KR102137235B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound capable of improving the luminous efficiency, stability and life of the device, and an organic electrical device using the same, and an electronic device thereof.

Description

Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electrical device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function.

On the other hand, the metal oxide from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, delays the penetration and diffusion of the metal oxide into the organic layer. There is a need to develop a hole injection layer material having a temperature. In addition, it has been reported that the low glass transition temperature of the hole transport layer material has a great influence on the device life, depending on the property that the uniformity of the thin film surface collapses when driving the device. In addition, in the formation of OLED devices, the deposition method is predominant, and a material capable of withstanding such a deposition method for a long time, that is, a material having strong heat resistance characteristics is required.

In order to sufficiently exhibit the excellent characteristics of the above-described organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, are supported by stable and efficient materials It should be preceded, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently performed, and therefore, the development of a new material is still required.

An object of the present invention is to provide a compound capable of improving the device's high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime, and an organic electric device using the same and its electronic device.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifetime of the device can be greatly improved.

1 is an exemplary view of an organic electroluminescent device according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible, even if they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known structures or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".

On the other hand, as used herein, the term "halo" or "halogen" includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

The term "alkyl" or "alkyl group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto unless otherwise specified.

The terms "alkenyl" or "alkynyl" as used in the present invention have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto.

As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

The term "alkoxy group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto, unless otherwise specified.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified.

In the present invention, the aryl group or arylene group means a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, or spirofluorene group.

As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 3 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. No, it includes a heterocycle as well as a single ring, and may be formed by combining adjacent groups.

The terms "heterocycloalkyl" and "heterocyclic group" used in the present invention include one or more heteroatoms, have 2 to 60 carbon atoms, and include heterocycles as well as monocycles unless otherwise specified. , Adjacent groups may be formed by combining. In addition, "heterocyclic group" may mean an alicyclic and/or aromatic group containing heteroatoms.

The term "heteroatom" as used herein refers to N, O, S, P and Si unless otherwise stated.

Unless otherwise stated, the term "aliphatic" used in the present invention means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic or heterocyclic ring having 6 to 60 carbon atoms.

Other hetero compounds or hetero radicals other than the above-described hetero compounds include one or more hetero atoms, but are not limited thereto.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₅ to C ₂₀ heterocyclic groups, and is not limited to these substituents.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 and a second electrode 180 formed on the substrate 110. ) Is provided with an organic material layer containing the compound represented by Formula 1. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 on the first electrode 120. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160, etc. may also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic material layer is the material of the host or dopant or capping layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, and the light emitting layer 150 Can be used as

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, an anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer are formed thereon. 160) and after forming an organic material layer including the electron injection layer 170, it can be manufactured by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is less by a method such as a solution process or a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), which is not a vapor deposition method using various polymer materials. It can be prepared by a number of layers. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

The organic electric device according to the present invention may be of a front emission type, a rear emission type, or a double emission type, depending on the material used.

In addition, the organic electric device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), a monochromatic or white lighting device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit for controlling the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described.

The compound according to an aspect of the present invention is represented by the following formula (1).

In Chemical Formula 1,

R ₁ to R ₇ and Ar ₁ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; -LN(Ar ₄ )(Ar ₅ ); And it is selected from the group consisting of fluorenyl group,

L is a direct bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And a divalent aliphatic hydrocarbon group; is selected from the group consisting of, wherein, the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group is a nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ It may be substituted with one or more substituents selected from the group consisting of an aryl group of ~C ₂₀ , a heterocyclic group of C ₂ ~C ₂₀ , an alkoxyl group of C ₁ ~C ₂₀ , and an amino group.

Ar ₂ is hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fluorenyl group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; And -N(Ar ₄ )(Ar ₅ ),

Ar ₄ and Ar ₅ are independently of each other, a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~ C ₅₀ alkyl group; Or a fluorenyl group.

