KR102169440B1 - 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 including the same. 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, 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, the organic electroluminescent device can display three colors of green, blue, and red, and thus has attracted much attention as a next-generation rich color display device.

The most important factor in determining the luminous efficiency in an organic electroluminescent device is a light emitting material. Currently, a fluorescent material is widely used as a light emitting material, but the development of a phosphorescent material is one of the methods that can theoretically improve luminous efficiency more due to the light emitting mechanism, and accordingly, various phosphorescent materials have been developed up to now. In particular, 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 comprises at least one organic light-emitting compound as the organic light-emitting compound. Provides a thin layer.

[Formula 1]

Each substituent in [Chemical Formula 1] 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 light-emitting device having excellent luminous efficiency and power efficiency and long lifespan characteristics.

1 is a schematic diagram of an organic light emitting diode 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], Y ¹ to Y ⁸ are each independently CR ₁ to CR ₈ (however, when Y ¹ and Y ⁸ are each bonded to Z, C is), Z is CR ₉ R ₁₀ , SiR ₁₁ R _{12 ,} NR ₁₃ , PR ₁₄ , P(=OR ₁₅ ), BR ₁₆ , O and S are any one selected from, and k, l and m are each independently an integer of 0 to 2, and W ¹ and W ² Is C, and when m is 0, W ¹ and W ² form a covalent bond with each other.

In addition, the R ₁ to R ₁₆ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, A substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, 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 C 1 to 20 carbon atom Of an alkylamino 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 Arylalkylamino group having 1 to 50 carbon atoms, substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, hydride It is selected from the group consisting of a hydroxyl group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a cyano group, a halogen group, deuterium and hydrogen, and the R ₁ to R ₁₆ may be the same as or different from each other, and may be bonded to each other with an adjacent substituent to form a saturated or unsaturated ring.

According to a preferred embodiment, the organic light-emitting compound [Chemical Formula 1] according to the present invention may be a compound represented by the following [Chemical Formula 1a] to [Chemical Formula 1f].

[Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f]

In [Chemical Formula 1a] to [Chemical Formula 1f], Y ¹ to Y ⁸ and Z are the same as defined in [Chemical Formula 1].

In addition, according to a more preferred embodiment, it may be a compound represented by the following [Chemical Formula 2] to [Chemical Formula 7].

[Chemical Formula 2] [Chemical Formula 3]

[Chemical Formula 4] [Chemical Formula 5]

[Formula 6] [Formula 7]

In the above [Formula 2] to [Formula 7],

A and Z are each independently selected from CR ₉ R ₁₀ , SiR ₁₁ R _{12 ,} NR ₁₃ , PR ₁₄ , P(=OR ₁₅ ), BR ₁₆ , O and S.

L ₁ is a chemical bond, substituted or unsubstituted alkylene having 1 to 60 carbon atoms, substituted or unsubstituted alkenylene having 2 to 60 carbon atoms, substituted or unsubstituted alkynylene having 2 to 60 carbon atoms, substituted or unsubstituted A substituted or unsubstituted heterocycloalkylene having 2 to 60 carbon atoms, including at least one selected from a cycloalkylene having 3 to 60 carbon atoms, N, O and S, a substituted or unsubstituted arylene having 6 to 50 carbon atoms, and Is selected from the group consisting of substituted or unsubstituted heteroarylene having 3 to 50 carbon atoms, a and b are each independently an integer of 0 to 3, and when a and b are 2 or more, a plurality of L may be the same or different from each other I can.

R ₉ 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 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or substituted or unsubstituted A substituted or unsubstituted C3-C20 heteroaryl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C20 alkylamino 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 carbon number 50 arylalkylamino group, substituted or unsubstituted arylthio group having 5 to 60 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, It is selected from the group consisting of a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a cyano group, a halogen group, deuterium and hydrogen.

The L ₁ may be a substituted or unsubstituted arylene group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms, and specifically, an aryl group having 6 to 50 carbon atoms or a heteroarylene group having 3 to 50 carbon atoms An aryl group is a divalent linking group, and in the case of an arylene group, a phenylene group, a biphenylene group, a terphenylene group, a quarterphenylene group, a naphthylene group, an anthracenylene group, a phenanthrylene group, a chrysenylene group, a pyrenylene group, and peryl It may be a renylene group, a fluorenylene group, and the like, more preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a phenanthrylene group or a fluorenylene group, and in the case of a heteroarylene group, It may be a rollylene group, a furanylene group, a thiophenylene group, a silolylene group, a pyridylene group, an imidazolylene group, a pyrimidine group, a carbazolylene group, a selenophenylene group, an oxadiazolylene group, a triazolylene group, etc. , A plurality of such arylene groups and heteroarylene groups may be connected identically or differently.

