KR20120051598A - New compounds and organic electronic device using the same - Google Patents

Abstract

PURPOSE: A compound is provided to have excellent properties like the increase of efficiency, the reduction of driving voltage, the increase of stability, etc in case of forming an organic material layer, and using as a hole injection, a hole transport, an electron injection and transport material, phosphor material, etc. CONSTITUTION: A compound is in chemical formula 1 or chemical formula 2. In chemical formulas, Ar1, Ar2, Ar4 and Ar5 is respectively selected from a group consisting of substituted or unsubstituted arylene groups, substituted or unsubstituted heteroarylene groups, Ar3 is selected from a group consisting of hydrogen, deuterium, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. An organic electronic device comprises a first electrode, a second electrode, and organic material layers of one or more layers arranged between the first electrode and the second electrode. At least one o more layers of the organic layers comprise the compound.

Description

Novel compounds and organic electronic device using the same {NEW COMPOUNDS AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

The present invention relates to a novel compound and an organic electronic device using the same. This application claims the benefit of the filing date of Korean Patent Application No. 10-2010-0113024 filed with the Korea Intellectual Property Office on November 12, 2010, the entire contents of which are incorporated herein.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires an exchange of holes and / or electrons between an electrode and an organic semiconductor material. The organic electronic device can be divided into two types according to the operating principle. First, an exciton is formed in the organic layer by photons introduced into the device from an external light source, and the exciton is separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is an electronic device of the form. The second type is an electronic device in which holes and / or electrons are injected into the organic semiconductor material layer that interfaces with the electrodes by applying voltage or current to two or more electrodes, and is operated by the injected electrons and holes.

Examples of organic electronic devices include organic light emitting devices, organic solar cells, organic photoconductor (OPC) drums, and organic transistors, all of which are electron / hole injection materials, electron / hole extraction materials, and electron / hole transport materials for driving the devices. Materials or luminescent materials are required. Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, an electron / hole injection material, an electron / hole extraction material, an electron / hole transport material, or a light emitting material may all operate on a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode and an organic material layer therebetween. In this case, the organic material layer is often formed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The luminescent material includes blue, green, and red luminescent materials and yellow and orange luminescent materials necessary to realize better natural colors depending on the emission color. In addition, in order to increase luminous efficiency through increase in color purity and energy transfer, a host / dopant system may be used as the light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to fully exhibit the excellent characteristics of the above-described organic light emitting device, a material forming the 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, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been sufficiently achieved, and therefore, the development of new materials is continuously required.

The present invention provides novel compounds.

In addition, the present invention is an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one layer of the organic layer is the novel compound It provides an organic electronic device comprising.

The novel compounds according to the present invention can be used as organic material layers of organic electronic devices including organic light emitting devices by introducing various aryl groups, heteroaryl groups, arylamino groups, and the like. The organic electronic device including the organic light emitting device using the compound according to the present invention as a material of the organic material layer exhibits excellent characteristics in efficiency, driving voltage, lifetime, and the like.

1 illustrates an organic light emitting device structure in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101.
2 illustrates an organic light emitting device structure in which an anode 102, a hole injection / hole transport and light emitting layer 105, an electron transport layer 106, and a cathode 107 are sequentially stacked on a substrate 101.
3 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport and light emitting layer 105, an electron transport layer 106 and a cathode 107 are sequentially stacked. .
4 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially stacked. .

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

We have found compounds with novel structures. In addition, it has been found that when the organic compound layer of the organic electronic device is formed using the novel compound, effects such as efficiency increase, driving voltage drop, and stability increase of the device may be exhibited.

Accordingly, an object of the present invention is to provide a novel compound and an organic electronic device using the same.

The novel compounds according to the present invention include compounds represented by the following general formula (1) or (2):

[Formula 1]

[Formula 2]

In the above Formulas 1 and 2,

Ar1, Ar2, Ar4 and Ar5 are each independently deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and An arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of nitrile groups; And one or more substituents selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and nitrile groups It is selected from the group consisting of a hetero arylene group substituted or unsubstituted with a hetero atom containing O, N or S,

Ar3 is hydrogen; heavy hydrogen; One or more substituents selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and nitrile groups Substituted or unsubstituted aryl group; And one or more substituents selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and nitrile groups It is selected from the group consisting of a heteroaryl group which is unsubstituted or substituted with a hetero atom containing O, N or S as a hetero atom.

