KR102109485B1 - 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 lifespan of a device, 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 organic materials. 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 made of different materials in order to increase the efficiency and stability of the organic electric device. In many cases, the structure of the layer is formed, 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 electric 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 the function. In addition, the light emitting material may be classified into a high molecular weight type and a low molecular weight type according to the molecular weight, and may be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. Can be. In addition, the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.

On the other hand, if only one material is used as the light emitting material, the maximum emission wavelength moves to a long wavelength due to the interaction between molecules, and the color purity decreases or the efficiency of the device decreases due to the light emission attenuation effect, resulting in an increase in color purity and energy transfer. To increase the luminous efficiency through, a host / dopant system may be used as a luminescent material. The principle is that when a small amount of the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to produce light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

The most important issues in organic electroluminescent devices are life and efficiency. As the display becomes larger, these efficiency and life problems must be solved. Efficiency, life, and driving voltage are related to each other. When the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in a lifetime. This tends to increase.

However, it is not possible to maximize efficiency by simply improving the organic material layer, and the optimum combination of energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) When achieved, long life and high efficiency can be achieved simultaneously. Therefore, there is a need to develop a light emitting material having high thermal stability and efficiently achieving charge balance in the light emitting layer. That is, in order to sufficiently exhibit the excellent characteristics of the 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, and an electron injection material, are supported by stable and efficient materials. It should be preceded, and among them, development of a host material of a light emitting layer is urgently 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 though 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, the component may be directly connected to or connected to the other component, but another component between each component It will be understood that elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise stated, the meaning of the following terms is as follows:

The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise noted.

The term "alkyl" or "alkyl group" used in the present invention has a single bond of 1 to 60 carbon atoms, unless otherwise specified, a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo By radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen, unless otherwise specified.

The term "heteroalkyl group" used in the present invention means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

The term "alkenyl group" or "alkynyl group" used in the present invention has a double or triple bond having 2 to 60 carbon atoms, and includes straight or branched chain groups, and is not limited thereto, unless otherwise specified. It is not.

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 "alkoxyl group", "alkoxy group", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and 2 to 60 unless otherwise specified. It has a carbon number, and is not limited thereto.

The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group to which an oxygen radical is attached, and has a carbon number of 6 to 60 unless otherwise specified, and is not limited thereto.

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, an aryl group or an arylene group means a single ring or multi-ring 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.

The prefix "aryl" or "ar" refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has a carbon number described herein.

Also, when the prefix is named in succession, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonyl alkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise noted. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 2 to 60 carbon atoms, each of which contains one or more heteroatoms, unless otherwise specified. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional devices.

The term "heterocyclic group" used in the present invention includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, heteroaliphatic ring and hetero, unless otherwise specified. Aromatic rings. Adjacent functional groups may also be formed by bonding.

As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless stated otherwise.

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 ring or heterocycle 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.

Unless otherwise specified, the term "carbonyl" used in the present invention is represented by -COR ', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms. Is a cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" used in the present invention is represented by -RO-R ', wherein R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or 6 to 30 carbon atoms. It is an aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

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 alkoxyl 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, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₂ 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. ) Between the organic material layer containing the compound according to the present invention. At this time, 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 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 or a light efficiency improving layer (Capping layer) formed on a 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 a host or dopant or light efficiency improving 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 It can be used as a material.

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 prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is a solution process or a solvent process (e.g., spin coating process), nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blade using various polymer materials It can be produced with fewer layers by a method such as a ding process, a screen printing process, or a thermal transfer method. 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 a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, R (Red), G (Green), B (Blue) light-emitting units are arranged in a mutually planar side-by-side manner, and a stacking method in which R, G, and B light-emitting layers are stacked vertically. There is a color conversion material (CCM) method using electroluminescence by the blue (B) organic light-emitting layer and photo-luminescence of the inorganic phosphor using light therefrom. Can be applied to these WOLEDs.

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 or 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 one aspect of the present invention is represented by the following formula (1).