According to a preferred embodiment, L ₁ may be any one selected from the following [Structural Formula 1].

[Structural Formula 1]

In the [Structural Formula 1], X is selected from CR ₁₉ R ₂₀ , SiR ₂₁ R _{22 ,} NR ₂₃ , PR ₂₄ , P(=OR ₂₅ ), BR ₂₆ , O and S.

The R ₁₉ to R ₂₆ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 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 Arylalkylamino group of to 50, substituted or unsubstituted arylthio group having 5 to 60 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 , A nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a cyano group, a halogen group, deuterium and hydrogen.

According to a preferred embodiment, R ₁₇ and R ₁₈ may each independently be any one selected from the following [Structural Formula 2].

[Structural Formula 2]

In the [Structural Formula 2], R is each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C6-C40 aryl group, A substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, 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 C 1 to 20 carbon atom Of an alkylamino 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 Arylalkylamino group having 1 to 50 carbon atoms, substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, hydride It is selected from the group consisting of a hydroxyl group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a cyano group, a halogen group, deuterium and hydrogen, and c is It is an integer of 0 to 5, and when c is an integer of 2 or more, a plurality of Rs are the same or different, and may be bonded to each other with adjacent substituents to form a saturated or unsaturated ring.

In addition, when R, R ₁ to R ₂₆ and L ₁ are each substituted, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, C 1 to C 60 alkoxy group, C 6 to C 30 aryloxy group, C 1 to C 20 alkylamino group, C 6 to C 30 arylamino group, C 1 to C 20 alkylsilyl group, C 6 to C 30 arylsilyl group , Arylalkylamino group having 1 to 50 carbon atoms, arylthio group having 5 to 60 carbon atoms, alkenyl group having 2 to 60 carbon atoms, alkynyl group having 2 to 60 carbon atoms, 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 cyano group, a halogen group, deuterium and hydrogen, substituted with at least one selected from the group consisting of, and the R, R ₁ to R ₂₆ and L ₁ Substituents substituted with may be bonded to adjacent substituents to form a saturated or unsaturated ring.

According to a preferred embodiment of the present invention, [Chemical Formula 1] may be selected from compounds represented by the following [Chemical Formula 8] to [Chemical Formula 311].

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 [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 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 represent 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, and L ^A11 , L ^A12 , L ^A13 , L ^A14 are each a linking group as previously defined. 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 the 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, the hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

The hole injection layer material 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-quinolinolate)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 single molecule 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 describing the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

Synthesis example 1. Synthesis of Formula 19

Synthesis example 1-1. Synthesis of <1-a>

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

[Scheme 1]

<1-a>

To a 2 L round bottom flask purged with nitrogen at room temperature, cyanuric acid chloride (50.0 g, 271 mmol) and tetrahydrofuran (500 mL) were added, and the mixture was cooled to 0°C and stirred. Phenylmagnesium bromide (316 mL, 949 mmol, 3.0 M in diethyl ether) was added dropwise over 1 hour, and then heated to room temperature and stirred for 12 hours. Upon completion of the reaction, the reaction solution was cooled to 0°C, and then a saturated aqueous ammonium chloride solution was added. Ethyl acetate and distilled water were added to separate the layers. The organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography and recrystallization to obtain <1-a> (58.4 g, 218 mmol). (Yield 80.5%)

Synthesis example 1-2. Synthesis of <1-b>

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

[Scheme 2]

<1-b>

In a 1 L round bottom flask purged with nitrogen at room temperature, <1-a> (20.0 g, 102 mmol) obtained from [Scheme 2], sodium hydride (60%, dispersion in paraffin liquid) (4.9 g, 122 mmol), N,N-dimethylformamide (200 mL) was added. After cooling to 0 ℃, 9-bromoindole (32.8 g, 122 mmol) was added and stirred for 1 hour. The temperature was raised to room temperature and further stirred for 1 hour. Distilled water was added to the reaction solution, and the resulting solid was filtered and purified by silica gel column chromatography to obtain <1-b> (38.6 g, 90.3 mmol). (Yield 88.5%)

Synthesis example 1-3. Synthesis of <1-c>

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

[Scheme 3]