In Formulas 1 and 2, Ar1, Ar2, Ar3, Ar4 and Ar5 may each independently include a chromophore.

In the compound according to the present invention, the substituents of Chemical Formulas 1 and 2 will be described in detail below.

Examples of the halogen group include fluorine, chlorine, bromine and iodine, but are not limited thereto.

The alkyl group may be straight or branched chain, carbon number is not particularly limited, but is preferably 1 to 12. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, and the like.

The alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 12. Specific examples thereof include alkenyl groups in which aryl groups such as stylbenyl and styrenyl are connected, but are not limited thereto.

The alkoxy group preferably has 1 to 12 carbon atoms, more specifically methoxy, ethoxy, isopropyloxy, and the like, but is not limited thereto.

The aryl group may be monocyclic or polycyclic, and the carbon number is not particularly limited, but is preferably 5 to 30. Examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene, and the like. Examples of the polycyclic aryl group include naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, perrylenyl group, and cryo. Although a cenyl group, a fluoroanthene group, etc. are mentioned, It is not limited to this.

The heteroaryl group is a ring group containing O, N, S or P as a hetero atom, and the carbon number is not particularly limited, but is preferably 5 to 30 carbon atoms. Examples of the heterocyclic group include carbazole group, thiophene group, furan group, pyrrole group, imidazole group, imidazoquinazolin group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, pyrazine group, qui There are nolinyl group, isoquinoline group, acridil group and the like, and compounds such as the following structural formula are preferred, but are not limited thereto.

Specific examples of the arylene group may include a phenylene group, a biphenylene group, a naphthalenyl group, a binaphthalene group, an anthracenylene group, a fluorenylene group, a chrysenylene group, a phenanthrenylene group, and the like, but are not limited thereto. .

In the present specification, the term "substituted or unsubstituted" is deuterium, halogen, alkyl, alkenyl, alkoxy, silyl, arylalkenyl, aryl, heteroaryl, carbazole, arylamine, aryl It means that it is substituted with one or more substituents selected from the group consisting of a fluorenyl group and a nitrile group unsubstituted or substituted with a group or does not have any substituent.

Substituents which may be further substituted with Ar 1, Ar 2, Ar 3, Ar 4, and Ae 5 of Formulas 1 and 2 may be a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, an aryl alkenyl group, an aryl group, a heteroaryl group, and a carba. A sol group, an arylamine group, a fluorenyl group unsubstituted or substituted with an aryl group, a nitrile group, etc. can be mentioned, It is not limited to this.

Specific examples of Ar 1 of Chemical Formula 1 include the following structural formulas, but are not limited thereto.

Specific examples of Ar 2 in Formula 1 may include the following structural formulas, but are not limited thereto.

Specific examples of Ar 3 of Formula 1 may include the following structural formulas, but are not limited thereto.

In the above structural formula, each X is independently N, S or O, and CY represents an aryl group or a heteroaryl group.

Specific examples of Ar 4 of Formula 2 may include the following structural formulas, but are not limited thereto.

In the above structural formula, CY represents an aryl group or a heteroaryl group.

Specific examples of Ar 5 of Formula 2 may include the following structural formulas, but are not limited thereto.

The compound represented by Formula 1 or Formula 2 may be any one selected from the group consisting of the following structural formulas.

Compounds represented by Formula 1 and Formula 2 according to the present invention can generally be prepared by a multi-step chemical reaction. That is, some intermediate compounds are prepared first, and compounds of formula 1 or formula 2 are prepared from the intermediate compounds.

Hereinafter, a method for preparing the compound represented by Chemical Formula 1 will be described.

The compound represented by Chemical Formula 1 may be prepared using general methods known in the art, such as alcohol production and Suzuki binding reaction.

The compound represented by Chemical Formula 1 may be prepared as in the reaction process of Scheme 1 below. In addition, Scheme 1 is only an example for synthesizing the formula (1) is not limited thereto.