Formula (1)

In the above formula,

n is an integer of 2 or 3,

when n is 2, Z is a single bond; C ₆ ~ C ₆₀ Arylene group; A C ₃ to C ₆₀ heteroarylene group including at least one hetero atom among O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₆₀ Alkylene group; C ₂ ~ C ₆₀ Alkenylene group; And C ₂ ~ C ₆₀ Alkylene group; is selected from the group consisting of,

when n is 3, Z is a trivalent C ₆ ~ C ₆₀ aryl group; A trivalent C ₃ to C ₆₀ heteroaryl group including at least one hetero atom from O, N, S, Si, and P; And C ₃ ~ fused ring group of an aromatic ring of C ₆₀ of aliphatic rings and C ₆ ~ C _60; is selected from the group consisting of,

Y is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And O, N, S, Si, and C ₂ to C ₆₀ heteroarylene groups including at least one heteroatom; C ₁ ~ C ₆₀ Alkylene group; C ₂ ~ C ₆₀ Alkenylene group; And C ₂ ~ C ₆₀ alkynylene group; is selected from the group consisting of (but, except that Y and Z are a single bond at the same time),

R ¹ to R ¹² are each independently of each other hydrogen; heavy hydrogen; Tritium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; Silane group; C ₆ ~ C ₃₀ Aryloxy group; And -LN (Ar ² ) (Ar ³ ); (wherein, L is a single bond; an arylene group of C ₆ ~ C ₆₀ ; at least one hetero of O, N, S, Si, and P) C ₂ ~ C ₆₀ heteroarylene group containing an atom; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₆₀ alkylene group; C ₂ ~ C ₆₀ alkenylene group; and C ₂ ~ C ₆₀ alkynylene group; is selected from the group consisting of, wherein Ar ² And Ar ³ are independently of each other, C ₆ ~ C ₆₀ aryl group; O, C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~ C ₃₀ alkoxy A real group; and a fluorenyl group; selected from the group consisting of), or adjacent groups of them combine with each other to form a ring,

X is N (Ar ¹ ) or C (R ') (R "), wherein R' and R" are independently of each other, a C ₆ to C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₁ ~ C ₅₀ alkyl group; is selected from the group consisting of,

Ar ¹ 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; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Fluorenyl group; C ₁ ~ C ₃₀ Alkoxy group; And -L'-N (Ar ⁴ ) (Ar ⁵ ); (where L ', Ar ⁴ and Ar ⁵ are the same as the definitions of L, Ar ² and Ar ³ , respectively),

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group independently of each other, deuterium, halogen, silane group, silosiloxane Acid group, boron group, germanium group, cyano group, nitro group, -L "-N (Ar ⁶ ) (Ar ⁷ ) (where L", Ar ⁶ and Ar ⁷ are the definitions of L, Ar ² and Ar ³ , respectively, Same), C ₁ ~ C ₂₀ alkylthio, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₆ to C ₂₀ aryl group, substituted with deuterium, C ₆ to C ₂₀ aryl group, fluorenyl group, C ₂ to C ₂₀ heterocyclic group, C ₃ to C ₂₀ cycloalkyl group, C ₇ to C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of arylalkyl groups, and C ₈ ~ C ₂₀ arylalkenyl groups.

The single bond means a case where a separate atom does not exist. For example, in Formula 1, when Y is a single bond, atoms N and Z in the nucleus atom group are directly connected to form a structure corresponding to Formula 1-1, 1-2, or 1-9 in Formula 1 below. .

Meanwhile, the compound represented by the formula (1) may be represented by the following formula (2) or formula (3).

<Formula 2> <Formula 3>

In the above formula, R ¹ to R ¹² , X, Y and Z are as defined in formula (1).

Specifically, the compound represented by Formula (1) is a compound represented by one of the following compounds, but is not limited thereto.

In another embodiment according to the present invention, the present invention includes a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode, the organic material layer according to an embodiment of the present invention It provides an organic electric device characterized in that it contains a compound.

In another embodiment according to the present invention, the present invention provides an organic electric device further comprising a light efficiency improving layer formed on at least one of the lower portion of the first electrode or the upper portion of the second electrode.

In another embodiment according to the present invention, the present invention provides an organic electric device that forms an organic material layer by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.

In another embodiment according to the present invention, the present invention provides an organic electric device characterized in that it contains a compound according to an embodiment of the present invention as a host material of the light emitting layer.

In another embodiment according to the present invention, the present invention provides an electronic device including a display device including the above-described organic electric element and a control unit for driving the display device.