<1-c>

In a 1 L round bottom flask purged with nitrogen at room temperature, <1-b> (20.0 g, 46.8 mmol) obtained from [Scheme 2], bis(pinacolato)diboron (13.1 g, 51.6 mmol), potassium acetate (10.1 g, 103 mmol), PdCl ₂ (dppf) (1.0 g, 1.37 mmol) and toluene (200 mL) were added and refluxed for 12 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain <1-c> (16.3 g, 34.4 mmol). (Yield 73.4%)

Synthesis example 1-4. Synthesis of <1-d>

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

[Scheme 4]

<1-d>

In a 2 L round bottom flask purged with nitrogen at room temperature, tetrahydroquinoline (50.0 g, 375 mmol), 1-bromo-2-iodobenzene (127 g, 450 mmol), tris(dibenzylideneacetone)dipalladium (8.4 g, 15.0 mmol), BINAP (28.1 g, 45.0 mmol) and sodium tertiarybutoxide (108 g, 1126 mmol) were added and refluxed for 48 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain <1-d> (14.4 g, 69.5 mmol). (Yield 18.5%)

Synthesis example 1-5. Synthesis of <1-e>

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

[Scheme 5]

<1-e>

In a 500 mL round bottom flask purged with nitrogen at room temperature, <1-d> (14.4 g, 69.5 mmol) obtained from [Scheme 4] and dimethylformamide (140 mL) were added and stirred. After cooling to -20 °C, N-bromosuccinimide (12.7 g, 76.5 mmol) was added dropwise. The mixture was stirred at -20 °C for 1 hour. The organic layer was extracted using ethyl acetate and distilled water, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain <1-e> (18.7 g, 65.4 mmol). (Yield 94.1%)

Synthesis example 1-6. Synthesis of <Formula 19>

<Chemical Formula 19> was synthesized by the following Scheme 6.

[Scheme 6]

<Formula 19>

In a 500 mL round-bottom flask at room temperature, <1-c> (5.0 g, 17.5 mmol) obtained from [Scheme 3] and <1-e> (9.1 g, 19.2 mmol) obtained from [Scheme 5], potassium carbonate (7.2 g, 52.4 mmol), tetrakistriphenylphosphine palladium (0.8 g, 0.699 mmol), tetrahydrofuran (50 mL), and distilled water (10 mL) were added, followed by refluxing for 12 hours. After cooling the reaction solution to room temperature, ethyl acetate and distilled water were added to separate the layers. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain <Chemical Formula 19> (8.1 g, 14.6 mmol). (Yield 83.7%)

MS(MALDI-TOF): m/z 553.2[M] ⁺

Anal. Calc. for C ₃₈ H ₂₇ N ₅ C, 82.44; H, 4.92; N, 12.65. Found C, 82.44; H, 4.93; N, 12.64.

Synthesis example 2. Synthesis of Formula 28

Synthesis example 2-1. Synthesis of <2-a>

<2-a> was synthesized according to Scheme 7 below.

[Scheme 7]

<2-a>

In a 2 L round bottom flask at room temperature, 2,4,6-trichloropyrimidine (50.0 g, 273 mmol), phenylboronic acid (69.8 g, 572 mmol), potassium carbonate (113 g, 818 mmol), and tetrakistri Phenylphosphine palladium (9.5 g, 8.18 mmol), 1,2-dimethoxyethane (400 mL), and distilled water (100 mL) were added, followed by refluxing for 12 hours. After cooling the reaction solution to room temperature, ethyl acetate and distilled water were added to separate the layers. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain <2-a> (37.6 g, 141 mmol). (Yield 51.7%)

Synthesis example 2-2. Synthesis of <2-b>

<2-b> was synthesized according to Scheme 8 below.

[Scheme 8]

<2-b>

At room temperature, 2,4-dibromoaniline (50.0 g, 199 mmol) was added to a 2 L round bottom flask, cooled to 0 degrees, and an aqueous hydrochloric acid solution (3 M, 300 mL) was added and stirred. An aqueous sodium nitrite solution (3 M, 73 mL) was added dropwise, followed by stirring for 1 hour. After adding an aqueous potassium iodide solution (3 M, 665 mL) dropwise, the temperature was raised to room temperature and stirred for 4 hours. After confirming the completion of the reaction by TLC, sodium thiosulfate pentahydrate (9.9 g, 39.9 mmol) was added to the reactor. Ethyl acetate and distilled water were added to separate the layers, and the organic layer was concentrated under reduced pressure and purified by column chromatography to obtain <2-b> (55.3 g, 153 mmol). (Yield 76.7%)

Synthesis example 2-3. Synthesis of <2-c>

<2-c> was synthesized according to Scheme 9 below.

