.3g (43%).

MS(MALDI-TOF): m/z 723.34[M] ⁺

Anal. Calc. for C ₄₈ H ₃₅ N ₅ : C, 84.62; H, 5.71; N, 9.67. Found C, 84.61; H, 5.72; N, 9.66.

Synthesis Example 3. Synthesis of Formula 14

Synthesis Example 3-1. <3-a> was synthesized according to Scheme 16 below.

[Scheme 16]

<3-a>

<3-a> 18g (67%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Formula 2 above.

Synthesis Example 3-2. <3-b> was synthesized according to Scheme 17 below.

[Scheme 17]

<3-b>

In a 500 mL round-bottom flask, add 100 mL of yen, ene-dimethylamide to 18 g (0.037 mol) of the compound represented by 3-a obtained in Scheme 16, stir under nitrogen for 30 minutes, and cool the reaction product to 0 °C. Let it. 6.7 g (0.04 mol) of N-bromosuccinimide was dissolved in 100 mL of N,N-dimethylamide and added dropwise. After dropwise addition, it was stirred at room temperature. When the reaction was completed, the resultant of the reaction was poured into water, stirred, filtered, and washed with water and methanol to obtain 17 g (80%) of the compound represented by Chemical Formula 3-b.

Synthesis Example 3-3. <Chemical Formula 14> was synthesized by the following Scheme 18.

[Scheme 18]

<Formula 14>

<14> 6.0gg (72%) was obtained by synthesizing in the same manner as the method for synthesizing the compound represented by Chemical Formula 3 above.

MS(MALDI-TOF): m/z 671.23 [M] ⁺

Anal. Calc. for C ₄₅ H ₂₉ N ₅ O ₂ : C, 80.46; H, 4.35; N, 10.43; O, 4.76. Found C, 80.48; H, 4.34; N, 10.42; O, 4.77.

Synthesis Example 4. Synthesis of Chemical Formula 77

Synthesis Example 4-1. <4-a> was synthesized according to Scheme 19 below.

[Scheme 19]

<4-a>

2,4,6-trichlorotriazine 20.0 g (109 mmol), bromobenzene 17.1 g (109.0 mmol) and tetrakis (triphenylphosphine) palladium 2.5 g (2.2 mmol), potassium carbonate 30.1 g (218.0 mmol) Was added to a mixed solvent of 600 mL of tetrahydrafuran, 400 mL of toluene, and 400 mL of distilled water, stirred for 9 hours, and refluxed. When the reaction is complete, the organic layer is washed with a saturated aqueous sodium chloride solution after extraction and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and then recrystallized from toluene to obtain 20.7 g (84%) of the compound represented by <4-a>.

Synthesis Example 4-2. <4-b> was synthesized according to Scheme 20 below.

[Scheme 20]

<4-b>

Compound 20.7 g (91.56 mmol) represented by 4-a obtained in Scheme 19, dibenzothiophene-4-boronic acid 20.9 g (91.56 mmol) and tetrakis (triphenylphosphine) palladium 2.1 g (1.8 mmol) , Potassium carbonate 25.3 g (183.1 mmol) was added to a mixed solvent of 600 mL of tetrahydrafuran, 400 mL of toluene, and 400 mL of distilled water, and stirred for 12 hours and refluxed. When the reaction is complete, the organic layer is washed with a saturated aqueous sodium chloride solution after extraction and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and then recrystallized from methylene chloride and nucleic acid to obtain 23.6 g (69%) of the compound represented by <4-b>.

Synthesis Example 4-3. <4-c> was synthesized according to the following Scheme 21.

[Scheme 21]

<4-c>

<4-c> 15g (68.7%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Chemical Formula 1-h.

Synthesis Example 4-4. <4-d> was synthesized according to Scheme 22 below.

[Scheme 22]

<4-d>

<4-d> 13.5g (82.7%) was obtained by synthesizing by the same method as the synthesis method for the compound represented by Chemical Formula 3 above.

Synthesis Example 4-5. <Chemical Formula 77> was synthesized according to Reaction Scheme 23 below.

[Scheme 23]

<Formula 77>

It was synthesized by the same method as the synthesis method for the compound represented by Chemical Formula 3 above to obtain 5.5g (61%).

MS(MALDI-TOF): m/z 802.29 [M] ⁺

Anal. Calc. for C ₅₄ H ₃₈ N ₆ S: C, 80.77; H, 4.77; N, 10.47; S, 3.99. Found C, 80.78; H, 4.78; N, 10.46; S, 3.97.