In another embodiment according to the present invention, the present invention is an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a device for monochromatic or white lighting It provides an electronic device characterized in that at least one of the.

Hereinafter, examples of the synthesis of the compound represented by the formula (1) according to the present invention and the production 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

Synthesis of the compound was carried out in the following manner.

Final product ( final products ) Synthesis Example

Illustratively, the compounds according to the present invention (Final Products: products 1-1 to 2-24) may be prepared by reacting as in Scheme 1 below.

The final product according to the present invention is prepared by reacting as in Reaction Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1> X = N (Ar ¹ ) or CR'R ", n = 2 or 3, Hal = Br or I

One. Sub  1 compound

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

<Reaction Scheme 2> X = N (Ar ¹ ) or CR'R ", R = R 'or R"

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

(One) Sub  1-1 Compound Synthesis

<Scheme 3>

Synthesis of intermediate M 1-I-1

After the starting material 1,4-dibromonaphthalene (181.32 g, 634.1 mmol) was dissolved in THF in a round bottom flask, methyl 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) benzoate (110.8 g, 422.7 mmol), Pd (PPh ₃ ) ₄ (24.42 g, 21.1 mmol), K ₂ CO ₃ (175.27 g, 1268.2 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 the product 102.41 g (yield 71%).

Intermediate M 1- II -1 synthesis

M 1-I-1 (102.41 g, 300.1 mmol) obtained in the above synthesis was dissolved in Methanesulfonic acid (974 ml, 15007.3 mmol) and stirred at 50-60 ° C. Upon completion of the reaction, the mixture was lowered to 0 ° C., water was added, and the precipitated solid was filtered and washed with a small amount of water. After dissolving in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated, the resulting compound was silicagel column and recrystallized to obtain 77.95 g of product (yield: 84%).

Intermediate M 1- III -1 synthesis

After dissolving M 1-II-1 (77.95 g, 252.1 mmol) obtained in the above synthesis in Ethylene glycol, Hydrazine monohydrate (378.66 g, 7564 mmol), KOH (35.37 g, 630.3 mmol) was added, followed by stirring at 185 ° C. Upon completion of the reaction, the mixture was lowered to 0 ° C., water was added, and the precipitated solid was filtered and washed with a small amount of water. After dissolving in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated, the resulting compound was silicagel column and recrystallized to obtain 69.96 g of product (yield: 94%).

Intermediate Sub  1-I-1 synthesis

M 1-III-1 (69.96 g, 237 mmol), KO t -Bu (79.79 g, 711 mmol) obtained in the above synthesis was dissolved in DMSO, stirred at 0 ° C. for 5 minutes, and raised to room temperature to raise Iodomethane (100.93 g, 711 mmol) was added. 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 70.48 g of product (yield: 92%).

Intermediate Sub  One- II -1 synthesis

After dissolving Sub 1-I-1 (70.48 g, 218 mmol) obtained in the above synthesis in DMF in a round bottom flask, Bis (pinacolato) diboron (60.91 g, 239.9 mmol), Pd (dppf) Cl ₂ (5.34 g, 6.5 mmol), KOAc (64.2 g, 654.1 mmol) was added and stirred at 90 ° C. When the reaction was completed, DMF was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 63.79 g of product (yield: 79%).

Intermediate Sub  One- III -1 synthesis

After dissolving Sub 1-II-1 (63.79 g, 172.3 mmol) obtained in the above synthesis in THF in a round bottom flask, 1-bromo-2-nitrobenzene (61.82 g, 206.7 mmol), Pd (PPh ₃ ) ₄ (9.95 g, 8.6 mmol), K ₂ CO ₃ (71.43 g, 516.8 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 56.66 g of product (yield: 90%).

Sub  1-1 synthesis

Sub 1-III-1 (56.66 g, 155.1 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene in a round bottom flask, triphenylphosphine (101.67 g, 387.6 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 40.33 g of product (yield: 78%).

(2) Sub  1-7 Compound Synthesis

<Reaction Scheme 4>

Synthesis of intermediate M 2-I-7

After the starting material 1,4-dibromonaphthalene (223.81 g, 782.7 mmol) was dissolved in THF in a round bottom flask, (2-nitrophenyl) boronic acid (87.1 g, 521.8 mmol), Pd (PPh ₃ ) ₄ (26.1 g, 30.15 mmol), K ₂ CO ₃ (216.34 g, 1565.3 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 124.99 g (yield 73%) of the product.