Scheme 1

According to Scheme 1, a compound including Ar 2 and a compound containing Ar 3 are reacted by Suzuki coupling under a palladium (Pd) catalyst to synthesize Compound B, and a compound comprising a cyano group and Ar 1. And Suzuki bond with Compound B under the Pd catalyst and the compound represented by the formula (1) can be synthesized.

Scheme 2

According to the above Reaction Scheme 2, the compound represented by the formula (2) can be synthesized by Suzuki bond with the compound C under the compound D and Pd catalyst containing a cyano group and Ar4.

In Schemes 1 and 2, Ar1, Ar2, Ar3, Ar4 and Ar5 are the same as defined in the formula (1) and (2).

Compounds represented by Formula 1 may have properties suitable for use as an organic material layer used in an organic light emitting device by introducing various substituents in the core structure represented by the formula. The compound of Formula 1 may exhibit properties even when used in any layer of the organic light emitting device, but may exhibit the following properties.

Compounds in which substituted or unsubstituted arylamine groups are introduced are suitable as light emitting layer, hole injection and hole transport layer materials, and when heterocyclic ring substituents containing N are introduced, they are suitable as electron injection, electron transport layer and hole blocking layer materials. Do.

The conjugation length of the compound and the energy bandgap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. As described above, since the cores of the compounds represented by Formula 1 contain limited conjugation, they have properties ranging from small energy band gaps to large properties.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, the hole injection layer material and the hole transport layer material used in manufacturing an organic light emitting device have an energy level sufficient to transfer holes along the HOMO, and an energy level sufficient to block electrons from passing through the LUMO from the light emitting layer. It may be a compound which may have. In particular, the core structure of the compound exhibits stable properties to the electrons and may contribute to improving the life of the device. Derivatives made by introducing substituents to be used in the light emitting layer and the electron transporting material can be manufactured to have an appropriate energy band gap in a variety of arylamine dopants, aryl dopants, metal dopants and the like.

In addition, by introducing a variety of substituents in the core structure it is possible to finely control the energy band gap, on the other hand to improve the properties at the interface between the organic material and to vary the use of the material.

On the other hand, the compounds of Formula 1 have a high glass transition temperature (Tg) is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

In addition, the organic electronic device according to the present invention is an organic electronic device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, one or more of the organic material layer It is characterized by including a compound represented by the formula (1).

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that at least one organic material layer is formed using the above-described compounds.

The compound of Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in manufacturing an organic electronic device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.

The organic material layer of the organic electronic device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic electronic device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic electronic device is not limited thereto and may include a smaller number of organic material layers.

Therefore, in the organic electronic device of the present invention, the organic material layer may include at least one of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is represented by Chemical Formula 1 It may include a compound represented by.

In addition, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1.

In addition, the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include a compound represented by Formula 1 above. have.

In the organic layer of the multilayer structure, the compound of Formula 1 may be included in a light emitting layer, a layer for simultaneously injecting / holes transporting and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting light.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in Figs. 1 to 4, but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound of Formula 1 may be included in the light emitting layer 105.

2 illustrates a structure of an organic light emitting device in which an anode 102, a hole injection / hole transport and light emitting layer 105, an electron transport layer 106, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound of Formula 1 may be included in the hole injection / hole transport and the light emitting layer 105.

3 illustrates a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport and emission layer 105, an electron transport layer 106, and a cathode 107 are sequentially stacked. It is. In such a structure, the compound of Formula 1 may be included in the hole injection / hole transport and the light emitting layer 105.

4 illustrates a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron transport and light emitting layer 105, and a cathode 107 are sequentially stacked. It is. In such a structure, the compound of Formula 1 may be included in the electron transport and emission layer 105.

For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer may be prepared by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The electron transporting material is a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer. A material having high mobility to electrons is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

In particular, when the compound of Formula 1 or 2 according to the present invention is included in the electron transport layer, the electron transport layer is a plate selected from the group consisting of alkali metals, alkali metal compounds, alkaline earth metals, alkaline earth metal compounds and combinations thereof It may further include, and preferably include Li, Ca, LiQ, LiF and the like, but is not limited thereto.

The compound according to the present invention may also operate on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.

Therefore, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention, whereby the scope of the invention is not limited.

In the Example, the evaluation method is as follows.