Meanwhile, R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ may be further substituted with other substituents.

When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are aryl groups, they are hydrogen, deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C ₂₀ Import of an alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups (alkenyl), an alkynyl of C ₂ ~ C ₂₀ group (alkynyl) a, C ₆ ~ Aryl group of C ₂₀ , C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ Of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are heterocyclic groups, they are hydrogen, deuterium, halogen, silane group, cyano group, nitro group, alkoxyl group of C ₁ to C ₂₀ , C ₁ to a C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ - C ₂₀ substituted by deuterium aryl group, a heterocyclic group of C ₂ ~ C ₂₀ , C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are fluorenyl groups, they are hydrogen, deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C ₂ to C consisting of a cycloalkyl group ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group,

When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are alkyl groups, they are halogen, silane group, boron group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a heterocyclic group of _{C 2 ~ C 20, C 7} ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are alkenyl groups, they are hydrogen, deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ Cycloalkyl group of ~C ₂₀ , C ₇ ~C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ to R ₇ , Ar ₁ and Ar ₂ are alkoxy groups, they are hydrogen, deuterium, halogen, silane group, C ₁ to C ₂₀ alkyl group, C ₆ to C ₂₀ aryl group, C substituted with deuterium ₆ to C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of,

When R ₁ to R ₇ , Ar ₁ and Ar ₂ are aryloxy groups, they are substituted with hydrogen, deuterium, silane groups, cyano groups, C ₁ to C ₂₀ alkyl groups, C ₆ to C ₂₀ aryl groups, and deuterium. It may be substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group.

Meanwhile, the compound represented by Chemical Formula 1 may be represented by one of the following Chemical Formulas.

At this time, in Chemical Formulas 2 to 4, R ₁ to R ₇ , Ar ₂ and L are the same as defined in Chemical Formula 1,

R ₈ to R ₁₃ and Ar ₃ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; -LN(Ar ₄ )(Ar ₅ ); And a fluorenyl group, wherein Ar ₄ , Ar ₅ and L are as defined in Formula 1 above.

And R ₈ ~ R ₁₃ And Ar ₃ may be further substituted with other substituents.

When R ₈ to R ₁₃ and Ar ₃ are aryl groups, they are hydrogen, deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C ₂₀ alkylthio, C ₁ to C Alkoxy group of ₂₀ , C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C ₂ ~ C ₂₀ alkynyl group (alkynyl), C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₈ ~ R ₁₃ And Ar ₃ Is a heterocyclic group, it is hydrogen, deuterium, halogen, silane group, cyano group, nitro group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ heterocyclic group of C _20, C ₃ ~ cycloalkyl group of C ₂₀ , C ₇ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₈ ~ R ₁₃ And Ar ₃ Is a fluorenyl group, it is hydrogen, deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C optionally substituted with one or more substituents selected from the group consisting of ₆ ~ C ₂₀ aryl group, a cycloalkyl group of C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium Can,

When R ₈ to R ₁₃ and Ar ₃ are alkyl groups, they are halogen, silane group, boron group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkene Diary (alkenyl), C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₈ ~ R ₁₃ And Ar ₃ Is an alkenyl group, it is hydrogen, deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ the alkenyl group _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ C heterocyclic group of _20, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ Of C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₈ ~ R ₁₃ And Ar ₃ Is an alkoxyl group, it is hydrogen, deuterium, halogen, silane group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C substituted with deuterium ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of,

When R ₈ ~ R ₁₃ And Ar ₃ is an aryloxy group, it is hydrogen, deuterium, silane group, cyano group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ substituted with deuterium C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of.

Meanwhile, Chemical Formula 1 may be represented by the following compounds.

Hereinafter, examples of the synthesis of the compound represented by Chemical Formula 1 according to the present invention and the manufacturing example of the organic electric device will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

Synthetic example

Illustratively, the final product according to the present invention is prepared by reacting with Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

<Scheme 1>

[ Example One]

Sub Synthesis of 1

Sub 1 may be synthesized by the reaction route of Scheme 2 below.