Synthesis Example 5. Synthesis of Chemical Formula 134

Synthesis Example 5-1. <5-a> was synthesized according to Reaction Scheme 24 below.

[Scheme 24]

<5-a>

Synthesis was carried out in the same manner as for the synthesis of the compound represented by Chemical Formula 4-b to obtain 21.9g (69%) of <5-a>.

Synthesis Example 5-2. <5-b> was synthesized according to Scheme 25 below.

[Scheme 25]

<5-b>

<5-b> 18g (66.6%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Formula 2-a.

Synthesis Example 5-3. <5-c> was synthesized according to Scheme 26 below.

[Scheme 26]

<5-c>

<5-c> 36g (43.2%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Chemical Formula 3-b.

Synthesis Example 5-4. <5-d> was synthesized according to Scheme 27 below.

[Scheme 27]

<5-d>

<5-d> 38g (82.6%) was obtained by synthesizing in the same manner as the synthesis method for the compound represented by Chemical Formula 1-h.

Synthesis Example 5-5. <5-e> was synthesized according to Scheme 28 below.

[Scheme 28]

<5-e>

Synthesized by the same method as the synthesis method for the compound represented by Chemical Formula 3 above to obtain 28.3g (55.4%) of <5-e>.

Synthesis Example 5-6. <134> was synthesized according to Scheme 29 below.

[Scheme 29]

<Formula 134>

It was synthesized in the same manner as for the synthesis of the compound represented by Chemical Formula 1-h, to obtain 7.1g (58%).

MS(MALDI-TOF): m/z 849.28 [M] ⁺

Anal. Calc. for C ₄₈ H ₃₁ D ₅ N ₆ : C, 84.78; H, 4.62; N, 4.94; O, 1.88; S, 3.77. Found C, 84.77; H, 4.64; N, 4.92; O, 1.89; S, 3.76.

Synthesis Example 6. Synthesis of Chemical Formula 178

Synthesis Example 6-1. <6-a> was synthesized according to Reaction Scheme 30 below.

[Scheme 30]

<6-a>

Synthesis was carried out in the same manner as the method for synthesizing the compound represented by Chemical Formula 3 above to obtain 77.1g (78%).

Synthesis Example 6-2. <6-b> was synthesized according to Reaction Scheme 31 below.

[Scheme 31]

<6-b>

After dissolving 77.0 g (18.60 mmol) of the compound represented by Formula 6-a obtained from Scheme 30 in 600 mL of tetrahydrofuran under a nitrogen stream, 128 mL (20.40 mmol) of 1.6 M normal-butyllithium was slowly added while stirring at -78 °C. It is added dropwise, and when the dropping is completed, the mixture is stirred for 1 hour while maintaining -78°C. After that, 29.0 g (27.90 mmol) of trimethylborate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 3 hours. When the reaction is complete, 300 mL of a 1 M aqueous hydrochloric acid solution is added dropwise at room temperature, followed by stirring for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized from methylene chloride and nucleic acid to obtain 56.0 g (76.2%) of the compound represented by <6-b>.

Synthesis Example 6-3. <6-c> was synthesized according to Scheme 32 below.

[Scheme 32]

<6-c>

<6-c> 58g (82.5%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Formula 1-b.

Synthesis Example 6-4. <6-d> was synthesized according to Reaction Scheme 33 below.

[Scheme 33]

<6-d>

<6-d> 36.3 g (65.3%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Formula 1-c.

Synthesis Example 6-5. <6-f> was synthesized according to Scheme 34 below.

[Scheme 34]

<6-f>

<6-d> 11.3 g (75.3%) was obtained by synthesizing in the same manner as for the synthesis of the compound represented by Chemical Formula 10 above.

Synthesis Example 6-6. <178> was synthesized according to Scheme 35 below.

[Scheme 35]

<Formula 178>

Synthesis was performed in the same manner as for the synthesis of the compound represented by Chemical Formula 8 above to obtain 9.4 g (80.3%).

MS(MALDI-TOF): m/z 847.37 [M] ⁺

Anal. Calc. for C ₆₅ H ₄₇ N ₅ : C, 86.93; H, 5.27; N, 7.80. Found C, 86.95; H, 5.26; N, 7.81.

Synthesis Example 7. Synthesis of Chemical Formula 192

Synthesis Example 7-1. <7-a> was synthesized according to Scheme 29 below.