Intermediate M 2- II -7 synthesis

After dissolving M 2-I-7 (124.99 g, 380.9 mmol) obtained in the above synthesis in o- dichlorobenzene in a round bottom flask, triphenylphosphine (249.75 g, 952.2 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 78.96 g of product (yield: 70%).

Intermediate Sub  1-I-7 synthesis

After dissolving M 2-II-7 (78.96 g, 266.6 mmol) obtained in the above synthesis in nitrobenzene in a round bottom flask, iodobenzene (81.59 g, 399.9 mmol), Na ₂ SO ₄ (37.87 g, 266.6 mmol), K ₂ CO ₃ (36.85 g, 266.6 mmol), Cu (5.08 g, 80 mmol) was added and stirred at 200 ° C. When the reaction was completed, nitrobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 74.44 g of product (yield: 75%).

Intermediate Sub  One- II -7 synthesis

Bis (pinacolato) diboron (55.86 g, 220 mmol), Pd (dppf) Cl ₂ (4.9 g, 6 mmol), KOAc in Sub 1-I-7 (74.44 g, 200 mmol) obtained in the above synthesis (58.87 g, 599.9 mmol), DMF was obtained using the above Sub 1-II-1 synthesis method to give the product 64.56 g (yield: 77%).

Intermediate Sub  One- III -7 synthesis

1-bromo-2-nitrobenzene (55.25 g, 184.8 mmol), Pd (PPh ₃ ) ₄ (8.9 g, 7.7 mmol), K ₂ CO in Sub 1-II-7 (64.56 g, 154 mmol) obtained in the above synthesis. ₃ (63.84 g, 461.9 mmol), THF, and water were obtained 55.65 g (yield: 87%) of the product using the above Sub 1-III-1 synthesis method.

Sub  1-7 synthesis

Tri-phenylphosphine (87.84 g, 334.9 mmol) and o- dichlorobenzene were added to Sub 1-III-7 (55.65 g, 134 mmol) obtained in the synthesis using 38.94 g (yield: 76%) of the product using the synthesis method of Sub 1-1. Got.

(3) Sub  1-11 Compound Synthesis

<Reaction Scheme 5>

Sub 1-III-11 (16.15 g, 38.9 mmol) triphenylphosphine (25.49 g, 97.2 mmol), o -dichlorobenzene was obtained using the above Sub 1-1 synthesis method to give the product 10.29 g (yield: 69%).

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

2. Final product ( Final Product)  synthesis

After dissolving (Br-Y) _n -Z (1 eq) in a round bottom flask with nitrobenzene, Sub 1 (n + (0.2 ~ 1) eq), 18-crown-6 (0.8 equivalent), K ₂ CO ₃ (5 equivalents), Cu (2.5 equivalents) was added and stirred at 200 ° C. When the reaction was completed, nitrobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain final products.

(1) Synthesis Example of Compound 1-4

<Scheme 6>

After dissolving 4,4'-diiodo-1,1'-biphenyl (5.16 g, 12.7 mmol) obtained in the synthesis with nitrobenzene in a round bottom flask, Sub 1-1 (9.32 g, 28 mmol), 18-crown- 6 (2.69 g, 10.2 mmol), K ₂ CO ₃ (8.78 g, 63.5 mmol), Cu (2.02 g, 31.8 mmol) was added and stirred at 200 ° C. When the reaction was completed, nitrobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain 6.65 g (yield: 64%) of the product.

(2) Compound 1-15 Synthesis Example

<Scheme 7>

4,6-bis (4-bromophenyl) pyrimidine (4.91 g, 12.6 mmol) obtained in the above synthesis, Sub 1-1 (9.23 g, 27.7 mmol), 18-crown-6 (2.66 g, 10.1 mmol), K ₂ CO ₃ (8.7 g, 62.9 mmol), Cu (2 g, 31.5 mmol) and nitrobenzene were obtained 6.87 g (yield: 61%) using the product 1-4 synthesis method.