<Reaction Scheme 2>

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

(One) Sub 1-7 synthesis

<Scheme 3>

After dissolving the starting material 2-chloro-1 H -benzo[ de ]quinoline (41.78 g, 207.2 mmol) in THF in a round bottom flask, 2-([1,1'-biphenyl]-4-yl)-4 ,4,5,5-tetramethyl-1,3,2-dioxaborolane (63.85 g, 227.9 mmol), Pd(PPh ₃ ) ₄ (7.18 g, 6.2 mmol), K ₂ CO ₃ (57.27 g, 414.4 mmol), Water was added and stirred at 80 °C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 48.31 g of product (yield: 73%).

(2) Sub 1-21 Synthetic example

<Reaction Scheme 4>

Starting material 2-chloro-1 H -benzo[ de ]quinoline (55.31 g, 274.3 mmol) with 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)-9 H- carbazole (111.41 g, 301.7 mmol), Pd(PPh ₃ ) ₄ (9.51 g, 8.2 mmol), K ₂ CO ₃ (75.82 g, 548.6 mmol), THF, water of Example 1 above. Using the same synthesis method as for Sub 1-7 synthesis, 76.19 g of product (yield: 68%) was obtained.

(3) Sub 1-43 synthesis

<Reaction Scheme 5>

Starting material 2-chloro-1 H -benzo[ de ]quinoline (36.64 g, 181.7 mmol) to 9-(4-(2,6-diphenylpyrimidin-4-yl)phenyl)-2-(4,4,5 ,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9 H -carbazole (119.83 g, 199.9 mmol), Pd(PPh ₃ ) ₄ (6.3 g, 5.5 mmol), K ₂ CO ₃ (50.23 g, 363.4 mmol), THF, and water were obtained using the same synthesis method as in Sub 1-7 synthesis of Example 1 to obtain 75.44 g of product (yield: 65%).

(4) Sub 1-50 synthesis

<Scheme 6>

Starting material 2-chloro-1 H -benzo[ de ]quinoline (39.09 g, 193.9 mmol) with 1,2-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl)-1 H- indole (84.29 g, 213.2 mmol), Pd(PPh ₃ ) ₄ (6.72 g, 5.8 mmol), K ₂ CO ₃ (53.58 g, 387.7 mmol), THF, water in the above example The same synthesis method as Sub 1-7 synthesis of 1 was used to obtain 58.96 g of product (yield: 70%).

Meanwhile, examples of Sub 1 are as follows, but are not limited thereto, and their FD-MS are shown in Table 1 below.

[Table 1]

[ Example 2]

Sub Example 2

Examples of Ar ₂ -LX (X= Br, Cl, F) of Sub 2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

[Table 2]

[ Example 3]

Product synthesis

< Method 1>

After dissolving Sub 1 (1 eq) in a round bottom flask with toluene, Sub 2 (1.2 eq), Pd ₂ (dba) ₃ (0.03 eq), P(t-Bu) ₃ (0.08 eq), NaO t -Bu (3 eq) was added and stirred at 100 °C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain final products.

< Method 2>

Sub 1 (1 eq) was dissolved in dimethyl sulfoxide in a round bottom flask, Sub 2 (1.1 eq) and K ₂ CO ₃ (6 eq) were added and stirred at 150°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain final products.

(One) Product 1-1 synthesis

<Scheme 7>

After dissolving Sub 1-1 (6.34 g, 37.9 mmol) obtained in the above synthesis in toluene in a round bottom flask, Sub 2-15 (18.12 g, 45.5 mmol), Pd ₂ (dba) ₃ (1.04 g, 1.1 mmol) , 50% P( t -Bu) ₃ (1.5ml, 3 mmol), NaO t -Bu (10.93 g, 113.7 mmol) was added and stirred at 100°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 13.6 g of product (yield: 74%).