Drive voltage: measured using Kethley 236 (source measure unit)

2. Current efficiency: measured using SpectraScan Pr-650

3. Color coordinates: measured using SpectraScan Pr-650

< Example >

< Synthetic example  1>

This synthesis yielded Compounds 1A and 1B in the same manner as in the following reaction scheme.

<References>

Synthesis , 2005, 1 , 47-56

-Bioorg . & Med . Chem . Lett . , 2009, 5191-5194

More specifically, the commercially available 1-fluoro-2-nitrobenzene (10.55ml, 0.100mol) and 4-aminobenzonitrile (11.8g, 0.100mol) ) Was dissolved in 100 ml of DMSO (dimethylsulfoxide, Dimethylsulfoxide) and reacted overnight at 100 ° C. Reaction termination was confirmed using thin layer chromatography (TLC) and liquid chromatography (LC). After the reaction is completed, the reaction solvent is cooled to room temperature, and excess water is added to obtain a precipitate. The precipitate is dissolved in chloroform, and water is removed with anhydrous magnesium sulfate (MgSO ₄ anhydrous) to remove activated carbon. activated carbon) to remove the off-white. After filtration, the filtrate was removed with a rotary evaporator to obtain a compound (87%, 20.79 g).

MS: [M] ⁺ = 239

Compound a (20 g, 0.084 mol) and 4-bromobenzaldehyde (4-bromobenzaldehyde, 22.20 g, 0.12 mol) synthesized above were dissolved in ethanol, followed by Na ₂ S ₂ O ₄ (Sodium dithionite, 52.23 g, 0.300). mol) was added to the reaction solution. The reaction solution was subjected to overnight reflux reaction at 80 ° C. Reaction termination was confirmed using TLC and LC. After the reaction was completed, the reaction solution was cooled to room temperature, and the remaining Na ₂ S ₂ O ₄ was filtered, and the filtrate was removed using rotary evaporator to maximize ethanol and concentrated with chloroform. (concentrated) was extracted. The extraction solution was purified through a column separation tube (Ethyl acetate: n-hexane = 1: 9) to obtain a compound b (65.3%, 20.42g).

MS: [M] ⁺ = 374

Synthesized compound b (9.71g, 0.026mol), di (pinacoloboron) (di (pinacoloboron), 7.91g, 0.031mol) and potassium acetate (KOAc, Potassium acetate, 7.64g, 0.079mol) The mixture was placed in dioxane (1,4-dioxane, 100 ml) and heated and stirred under nitrogen for about an hour. After stirring for 1 hour, Pd (dppf) ₂ Cl ₂ (1,1'-Bis (diphenylphosphino) ferrocene-palladium (II) dichloride, 0.64g, 0.78mmol) was added, followed by heating stirring until the reaction was completed. I was. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated and THF was removed by a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated by a concentrator. . The concentrated solution was recrystallized in ethanol to give compound c (8.24g, 75.4%).

< Manufacturing example  1> Preparation of Compound 1-1-1

Compound 1A (10- (1-naphthyl) -9-bromoanthracene, 8 g, 21 mmol) and commercially available compound 1B (4-cyanophenyl boronic acid, 3.37 g, 0.023 mmol) in THF (50 ml) were dissolved in potassium phosphate. (K ₃ PO ₄ , potassium phosphate tribasic, 13.29 g, 63 mmol) was added to the reaction solution with water, and the mixture was heated and stirred under nitrogen for about an hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.72g, 0.63mmol) was added thereto, followed by heating and stirring until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed with a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-1 (9- (4-cyanophenyl) -10- (1-naphthyl) anthracene, 6.60 g, 78%).

MS: [M + H] = 406

< Manufacturing example  2> Preparation of Compound 1-1-2

Compound 2A (10- (1-naphthyl) -9-bromoanthracene, 8 g, 21 mmol) and commercially available compound 2C (3-cyanophenyl boronic acid, 3.37 g, 0.023 mmol) in THF (50 ml) were dissolved in potassium phosphate. (K ₃ PO ₄ , potassium phosphate tribasic, 13.29 g, 63 mmol) was added to the reaction solution with water, and the mixture was heated and stirred under nitrogen for about an hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.72g, 0.63mmol) was added thereto, followed by heating and stirring until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed with a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-2 (9- (3-cyanophenyl) -10- (1-naphthyl) anthracene, 6.37 g, 75.3%).