[Scheme 9]

<2-c>

In the same synthesis method as in [Scheme 4], 1,2,3,4-tetrahydroquinoline and <2-b> obtained from [Scheme 8] were reacted to obtain <2-c> (7.6 g, 26.6 mmol). .(Yield 13.9%)

Synthesis example 2-4. Synthesis of <2-d>

<2-d> was synthesized according to Scheme 10 below.

[Scheme 10]

<2-d>

In a 1 L round bottom flask purged with nitrogen at room temperature, indole (20.0 g, 171 mmol), <2-c> (58.6 g, 205 mmol) obtained from [Scheme 9], potassium carbonate (70.8 g, 512 mmol), tetra Kistriphenylphosphine palladium (7.9 g, 6.84 mmol) and tetrahydrofuran (200 mL) were added and refluxed for 48 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain <2-d> (28.1 g, 87.2 mmol). (Yield 51.1%)

Synthesis example 2-5. Synthesis of <2-e>

<Chemical Formula 28> was synthesized by the following Scheme 11.

[Scheme 11]

<Formula 28>

In the same synthesis method as [Scheme 2], <2-a> obtained from [Scheme 7] and <2-d> obtained from [Scheme 10] were reacted to obtain <Chemical Formula 28> (5.3 g, 9.59 mmol). (Yield 83.1%)

MS(MALDI-TOF): m/z 552.2[M] ⁺

Anal. Calc. for C ₃₉ H ₂₈ N ₄ C, 84.76; H, 5.11; N, 10.14. Found C, 84.77; H, 5.11; N, 10.13.

Synthesis example 3. Synthesis of Formula 72

Synthesis example 3-1. Synthesis of <3-a>

<3-a> was synthesized according to Scheme 12 below.

[Scheme 12]

<3-a>

In the same synthesis method as in [Scheme 2], <1-a> obtained from [Scheme 1] and 2-bromocarbazole were reacted to obtain <3-a> (31.6 g, 66.2 mmol). (Yield 80.4%)

Synthesis example 3-2. Synthesis of <3-b>

<3-b> was synthesized according to Scheme 13 below.

[Scheme 13]

<3-b>

In the same synthesis method as in [Scheme 3], <3-a> obtained from [Scheme 12] was reacted to obtain <3-b> (17.3 g, 33.0 mmol). (Yield 84.2%)

Synthesis example 3-3. Synthesis of <3-c>

<3-c> was synthesized according to Scheme 14 below.

[Scheme 14]

<3-c>

In the same synthesis method as in [Scheme 4], 3,4-dihydro-2H-benzoxazine and 1-bromo-2-iodobenzene were reacted to obtain <3-c> (16.9 g, 80.8 mmol). .(Yield 34.2%)

Synthesis example 3-4. Synthesis of <3-d>

<3-d> was synthesized according to Scheme 15 below.

[Scheme 15]

<3-d>

In the same synthesis method as in [Scheme 5], <3-c> obtained from [Scheme 14] was reacted to obtain <3-d> (19.3 g, 67.1 mmol). (Yield 84.2%)

Synthesis example 3-5. Synthesis of <3-e>

<3-e> was synthesized according to Scheme 16 below.

[Scheme 16]

<Formula 72>

In the same synthesis method as in [Scheme 6], <3-b> obtained from [Scheme 13] and <3-d> obtained from [Scheme 15] were reacted to obtain <Formula 72> (6.3 g, 10.4 mmol). (Yield 87.1%)

MS(MALDI-TOF): m/z 605.2[M] ⁺

Anal. Calc. for C ₄₁ H ₂₇ N ₅ OC, 81.30; H, 4.49; N, 11.56; O, 2.64. Found C, 81.31; H, 4.49; N, 11.57; O, 2.64.

Synthesis example 4. Synthesis of Formula 102

Synthesis example 4-1. Synthesis of <4-a>

[Scheme 17]

<4-a>

In a 1 L round bottom flask at room temperature, 2-bromoaniline (50 g, 291 mmol), 1,4-dibromonaphthalene (91.4 g, 320 mmol), sodium tertiarybutoxide (41.9 g, 436 mmol), tris Dibenzylideneacetone (5.3 g, 5.81 mmol), DPPF (6.4 g, 11.6 mmol) and toluene (500 mL) were added, followed by refluxing for 12 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain <4-a> (76.9 g, 204 mmol). (Yield 70.2%)

Synthesis example 4-2. Synthesis of <4-b>

[Scheme 18]