(2) Product 1-35 synthesis

<Scheme 8>

Sub 2-7 (15.77 g, 40.6 mmol), Pd ₂ (dba) ₃ (0.93 g, 1 mmol), 50% P( t -Bu) to Sub 1-7 (10.81 g, 33.8 mmol) obtained in the above synthesis. ₃ (1.3ml, 2.7 mmol), NaO t -Bu (9.76 g, 101.5 mmol), toluene was obtained using the same method as in the synthesis of Product 1-1 of Example 2, to obtain 14.42 g of product (yield: 68%). .

(3) Product 1-54 Synthesis

<Scheme 9>

Sub 2-17 (10.53 g, 27.2 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.7 mmol), 50% P( t -Bu) to Sub 1-21 (9.26 g, 22.7 mmol) obtained in the above synthesis. ₃ (0.9ml, 1.8 mmol), NaO t -Bu (6.54 g, 68 mmol), toluene was obtained in the same manner as in the synthesis of Product 1-1 of Example 2 to obtain 10.53 g of product (yield: 65%). .

(4) Product 1-85 synthesis

<Reaction Scheme 10>

Sub 2-1 (3.76 g, 24 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.6 mmol), 50% P( t -Bu) to Sub 1-43 (12.75 g, 20 mmol) obtained in the above synthesis. ₃ (0.8 ml, 1.6 mmol), NaO t -Bu (5.76 g, 59.9 mmol), and toluene were obtained in the same manner as in the synthesis of Product 1-1 in Example 2 to obtain 10.13 g of product (yield: 71%). .

(5) Product 1-92 synthesis

<Scheme 11>

After dissolving Sub 1-50 (10.32 g, 23.7 mmol) obtained in the synthesis with dimethyl sulfoxide in a round bottom flask, Sub 2-32 (6.54 g, 26.1 mmol), K ₂ CO ₃ (19.69 g, 142.5 mmol) was added. It was added and stirred at 150°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 10.89 g of product (yield: 69%).

On the other hand, FD-MS values of the compounds 1-1 to 1-12 of the present invention prepared according to the above synthesis example are shown in Table 3 below.

[Table 3]

On the other hand, although the exemplary synthetic examples of the present invention represented by Formula 1 have been described above, they are all Suzuki cross-coupling reaction, Buchwald-Hartwig cross coupling reaction, and aromatic nucleophilic substitution reaction ( Ultrasonic Sonochemistry , 2003, 10 , 265). Those skilled in the art will readily understand that the reaction proceeds even if other substituents defined in Chemical Formula 1 (substituents such as R ₁ to R ₁₃ , L, Ar ₁ to Ar ₃ ) are combined in addition to the substituents specified in the specific synthesis examples as the basis. . For example, the method for synthesizing Sub 1 from the starting material in Scheme 2 is based on the Suzuki cross-coupling reaction, and the final product synthesis scheme is the Buchwald-Hartwig cross coupling reaction (Scheme 7 to Scheme 10) and aromatic nucleophilic. Based on the substitution reaction (Scheme 11), these reactions will proceed even if substituents not specifically specified are combined.

Manufacturing evaluation of organic electric devices

[ Experimental Example 1] (Phosphorus Green Host)

The organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention (one of 1-1 to 1-112) obtained through synthesis as a light emitting host material of the light emitting layer.

First, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) is vacuum-deposited on the ITO layer (anode) formed on the organic substrate to have a thickness of 60 nm. A hole injection layer was formed. Subsequently, a 4,4-bis[ N- (1-naphthyl) -N -phenylamino]biphenyl (hereinafter abbreviated as NPD) was vacuum-deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer. Next, the compound of the present invention was doped with a host material on the hole transport layer, and Ir(ppy)3 [tris(2-phenylpyridine)-iridium] was doped with a 95:5 weight ratio as a dopant to deposit a light emitting layer with a thickness of 30 nm. Subsequently, (1,1'-bisphenyl)-4-oleito)bis(2-methyl-8-quinolinoleito)aluminum (hereinafter abbreviated as BAlq) is vacuum-deposited to a thickness of 10 nm on the light emitting layer. A hole blocking layer was formed, and an electron transport layer was formed on the hole blocking layer with Tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

The electroluminescence (EL) characteristics were measured with the PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent device of the Examples and Comparative Examples prepared as described above, and the measurement result showed the luminance at the standard luminance of 300 cd/m ² . The T90 life was measured using a life measurement equipment manufactured by Max Science.

Table 5 below shows device fabrication and evaluation results for Experimental Example 1 and Comparative Examples 1 to 3 to which the compound according to the invention was applied.

[ Comparative example One]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the following Comparative Compound 1 was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative Compound 1>

[ Comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the following Comparative Compound 2 was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative Compound 2>

[ Comparative example 3]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the following Comparative Compound 3 was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative Compound 3>

The electroluminescence (EL) characteristics were measured with the PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent device of the Examples and Comparative Examples prepared as described above, and the measurement result showed the luminance at the standard luminance of 300 cd/m ² . The T90 life was measured using a life measurement equipment manufactured by Max Science.

Table 4 below shows device fabrication and evaluation results for Experimental Example 1 and Comparative Examples 1 to 3 to which the compound according to the invention was applied.

[Table 4]

As can be seen from the results of Table 4, the compounds of Comparative Examples 1 to 3 generally show higher driving voltages, lower efficiencies, and lower lifetimes than the compounds of the present invention. Particularly, Comparative Example 2 and Comparative Example 3 showed a similar form in which a benzene ring was fused to a six-membered heterocycle when compared with the compound of the present invention, but showed different results depending on the number or location of fused benzene rings.

In other words, in the six-membered hetero ring, the benzene ring on the side that does not contain the hetero atom N has a form fused over a total of two sides than the compounds of Comparative Example 2 and Comparative Example 3, which are a form fused over all four sides. It can be seen that the compound of the invention has significantly improved efficiency and life, and the driving voltage is also lower.

This is considered to be because it is relatively difficult to have a deep HOMO energy level in the case of a compound that is structurally too large. In the case of the compound of the present invention, the hole can be moved to the light emitting layer more quickly through the deep HOMO energy level, and it can exhibit not only an increase in life but also high efficiency by inducing light emission inside the light emitting layer rather than the hole transport layer interface.

Above, the present invention has been described by way of example, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100: organic electrical element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (9)