[Scheme 36]

<7-a>

Synthesis was carried out in the same manner as for the synthesis of the compound represented by 2-a to obtain 21.6 g (89.3%) of <7-a>.

Synthesis Example 7-2. <7-b> was synthesized according to Scheme 37 below.

[Scheme 37]

<7-b>

Synthesis was carried out in the same manner as in the method for synthesizing the compound represented by 1-a to obtain 20.7 g (85.0%) of <7-b>.

Synthesis Example 7-3. <7-c> was synthesized according to Scheme 38 below.

[Scheme 38]

<7-c>

Synthesis was carried out in the same manner as for the synthesis of the compound represented by 1-b to obtain 12.6 g (63.1%) of <7-c>.

Synthesis Example 7-4. <7-d> was synthesized according to Scheme 39 below.

[Scheme 39]

<7-d>

Synthesis was carried out in the same manner as in the method for synthesizing the compound represented by 1-c to obtain <7-d> 12.0 g (69.1%).

Synthesis Example 7-5. <Chemical Formula 192> was synthesized by the following Scheme 40.

[Scheme 40]

<192>

<192> 6.5 g (57.2%) was obtained by synthesizing in the same manner as the method for synthesizing the compound represented by Chemical Formula 3 above.

MS(MALDI-TOF): m/z 799.37 [M] ⁺

Anal. Calc. for C ₅₇ H ₄₅ N ₅ : C, 85.58; H, 5.67; N, 8.75. Found C, 85.56; H, 5.68; N, 8.74.

Synthesis Example 8. Synthesis of Formula 199

Synthesis Example 8-1. <8-a> was synthesized according to Scheme 41 below.

[Scheme 41]

<8-a>

Synthesis was performed in the same manner as for the synthesis of the compound represented by Chemical Formula 3 to obtain <8-a> 18.0 g (77.8%).

Synthesis Example 8-2. <199> was synthesized according to the following Scheme 42.

[Scheme 42]

<199>

Synthesis was performed in the same manner as in the method for synthesizing the compound represented by 1-h to obtain 10.3 g (78.14%).

MS(MALDI-TOF): m/z 713.26 [M] ⁺

Anal. Calc. for C ₄₈ H ₃₅ N ₅ S: C, 80.76; H, 4.94; N, 9.81; S, 4.49. Found C, 80.77; H, 4.95; N, 9.80; S, 4.47.

Synthesis Example 9. Synthesis of Formula 210

Synthesis Example 9-1. <9-a> was synthesized according to Scheme 43 below.

[Scheme 43]

<9-a>

Synthesis was carried out in the same manner as for the synthesis of the compound represented by 2-a to obtain 13.6 g (90.9%) of <9-a>.

Synthesis Example 9-2. <9-b> was synthesized according to Scheme 44 below.

[Scheme 44]

<9-b>

Synthesis was carried out in the same manner as for the synthesis of the compound represented by 6-b to obtain 8.5 g (94.1%) of <9-b>.

Synthesis Example 9-3. <9-c> was synthesized according to Scheme 45 below.

[Scheme 45]

<9-c>

Synthesis was performed in the same manner as in the compound synthesis method represented by 2-a to obtain 13.6 g (90.9%) of <9-c>.

Synthesis Example 9-4. <210> was synthesized according to Scheme 46 below.

[Scheme 46]

<210>

<210> 6.5 g (62.0%) was obtained by synthesizing in the same manner as the compound synthesis method represented by Chemical Formula 3.

MS(MALDI-TOF): m/z 923.40 [M] ⁺

Anal. Calc. for C ₆₇ H ₄₉ N ₅ : C, 87.08; H, 5.34; N, 7.58. Found C, 87.06; H, 5.35; N, 7.59.

Synthesis Example 10. Synthesis of Chemical Formula 256

Synthesis Example 10-1. <10-a> was synthesized according to Scheme 47 below.

[Scheme 47]

<10-a>

Synthesis was performed in the same manner as for the synthesis of the compound represented by Chemical Formula 3 to obtain 14.6 g (83.1%) of <10-a>.

Synthesis Example 10-2. <10-b> was synthesized according to Scheme 48 below.

[Scheme 48]

<10-b>

Synthesis was carried out in the same manner as in the method for synthesizing the compound represented by 2-a to obtain 12.7 g (62.6%) of <10-b>.

Synthesis Example 10-3. <256> was synthesized according to Scheme 49 below.