<4-b>

<4-a> (76.9 g, 204 mmol) obtained from [Scheme 17] in a 2 L round bottom flask at room temperature, PCy ₃ HBF ₄ (1.50 g, 4.08 mmol), potassium carbonate (56.4 g, 408 mmol), palladium acetate (0.5 g, 2.04 mmol) and dimethylacetamide (800 mL) were added and then refluxed for 12 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain <4-b> (35.3 g, 119 mmol). (Yield 58.4%)

Synthesis example 4-3. Synthesis of <4-c>

[Scheme 19]

<4-c>

In the same synthesis method as [Scheme 2], <4-b> obtained from [Scheme 18] and <1-a> obtained from [Scheme 1] were reacted to obtain <4-c> (49.0 g, 92.9 mmol). . (Yield 78.1%)

Synthesis example 4-4. Synthesis of <4-d>

[Scheme 20]

<4-d>

In the same synthesis method as in [Scheme 3], <4-c> obtained from [Scheme 19] was reacted to obtain <4-d> (39.2 g, 68.3 mmol). (Yield 73.5%)

Synthesis example 4-5. Synthesis of <Formula 102>

[Scheme 21]

<Formula 102>

In the same synthesis method as [Scheme 6], <4-d> obtained from [Scheme 20] and <3-d> obtained from [Scheme 15] were reacted to obtain <Chemical Formula 102> (6.7 g, 10.2 mmol). (Yield 73.9%)

MS(MALDI-TOF): m/z 655.2[M] ⁺

Anal. Calc. for C ₄₅ H ₂₉ N ₅ OC, 82.42; H, 4.46; N, 10.68; O, 2.44. Found C, 82.42; H, 4.45; N, 10.69; O, 2.43.

Synthesis example 5. Synthesis of Formula 122

Synthesis example 5-1. Synthesis of <5-a>

[Scheme 22]

<5-a>

In a 2 L round bottom flask purged with nitrogen at room temperature, iodobenzene 100 g (490 mmol), methyl anthranilate 88.9 g (588 mmol), palladium acetate 3.7 g (4.80 mmol), xantphos 8.5 g (14.7 mmol), cesium Carbonate 240 g (735 mmol) and toluene (1000 mL) were added and refluxed for 24 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain <5-a> (101 g, 449 mmol). (Yield 76.3%)

Synthesis example 5-2. Synthesis of <5-b>

[Scheme 23]

<5-b>

In a 2 L round bottom flask purged with nitrogen at room temperature, <5-a> (50 g, 220 mmol) obtained from Reaction Scheme 22 and diisopropyl ether (600 mL) were added, and then cooled to 0 °C. 3M methylmagnesium bromide solution (330 mL) was added dropwise. After raising the temperature to 50 degrees, the mixture was stirred for 6 hours. When the reaction was completed, ethyl acetate and an aqueous ammonium chloride solution were added to separate the layers, and the organic layer was concentrated under reduced pressure, and then purified by column chromatography to obtain <5-b> (42.7 g, 188 mmol). (Yield 85.4%)

Synthesis example 5-3. Synthesis of <5-c>

[Scheme 24]

<5-c>

<5-b> (42.7 g, 188 mmol) and phosphoric acid (200 mL) obtained from [Scheme 23] were added to a 500 mL round-bottom flask at room temperature, followed by stirring at room temperature for 12 hours. When the reaction was completed, water was added to the reactor and stirred, and the resulting solid was filtered. Purified by column chromatography to obtain <5-c> (31.1 g, 149 mmol). (Yield 79.1%)

Synthesis example 5-4. Synthesis of <5-d>

[Scheme 25]

<5-d>

In the same synthesis method as [Scheme 5], <5-c> obtained from [Scheme 24] was reacted to give <5-d> (37.6 g, 131 mmol). (Yield 87.6%)

Synthesis example 5-6. Synthesis of <5-e>

[Scheme 26]

<5-e>

In the same synthesis method as [Scheme 2], <5-d> obtained from [Scheme 25] and <1-a> obtained from [Scheme 1] were reacted to obtain <5-e> (13.6 g, 26.2 mmol). .(Yield 89.5%)

Synthesis example 5-7. Synthesis of <5-f>

[Scheme 27]

<5-f>

In the same synthesis method as [Scheme 3], <5-e> obtained from [Scheme 26] was reacted to give <5-f> (12.1 g, 21.4 mmol). (Yield 81.8%)

Synthesis example 5-8. Synthesis of <Formula 122>

[Scheme 28]

<Formula 122>

In the same synthesis method as [Scheme 6], <5-f> obtained from [Scheme 27] and <3-d> obtained from [Scheme 15] were reacted to obtain <Chemical Formula 122> (6.3 g, 9.73 mmol). (Yield 84.3%)

MS(MALDI-TOF): m/z 647.3[M] ⁺

Anal. Calc. for C ₄₄ H ₃₃ N ₅ OC, 81.58; H, 5.13; N, 10.81; O, 2.47. Found C, 81.57; H, 5.12; N, 10.82; O, 2.47.