(3) Synthesis Example of Compound 1-19

<Scheme 8>

2,4,6-tris (4-bromophenyl) -1,3,5-triazine (5.02 g, 9.2 mmol) obtained in the above synthesis, Sub 1-1 (12.26 g, 36.8 mmol), 18-crown-6 ( 1.94 g, 7.4 mmol), K ₂ CO ₃ (6.35 g, 46 mmol), Cu (1.46 g, 23 mmol) and nitrobenzene were obtained using the product 1-4 synthesis method to obtain 6.23 g (yield: 52%) of the product.

(4) Synthesis Example of Compound 1-21

<Scheme 9>

3,6-diiodo-9-phenyl-9 H -carbazole (5.94 g, 12 mmol) obtained in the above synthesis, Sub 1-1 (8.8 g, 26.4 mmol), 18-crown-6 (2.54 g, 9.6 mmol) , K ₂ CO ₃ (8.29 g, 60 mmol), Cu (1.91 g, 30 mmol) and nitrobenzene were obtained using the product 1-4 synthesis method to obtain 7.07 g (yield: 65%) of the product.

(5) Compound 2-2 Synthesis Example

<Reaction Scheme 10>

Sub 1-7 (9.62 g, 25.1 mmol), 18-crown-6 (2.42 g, 9.1 mmol) to 4,4'-diiodo-1,1'-biphenyl (4.64 g, 11.4 mmol) obtained in the above synthesis, K ₂ CO ₃ (7.9 g, 57.1 mmol), Cu (1.82 g, 28.6 mmol) and nitrobenzene were obtained 6.07 g (yield: 58%) using the product 1-4 synthesis method.

(6) Compound 2-5 Synthesis Example

<Scheme 11>

Sub 1-11 (9.5 g, 24.8 mmol), 18-crown-6 to 4,4 ''-diiodo-1,1 ': 4', 1 ''-terphenyl (5.43 g, 11.3 mmol) obtained in the above synthesis (2.38 g, 9 mmol), K ₂ CO ₃ (7.78 g, 56.3 mmol), Cu (1.79 g, 28.2 mmol) and nitrobenzene were obtained using the product 1-4 synthesis method to obtain 6.94 g of product (yield: 62%).

(7) Compound 2-12 Synthesis Example

<Reaction Scheme 12>

Sub 1-7 (10.21 g, 26.7 mmol), 18-crown-6 (2.57 g, 9.7 mmol), K _{2 to} 2,6-bis (3-bromophenyl) pyridine (4.72 g, 12.1 mmol) obtained in the above synthesis CO ₃ (8.38 g, 60.7 mmol), Cu (1.93 g, 30.3 mmol), nitrobenzene was obtained 6.74 g (yield: 56%) of the product using the product 1-4 synthesis method.

(8) Compound 2-15 Synthesis Example

<Scheme 13>

Sub 1-7 (14.28 g, to 4,4 ''-dibromo-5 '-(4-bromophenyl) -1,1': 3 ', 1''-terphenyl (5.07 g, 9.3 mmol) obtained in the above synthesis, 37.3 mmol), 18-crown-6 (1.97 g, 7.5 mmol), K ₂ CO ₃ (6.45 g, 46.7 mmol), Cu (1.48 g, 23.3 mmol), nitrobenzene was obtained 6.62 g (yield: 49%) of the product using the product 1-4 synthesis method.

Meanwhile, the FD-MS values of the compounds 1-1 to 1-28 and 2-1 to 2-24 of the present invention prepared according to the above synthesis example are shown in Table 2 below.