MS: [M + H] = 406

< Manufacturing example  3> Preparation of Compound 1-1-3

Compound 3A (1-bromopyrene, 5 g, 18 mmol) and commercially available compound 1B (4-cyanophenyl boronic acid, 3.14 g, 0.021 mmol) were dissolved in THF (50 ml), followed by potassium phosphate (K ₃ PO ₄ , potassium phosphate). tribasic, 11.33 g, 53 mmol) was added to the reaction solution with water, and the mixture was heated and stirred under nitrogen for about 1 hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.82 g, 0.71 mmol) was added, and the mixture was heated and stirred until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed with a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-3 (1- (4-cyanophenyl) pyrene, 4.25g, 78.8%).

MS: [M + H] = 303

< Manufacturing example  4> Preparation of Compound 2-1-1

Compound 4A (1,6-dibromopyrene, 4.26 g, 12 mmol) and commercially available compound 1 B (4-cyanophenyl boronic acid, 4.0 g, 27 mmol) were dissolved in THF (50 ml), followed by potassium phosphate (K ₃ PO ₄ , potassium phosphate tribasic, 12.56g, 59mmol) was added to the reaction solution with water and stirred under nitrogen for about an hour. After stirring for an hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 1.09g, 0.95mmol) was added thereto, followed by heating and stirring until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed with a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 2-1-1 (1,6-di (4-cyanophenyl) pyrene, 3.45 g, 73%).

MS: [M + H] = 404

< Synthetic example  2>

Commercially available 2-cyano-6-naphthol (5.0 g, 0.029 mol) and nonnafluorobutyl fluoride (5.93 ml, 0.034 ml) were treated with THF (50 ml). After dissolving in potassium carbonate (K ₂ CO ₃ , potassium carbonate, 11.89g, 0.086mol) was added and stirred until the reaction was completed. The resulting reaction was concentrated with a concentrator, and the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, filtered and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethanol to give compound 5B (10.57g, 81.7%).

MS: [M] ⁺ = 451

< Manufacturing example  5> Preparation of Compound 1-1-4

Compound 5B (10- (1-naphthyl) -9-anthracenylboronic acid, 6.79 g, 20 mmol) and compound 5B (2-cyano-6-naphthoyl nonaflate, 8.0 g, 18 mmol) synthesized in THF (50 ml) were dissolved in Potassium (K ₃ PO ₄ , potassium phosphate tribasic, 11.29g, 53mmol) was added to the reaction solution with water and stirred under nitrogen for about an hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.82 g, 0.71 mmol) was added, and the mixture was heated and stirred until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed with a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-4 (10- (1-naphthyl) -9- (2-cyano-6-naphthyl) -anthracene, 4.41 g, 54.6%).

MS: [M + H] 456

< Manufacturing example  6> Preparation of Compound 1-1-5

Compound 1B (4-cyanophenylboronic acid, 5.0 g, 27 mmol) synthesized with compound 6A (9,10-diphenylanthracen-2-yl boron pinacolate, 15.04 g, 33 mmol) was dissolved in THF (50 ml), followed by potassium phosphate (K ₃ PO). ₄ , potassium phosphate tribasic, 17.49 g, 82 mmol) was added to the reaction solution with water, and the mixture was heated and stirred under nitrogen for about 1 hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 1.27 g, 1.1 mmol) was added, and the mixture was heated and stirred until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed by rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, filtered and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-5 (9,10-diphenyl-2- (4-cyanophenyl) -anthracene, 8.17 g, 68.9%).

MS: [M + H] = 432

< Synthetic example  3>

1) Preparation of Compound 7B

Commercially available 9-bromoanthracene (25.7g, 0.100mol) and 4-cyanophenylboronic acid (17.63g, 0.120ml) were dissolved in THF (350ml) and phosphoric acid Potassium (K ₃ PO ₄ , potassium phosphate tribasic, 63.68g, 0.300mol) was added to the reaction solution with water and stirred under nitrogen for about an hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 4.62g, 4mmol) was added, followed by heating stirring until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed by a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated by a concentrator. The concentrated solution was recrystallized in ethanol to give compound 7B (9- (4-cyanophenyl) anthracene, 26.5g, 95.0%).