Synthesis example 6. Synthesis of Formula 160

Synthesis example 6-1. Synthesis of <6-a>

[Scheme 29]

<6-a>

In the same synthesis method as in [Scheme 3], 3,3-dimethylindoline and 2-bromo-1-iodobenzene were reacted to obtain <6-a> (38.3 g, 173 mmol). (Yield 31.8 g. %)

Synthesis example 6-2. Synthesis of <6-b>

[Scheme 30]

<6-b>

In the same synthesis method as in [Scheme 5], <6-a> obtained from [Scheme 29] was reacted to obtain <6-b> (7.92 g, 26.4 mmol). (Yield 83.0%)

Synthesis example 6-3. Synthesis of <Formula 160>

[Scheme 31]

<Formula 160>

In the same synthesis method as [Scheme 6], <5-f> obtained from [Scheme 27] and <6-b> obtained from [Scheme 30] were reacted to obtain <Formula 160> (5.2 g, 7.88 mmol). .(Yield 78.1%)

MS(MALDI-TOF): m/z 659.3[M] ⁺

Anal. Calc. for C ₄₆ H ₃₇ N ₅ C, 83.73; H, 5.65; N, 10.61. Found C, 83.73; H, 5.65; N, 10.62.

Synthesis example 7. Synthesis of Formula 174

Synthesis example 7-1. Synthesis of <7-a>

[Scheme 32]

<7-a>

In a 1 L round bottom flask purged with nitrogen at room temperature, 4-bromoaniline (50.0 g, 251 mmol), 60% sodium hydride (11.0 g, 276 mmol) and tetrahydrofuran (500 mL) were added, and 0 °C It was cooled to and stirred for 1 hour. After adding 2-bromobenzyl bromide (41.1 g, 276 mmol), the mixture was heated to room temperature and stirred for 2 hours. Upon completion of the reaction, the reaction solution was cooled to 0°C, and then a saturated aqueous ammonium chloride solution was added. Ethyl acetate and distilled water were added to separate the layers. The organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain <7-a> (80.2 g, 235 mmol). (Yield 93.7%)

Synthesis example 7-2. Synthesis of <7-b>

[Scheme 33]

<7-b>

In the same synthesis method as [Scheme 18], <7-a> obtained from [Scheme 32] was reacted to obtain <7-b> (19.6 g, 75.3 mmol). (Yield 32.1%)

Synthesis example 7-3. Synthesis of <7-c>

[Scheme 34]

<7-c>

In the same synthesis method as [Scheme 2], <7-b> obtained from [Scheme 33] and <1-b> obtained from [Scheme 1] were reacted to obtain <7-c> (30.4 g, 61.8 mmol). .(Yield 82.1%)

Synthesis example 7-4. Synthesis of <7-d>

[Scheme 35]

<7-d>

In the same synthesis method as [Scheme 2], <7-c> obtained from [Scheme 34] was reacted to obtain <7-d> (26.6 g, 49.3 mmol). (Yield 79.8%)

Synthesis example 7-5. Synthesis of <Formula 174>

[Scheme 36]

<Formula 174>

In the same synthesis method as in [Scheme 6], <7-d> obtained from [Scheme 35] and <3-d> obtained from [Scheme 15] were reacted to obtain <Chemical Formula 174> (5.1 g, 8.23 mmol). (Yield 80.8%)

MS(MALDI-TOF): m/z 619.2[M] ⁺

Anal. Calc. for C ₄₂ H ₂₉ N ₅ OC, 81.40; H, 4.72; N, 11.30; O, 2.58. Found C, 81.39; H, 4.71; N, 11.30; O, 2.59.