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 reactions, Methanesulfonic acid-catalyzed ring closure reactions ( J. Med . Chem . 1996, 39 , 4897), Wolff Based on -Kishner Reduction reaction, Nucleophilic substitution reaction, PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70 , 5014.), Miyaura boration reaction and Ullmann reaction reaction, etc. Those skilled in the art will readily understand that the reaction proceeds even when other substituents defined in (substituents such as X, Y, Z, and R ₁ to R ₁₂ ) are combined. For example, in Reaction Scheme 2, reactions from starting material-> M 1-I, starting material-> M 2-I, Sub 1-II-> Sub 1-III, etc. are all based on the Suzuki cross-coupling reaction. The M 1-I-> M 1-II reaction is based on the Methanesulfonic acid-catalyzed ring closure reaction, and in Scheme 2, the M 1-II-> M 1-III reaction is based on the Wolff-Kishner Reduction reaction. The M 1-III-> Sub 1-I reaction is based on the Nucleophilic substitution reaction. Subsequently, in Scheme 2, the M 2-I-> M 2-II, Sub 1-III-> Sub 1 reaction is based on the PPh ₃ -mediated reductive cyclization reaction, and in Scheme 2, Sub 1-I-> Sub 1-II The reaction is based on the Miyaura boration reaction, and in Scheme 2, the M 2-II-> Sub 1-I, Product synthesis schemes (Scheme 6 to Scheme 13) are based on the Ullmann reaction, and substituents not specifically specified are bound to them The reactions will proceed if possible.

Manufacturing evaluation of organic electric devices

[ Experimental Example  1] to [ Experimental Example  44] Red organic electroluminescent device (Phosphorescence Red  Host)

The organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention (one of 1-1 to 2-24) 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. Then, a 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as NPD) was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Next, doping the compound of the present invention as a host material on the hole transport layer, dopant (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] at a weight ratio of 95: 5, 30nm The light emitting layer was deposited to a thickness. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) on the light emitting layer was vacuum deposited to a thickness of 10 nm to form a hole. A 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.

[ Comparative example  1] to [ Comparative example  3]

As the host material of the light emitting layer, Comparative Example 1 is the same as in Experimental Example, except that Comparative Example 1 is used as the following Comparative Compound 1, Comparative Example 2 is used as the following Comparative Compound 3, and Comparative Example 3 is used as Comparative Compound 3 as the host material. An organic electroluminescent device was produced.

<Comparative compound 1> CBP <Comparative compound 2> <Comparative compound 3>

The electroluminescence (EL) characteristics were measured with the PR-650 of photoresearch by applying a direct bias DC voltage to the organic electroluminescent device of the experimental and comparative examples prepared as described above, and the measurement result showed the luminance at the standard of 2500 cd / m ² . The T95 life was measured using a life measurement equipment manufactured by Max Science.

Table 3 below shows the device fabrication and evaluation results for Experimental Examples 1 to 30 and Comparative Examples 1 to 3 to which the compounds according to the invention were applied.

As can be seen from the results of Table 3, when the compound of the present invention is used as a material for an organic electroluminescent device as a red emitting layer material, it is possible to not only lower the driving voltage of the organic electroluminescent device, but also significantly improve the luminous efficiency and lifetime. have.

Particularly, when using the comparative compound 2 and the comparative compound 3, in which a five-membered heterocycle in which one more benzene ring is fused than the comparative compound 1, which is CBP, is introduced as one of the materials for an organic electroluminescent device, it exhibits better luminous efficiency. In the case of using the compound of the present invention in which a five-membered heterocycle in which one more benzene ring is fused is introduced on both sides, comparatively lower driving voltage, higher efficiency, and higher lifespan were obtained than when Comparative Compound 2 and Comparative Compound 3 were used.

This is because when the benzene ring is further fused to the five-membered hetero ring, it exhibits high thermal stability and has a deep HOMO energy level as the core is introduced.

In other words, when the core is introduced to both sides, such as the compound of the present invention, it has a deeper HOMO energy level, and as a result, holes pass more quickly to the light-emitting layer and increase the lifespan, as well as light emission inside the light-emitting layer rather than the hole transport layer interface. It emits light to show higher efficiency. In addition, it is possible to implement an organic electric device having a low driving voltage with high thermal stability.

[ Experimental Example  45] and [ Experimental Example  46] Green organic electroluminescent device (phosphorescent green host)

The ITO (Indium Tin Oxide) layer on the substrate was patterned to have a size of 3 mm X 3 mm and then washed. After the substrate is mounted on a spin coater, PEDOT: PSS is spin-coated to a thickness of 50 nm on the ITO layer. Then, after drying for 10 minutes on a hot plate at 150 ° C to remove the solvent, HTL1, a hole transport material, is dissolved in xylene and spin-coated to a thickness of 30 nm. It was then dried for 10 minutes on a hot plate at 100 ° C, and then crosslinked by heating at 200 ° C for 30 minutes. Doping the present compound (1-28 or 2-17) as a dopant material on the hole transport layer as a light emitting layer host by doping with Ir (mppy) ₃ [tris (2- (4-tolyl) phenylpyridine) iridium (III)] at 95: 5 Then, spin-coating the solution dissolved in xylene to a thickness of 30 nm and drying it on a hot plate at 100 ° C. for 10 minutes, mount it in a vacuum chamber and set the base pressure to 1X10 ^-6 torr.