Compound represented by the formula (1).
<Formula 1>

In Chemical Formula 1,
R ₁ to R ₇ and Ar ₁ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; -LN(Ar ₄ )(Ar ₅ ); And it is selected from the group consisting of a fluorenyl group,
L is a direct bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And a divalent aliphatic hydrocarbon group; is selected from the group consisting of (in this case, the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₁ ~ C ₂₀ may be substituted with one or more substituents selected from the group consisting of alkoxyl groups and amino groups),
Ar ₂ is a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fluorenyl group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; And -N (Ar ₄₎ are selected from the group consisting of (Ar ₅₎ (however, L is a direct bond, when Ar ₂ is an alkyl group include an alkyl group of the _{Ar 2 C 3 ~ C 50)} ,
Ar ₄ and Ar ₅ are each independently a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~ C ₅₀ alkyl group; Or a fluorenyl group.
(When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are aryl groups, they are hydrogen, deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C Import of ₂₀ alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups (alkenyl), an alkynyl of C ₂ ~ C ₂₀ group (alkynyl) a, C ₆ ~C ₂₀ Aryl group, substituted with deuterium C ₆ ~ C ₂₀ Aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are heterocyclic groups, they are hydrogen, deuterium, halogen, silane group, cyano group, nitro group, alkoxyl group of C ₁ to C ₂₀ , C ₁ to a C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ - C ₂₀ substituted by deuterium aryl group, a heterocyclic group of C ₂ ~ C ₂₀ , C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are fluorenyl groups, they are hydrogen, deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C ₂ to C consisting of a cycloalkyl group ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group,
When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are alkyl groups, they are halogen, silane group, boron group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a heterocyclic group of _{C 2 ~ C 20, C 7} ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₁ to R ₇ , Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are alkenyl groups, they are hydrogen, deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ Cycloalkyl group of ~C ₂₀ , C ₇ ~C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₁ to R ₇ , Ar ₁ and Ar ₂ are alkoxyl groups, they are hydrogen, deuterium, halogen, silane group, C ₁ to C ₂₀ alkyl group, C ₆ to C ₂₀ aryl group, C substituted with deuterium ₆ to C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of,
When R ₁ to R ₇ , Ar ₁ and Ar ₂ are aryloxy groups, they are substituted with hydrogen, deuterium, silane groups, cyano groups, C ₁ to C ₂₀ alkyl groups, C ₆ to C ₂₀ aryl groups, and deuterium. C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and may be substituted with one or more substituents selected from the group consisting of C ₃ ~ C ₂₀ cycloalkyl group) According to claim 1,
A compound characterized by being represented by one of the following formulas.

(In the above formula, R ₁ ~ R ₇ , Ar ₂ And L are the same as defined in Formula 1,
R ₈ to R ₁₃ and Ar ₃ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; -LN(Ar ₄ )(Ar ₅ ); And fluorenyl group, wherein Ar ₄ , Ar ₅ and L are the same as defined in Chemical Formula 1,
When R ₈ to R ₁₃ and Ar ₃ are aryl groups, they are hydrogen, deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C ₂₀ alkylthio, C ₁ to C Alkoxy group of ₂₀ , C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C ₂ ~ C ₂₀ alkynyl group (alkynyl), C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₈ ~ R ₁₃ And Ar ₃ Is a heterocyclic group, it is hydrogen, deuterium, halogen, silane group, cyano group, nitro group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ heterocyclic group of C _20, C ₃ ~ cycloalkyl group of C ₂₀ , C ₇ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₈ ~ R ₁₃ And Ar ₃ Is a fluorenyl group, it is hydrogen, deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C optionally substituted with one or more substituents selected from the group consisting of ₆ ~ C ₂₀ aryl group, a cycloalkyl group of C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium Can,
When R ₈ to R ₁₃ and Ar ₃ are alkyl groups, they are halogen, silane group, boron group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkene Diary (alkenyl), C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₇ ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₈ ~ R ₁₃ And Ar ₃ Is an alkenyl group, it is hydrogen, deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ the alkenyl group _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ C heterocyclic group of _20, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ Of C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,
When R ₈ ~ R ₁₃ And Ar ₃ Is an alkoxyl group, it is hydrogen, deuterium, halogen, silane group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C substituted with deuterium ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of,
When R ₈ ~ R ₁₃ And Ar ₃ is an aryloxy group, it is hydrogen, deuterium, silane group, cyano group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ substituted with deuterium C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of) According to claim 1,
A compound characterized by being represented by one of the following formulas.

In the organic electric device including a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode,
The organic material layer is an organic electric device, characterized in that it contains a compound of any one of claims 1 to 3. The method of claim 4,
An organic electric device characterized in that the compound is formed into the organic material layer by a soluble process. The method of claim 4,
The organic material layer is at least one of a light emitting layer, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, an electron injection layer and an electron transport layer. The method of claim 6,
The light emitting layer is an organic electric device characterized in that it is formed of the compound. A display device comprising the organic electroluminescent element of claim 4; And
A control unit for driving the display device; Electronic device comprising a. The method of claim 8,
The organic electroluminescent device is an electronic device characterized in that it is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a monochromatic or white lighting device.

Images