[Scheme 49]

<256>

Synthesis was carried out in the same manner as for the synthesis of the compound represented by Formula 3 to obtain 7.6 g (60.5%).

MS(MALDI-TOF): m/z 618.30 [M] ⁺

Anal. Calc. for C ₄₆ H ₃₈ N ₂ : C, 89.28; H, 6.19; N, 4.53. Found C, 89.27; H, 6.18; N, 4.55

Examples 1 to 10 Preparation of organic light emitting diodes

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), NPD (300 Å), the compound prepared by the present invention + Ir (ppy) Films were formed in the order of ₃ (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å), and measured at 0.4 mA.

Comparative example

The organic light-emitting diode device for the comparative example was fabricated in the same manner, except that CBP, which is commonly used as a phosphorescent host material, was used instead of the compound prepared according to the invention in the device structure of the above example, and the structure of the CBP is as follows. .

division Host Dopant Doping concentration% V Cd/㎡ CIEx CIEy T ₉₇ (Hr) Comparative Example 1 CBP Ir(ppy) ₃ 10 7.93 3801 0.297 0.624 68 Example 1 3 Ir(ppy) ₃ 10 4.25 4989 0.262 0.629 178 Example 2 6 Ir(ppy) ₃ 10 4.31 5452 0.299 0.617 154 Example 3 14 Ir(ppy) ₃ 10 4.20 4945 0.280 0.625 135 Example 4 77 Ir(ppy) ₃ 10 4.41 4785 0.302 0.623 137 Example 5 134 Ir(ppy) ₃ 10 4.15 4897 0.315 0.621 171 Example 6 178 Ir(ppy) ₃ 10 4.32 5102 0.294 0.615 102 Example 7 192 Ir(ppy) ₃ 10 4.53 5045 0.293 0.620 178 Example 8 199 Ir(ppy) ₃ 10 4.35 5315 0.308 0.612 168 Example 9 210 Ir(ppy) ₃ 10 4.64 5212 0.297 0.631 197 Example 10 256 Ir(ppy) ₃ 10 4.54 4785 0.308 0.625 123

In [Table 1], T97 refers to the time required for the luminance to decrease to 97% compared to the initial luminance.

As shown in [Table 1], when the organic light-emitting compound embodied according to the present invention is employed as the host compound of the light-emitting layer of the organic light-emitting device, the lifespan characteristics are remarkably improved, the light-emitting characteristics are excellent, and the driving voltage is reduced. By lowering it, power consumption can be improved by inducing an increase in power efficiency.

10: substrate 20: anode
30: hole injection layer 40: hole transport layer
50: organic light emitting layer 60: electron transport layer
70: electron injection layer 80: cathode

Claims (13)

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

In the above [Formula 1],
R ₁ is a substituted or unsubstituted C 3 to C 20 heteroaryl group excluding a phenothiazine group,
X and Y are each independently CR ₂ , a plurality of X and Y are each the same or different, and R ₂ is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 It is selected from an aryl group of to 40 and a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms,
Z is selected from CR ₃ R ₄ , NR ₅ , O and S (however, except when both Z in [Formula 1] are CR ₃ R ₄ ),
The R ₃ to R ₅ are selected from among hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms Is selected,
L ¹ and L ² are the same as or different from each other, each independently a chemical bond or a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, and n and m are each independently an integer of 0 to 2.
In the above substituted or unsubstituted, L ¹ , L ² and R ₁ to R ₅ are each independently deuterium, a halogen group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 6 It means to be further substituted with one or more substituents selected from an aryl group having 3 to 20 carbon atoms and a heteroaryl group having 3 to 20 carbon atoms. delete delete delete delete delete The method of claim 1,
[Chemical Formula 1] is an organic light-emitting compound, characterized in that selected from the following formula:

An organic thin film layer for an organic light emitting device comprising at least one organic light emitting compound represented by [Chemical Formula 1] according to claim 1. The method of claim 8,
The organic thin film layer is an organic thin film layer comprising an organic light emitting compound represented by [Chemical Formula 1] as a host, and further includes at least one dopant compound. A first electrode; A second electrode; And the organic thin film layer according to claim 8 interposed between the first electrode and the second electrode. delete The method of claim 10,
An organic electroluminescent device, wherein the organic thin film layer interposed between the first electrode and the second electrode is an emission layer. The method of claim 10,
The organic light-emitting device is an organic light-emitting device, characterized in that it emits white light by including at least one organic light-emitting layer emitting blue, red, or green light.

Images