Synthesis example 8. Synthesis of Formula 198

Synthesis example 8-1. Synthesis of <8-a>

[Scheme 37]

<8-a>

In the same synthesis method as in [Reaction Scheme 32], phenothiazine and 1-bromo-3-methyl-2-butene were reacted to obtain <8-a> (58.2 g, 218 mmol). (Yield 86.7%)

Synthesis example 8-2. Synthesis of <8-b>

[Scheme 38]

<8-b>

<8-a> (58.2 g, 218 mmol) and sulfuric acid (50 mL) obtained from [Scheme 37] were added to a 250 mL round-bottom flask at 0° C., and the mixture was heated to 60° C. and stirred for 12 hours. After cooling to 0° C., NaOH aqueous solution was added to neutralize, and the layers were separated with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and then purified by column chromatography to obtain <8-b> (42.1 g, 157 mmol). (Yield 72.2%)

Synthesis example 8-3. Synthesis of <8-c>

[Scheme 39]

<8-c>

In the same synthesis method as in [Scheme 5], <8-b> obtained from [Scheme 38] was reacted to obtain <8-c> (49.6 g, 143 mmol). (Yield 91.2%)

Synthesis example 8-4. Synthesis of <Formula 198>

[Scheme 40]

<Formula 198>

In the same synthesis method as in [Scheme 6], <3-b> obtained from [Scheme 13] and <8-c> obtained from [Scheme 39] were reacted to obtain <Chemical Formula 198> (6.3 g, 9.49 mmol). (Yield 83.5%)

MS(MALDI-TOF): m/z 663.3[M] ⁺

Anal. Calc. for C ₄₄ H ₃₃ N ₅ SC, 79.61; H, 5.01; N, 10.55; S, 4.83. Found C, 79.61; H, 5.02; N, 10.56; S, 4.82.

Synthesis example 9. Synthesis of Formula 206

[Scheme 41]

<Formula 206>

In the same synthesis method as in [Scheme 6], <5-f> obtained from [Scheme 27] and <8-c> obtained from [Scheme 39] were reacted to obtain <Chemical Formula 206> (8.1 g, 11.5 mmol). (Yield 80.4%)

MS(MALDI-TOF): m/z 705.3[M] ⁺

Anal. Calc. for C ₄₇ H ₃₉ N ₅ SC, 79.97; H, 5.57; N, 9.92; S, 4.54. Found C, 79.98; H, 5.57; N, 9.91; S, 4.54.

Synthesis example 10. Synthesis of Formula 214

[Scheme 42]

<Formula 214>

In the same synthesis method as in [Scheme 6], <7-d> obtained from [Scheme 35] and <8-c> obtained from [Scheme 39] were reacted to obtain <Chemical Formula 214> (6.1 g, 9.00 mmol). (Yield 83.5%)

MS(MALDI-TOF): m/z 677.3[M] ⁺

Anal. Calc. for C ₄₅ H ₃₅ N ₅ SC, 79.73; H, 5.20; N, 10.33; S, 4.73. Found C, 79.72; H, 5.21; N, 10.33; S, 4.74.

Example : Preparation of organic light emitting diode

The ITO glass was patterned so that the light emitting area was 2 mm × 2 mm in size and washed. After mounting the substrate in the vacuum chamber, the base pressure is 1×10 ^-6 torr, and then the organic material is placed on the ITO DNTPD (700 Å), 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.The structure of the CBP is as follows.

division Host Dopant Doping concentration% V Cd/㎡ CIEx CIEy T ₈₀ (Hr) Comparative Example 1 CBP Ir(ppy) ₃ 10 7.93 3801 0.297 0.624 68 Example 1 Formula 19 Ir(ppy) ₃ 10 4.22 5410 0.296 0.624 187 Example 2 Formula 22 Ir(ppy) ₃ 10 4.10 5431 0.296 0.624 191 Example 3 Formula 28 Ir(ppy) ₃ 10 3.98 5380 0.298 0.623 210 Example 4 Formula 66 Ir(ppy) ₃ 10 3.88 5334 0.297 0.622 200 Example 5 Formula 72 Ir(ppy) ₃ 10 4.21 4991 0.297 0.625 183 Example 6 Formula 102 Ir(ppy) ₃ 10 4.11 4920 0.297 0.624 176 Example 7 Formula 104 Ir(ppy) ₃ 10 3.94 4934 0.296 0.625 200 Example 8 Formula 112 Ir(ppy) ₃ 10 3.99 5210 0.295 0.624 210 Example 9 Formula 118 Ir(ppy) ₃ 10 3.76 5322 0.296 0.625 208 Example 10 Chemical Formula 122 Ir(ppy) ₃ 10 3.86 5341 0.298 0.625 223 Example 11 Formula 160 Ir(ppy) ₃ 10 3.92 5112 0.298 0.624 223 Example 12 Formula 173 Ir(ppy) ₃ 10 3.69 5217 0.299 0.623 168 Example 13 Formula 174 Ir(ppy) ₃ 10 3.91 4994 0.299 0.626 173 Example 14 Formula 198 Ir(ppy) ₃ 10 3.93 4876 0.298 0.625 276 Example 15 Formula 200 Ir(ppy) ₃ 10 4.31 4981 0.298 0.624 251 Example 16 Formula 206 Ir(ppy) ₃ 10 4.21 4922 0.296 0.624 255 Example 17 Formula 208 Ir(ppy) ₃ 10 4.12 5001 0.297 0.624 243 Example 18 Formula 214 Ir(ppy) ₃ 10 3.91 4993 0.295 0.623 271 Example 19 Chemical Formula 216 Ir(ppy) ₃ 10 3.93 4876 0.297 0.624 254 Example 20 Formula 220 Ir(ppy) ₃ 10 4.87 4911 0.296 0.623 233