Subsequently, BAlq was vacuum deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was deposited to a thickness of 40 nm as an electron transport layer. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, as an electron injection layer to a thickness of 0.5 nm, and then depositing Al to a thickness of 150 nm to use as a cathode.

[ Comparative example  4]

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

The electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a direct bias DC voltage to the organic electroluminescent devices of Experimental Examples 45 and 46 and Comparative Examples prepared as described above, and the result was 500 cd / m ² T95 life was measured at a reference luminance through a life measurement equipment manufactured by Max Science.

Table 4 below shows device fabrication and evaluation results for Experimental Example 2 and Comparative Example 4 to which the compound according to the invention was applied.

As can be seen from the results of Table 4, when the compound of the present invention is used as a green light-emitting layer material for an organic electroluminescent device, it exhibits a lower driving voltage, higher efficiency, and higher lifetime than Comparative Compound 1, which is CBP.

And it can be seen that the compound of the present invention can be applied to a large area organic electroluminescent device by a spin coating method.

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,
n is an integer of 2 or 3,
when n is 2, Z is a single bond; C ₆ ~ C ₃₀ Arylene group; And C ₃ ~ C ₃₀ heteroarylene group containing at least one heteroatom of O, N and S; is selected from the group consisting of,
when n is 3, Z is a trivalent C ₆ ~ C ₃₀ aryl group; And O, N and S of a trivalent C ₃ ~ C ₃₀ heteroaryl group containing a hetero atom; is selected from the group consisting of,
Y is a single bond; C ₆ ~ C ₃₀ Arylene group; Fluorylene group; And C ₂ ~ C ₃₀ heteroarylene group containing at least one heteroatom of O, N and S; is selected from the group consisting of,
Except that Y and Z are single bonds at the same time,
R ¹ to R ¹² are each independently of each other hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl 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; Silane group; And C ₆ ~ C ₃₀ Aryloxy group; It is selected from the group consisting of,
X is N (Ar ¹ ) or C (R ') (R "), wherein
Ar ¹ is a C ₆ ~ C ₃₀ aryl group; C ₂ ~ C ₃₀ heterocyclic group containing at least one heteroatom of O, N and S; And fluorenyl group; is selected from the group consisting of,
R 'and R "are, independently of each other, an aryl group of C ₆ to C ₃₀ ; a fluorenyl group; a heterocyclic group of C ₂ to C ₃₀ including at least one hetero atom from O, N and S; and C ₁ ~ C ₅₀ alkyl group; is selected from the group consisting of,
The aryl group, fluorenyl group, heterocyclic group, alkyl group, alkenyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group independently of each other, deuterium, halogen, silane group, siloxane group, boron group, germanium group , Cyano group, nitro group, C ₁ ~ C ₂₀ alkylthio, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₆ ~ C ₂₀ aryl Group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, fluorenyl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ arylalkyl group, and C ₈ It may be further substituted with one or more substituents selected from the group consisting of ~ C ₂₀ aryl alkenyl group. According to claim 1,
Chemical Formula 1 is a compound characterized in that represented by the following Chemical Formula 2 or Chemical Formula 3:
<Formula 2><Formula3>

In Formulas 2 and 3, R ¹ to R ¹² , X, Y and Z are as defined in claim 1. According to claim 1,
The compound represented by Formula 1 is one of the following compounds:

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 comprises an organic electroluminescent device comprising the compound of any one of claims 1 to 3. The method of claim 4,
And an optical efficiency improving layer formed on at least one surface opposite to the organic material layer among one surface of the first electrode and one surface of the second electrode. The method of claim 4,
The organic layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process. The method of claim 4,
The compound is an organic electric device characterized in that it is used as a material of the light emitting layer. A display device comprising the organic electroluminescent element of claim 4; And
An electronic device comprising; a control unit for driving the display device. 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.

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