In [Table 1], T80 refers to the time required for the luminance to be reduced to 80% 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)

Any one organic light-emitting compound selected from the compounds represented by the following [Chemical Formula 2] to [Chemical Formula 7]:
[Chemical Formula 2] [Chemical Formula 3]

[Chemical Formula 4] [Chemical Formula 5]

[Formula 6] [Formula 7]

In the above [Formula 2] to [Formula 7],
A and Z are each independently any one selected from CR ₉ R ₁₀ , SiR ₁₁ R _12, NR ₁₃ , O and S,
L ₁ is each independently a chemical bond, a substituted or unsubstituted alkylene having 1 to 60 carbon atoms, a substituted or unsubstituted arylene having 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene having 3 to 50 carbon atoms Is selected, a and b are each independently an integer of 0 to 3, when a and b are 2 or more, a plurality of L ₁ is the same or different from each other,
R ₉ to R ₁₃ and R ₁₇ to R ₁₈ are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms It is chosen from among group. delete delete The method of claim 1,
The L ₁ is an organic light-emitting compound, characterized in that any one selected from the following [Structural Formula 1]:
[Structural Formula 1]

In [Structural Formula 1],
X is selected from CR ₁₉ R ₂₀ , SiR ₂₁ R _22, NR ₂₃ , O and S,
The R ₁₉ to R ₂₃ are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted carbon number 6 to It is selected from 40 aryl groups, substituted or unsubstituted C3-C20 heteroaryl groups, substituted or unsubstituted C1-C20 alkylsilyl groups, and substituted or unsubstituted C6-C30 arylsilyl groups. The method of claim 1,
The R ₁₇ and R ₁₈ are each independently an organic light emitting compound, characterized in that any one selected from the following [Structural Formula 2]:
[Structural Formula 2]

In the above [Structural Formula 2],
R is each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, Selected from a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, c is 0 to 5 Is an integer of, and when c is an integer of 2 or more, a plurality of Rs are the same or different, respectively. The method according to any one of claims 1, 4 and 5,
When the R, R ₉ to R ₁₃ , R ₁₇ to R ₁₈ , R ₁₉ to R ₂₃ and L ₁ are each substituted, hydrogen, deuterium, halogen group, cyano group, alkyl group having 1 to 20 carbon atoms, 3 to 60 carbon atoms Cycloalkyl group, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 30 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms and 6 to 30 carbon atoms Organic light-emitting compound, characterized in that substituted with at least one selected from the arylsilyl group. The method of claim 1,
Any one organic light-emitting compound selected from the compounds represented by the [Chemical Formula 2] to [Chemical Formula 7] is an organic light-emitting compound, characterized in that any one selected from the compounds represented by the following [Chemical Formula 8] to [Chemical Formula 311] compound:

An organic thin film layer for an organic light emitting device comprising at least one organic light emitting compound selected from compounds represented by [Chemical Formula 2] to [Chemical Formula 7] according to claim 1. The method of claim 8,
The organic thin film layer is an organic thin film layer comprising as a host any one organic light-emitting compound selected from compounds represented by [Chemical Formula 2] to [Chemical Formula 7], and further comprising 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. The method of claim 10,
The organic electroluminescent device further includes at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron blocking layer between the first electrode and the second electrode, ,
One of the light emitting layer, the hole injection layer, the hole transport layer, the hole blocking layer, the electron transport layer, the electron injection layer and the electron blocking layer is the organic thin film layer. The method of claim 11,
An organic electroluminescent device, wherein the emission layer is the organic thin film 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.

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