MS: [M] ⁺ = 279

2) Preparation of Compound 7C

Synthesized compound 7B (21g, 0.075mol) and NBS (N-bromosuccinimide, N-bromosuccinimide, 14.72g, 0.083mol) in CHCl ₃ (250ml), and then added acetic acid as catalytic amount. Stirred. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed by a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated by a concentrator. The concentrated solution was recrystallized in ethanol to give compound 7C (10- (4-cyanophenyl) -9-bromoanthracene, 22g, 81.7%).

MS: [M] ⁺ = 358

< Manufacturing example  7> Preparation of Compound 1-1-6

Compound 7C (5.0 g, 14 mmol) synthesized with compound 6A (9,10-diphenylanthracen-2-yl boron pinacolate, 7.01 g, 15 mmol) was dissolved in THF (100 ml), followed by potassium phosphate (K ₃ PO ₄ , potassium phosphate tribasic). , 8.89 g, 42 mmol) was added to the reaction solution together with water, followed by heating and stirring under nitrogen for about an hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.65g, 0.56mmol) was added, followed by heating stirring until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed by rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, filtered and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-6 (5.33 g, 62.9%).

MS: [M + H] 608

< Manufacturing example  8> Preparation of Compound 1-1-7

Compound b (3.0 g, 8.0 mmol) synthesized with compound 6A (9,10-diphenylanthracen-2-yl boron pinacolate, 4.02 g, 8.8 mmol) was dissolved in THF (30 ml), followed by potassium phosphate (K ₃ PO ₄ , potassium). phosphate tribasic, 5.11 g, 24 mmol) was added to the reaction solution together with water, and the mixture was heated and stirred under nitrogen for about an hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.37 g, 0.32 mmol) was added, and the mixture was heated and stirred until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed by rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, filtered and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-7 (3.95 g, 79.2%).

MS: [M + H] = 624

< Manufacturing example  9> Preparation of Compound 1-1-8

Compound 9A (9,10-di (2-naphthyl) anthracen-2-yl boron pinacolate, 4.91 g, 8.8 mmol) and compound b (3.0 g, 8.0 mmol) synthesized in THF (30 ml) were dissolved in potassium phosphate ( K ₃ PO ₄ , potassium phosphate tribasic, 5.11 g, 24 mmol) was added to the reaction solution with water, and the mixture was heated and stirred under nitrogen for about 1 hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.37 g, 0.32 mmol) was added, and the mixture was heated and stirred until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed with a rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 1-1-8 (4.57 g, 78.3%).

MS: [M + H] = 729

< Manufacturing example  10> Preparation of Compound 2-1-2

Compound 1B (4-cyanophenylboronic acid, 1.97 g, 13 mmol) and compound 7C (4.0 g, 11 mmol) synthesized in THF (30 ml) were dissolved in potassium phosphate (K ₃ PO ₄ , potassium phosphate tribasic, 7.11 g, 33 mmol). After addition to the reaction solution with water, the mixture was heated and stirred under nitrogen for about one hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.52g, 0.45mmol) was added, followed by heating and stirring until the reaction was completed. Reaction termination was confirmed by LC and TLC. After completion of the reaction, the water and the solution was separated, THF was removed by rotary evaporator, the concentrate was extracted with chloroform (CHCl ₃ ), the organic layer was removed with anhydrous magnesium sulfate, filtered and the filtrate was concentrated with a concentrator. The concentrated solution was recrystallized in ethyl acetate to give compound 2-1-2 (3.78 g, 88.9%).

MS: [M] ⁺ = 380

< Manufacturing example  11> Preparation of Compound 2-1-3

Compound 4A (1,6-dibromopyrene, 2.5g, 7mmol) and Compound c (6.73g, 16mmol) synthesized in THF (70ml) were dissolved in potassium phosphate (K ₃ PO ₄ , potassium phosphate tribasic, 8.84g, 42mmol) Was added to the reaction solution with water, and the mixture was heated and stirred under nitrogen for about one hour. After stirring for one hour, Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium, 0.64g, 0.56mmol) was added and the mixture was heated and stirred until the reaction was completed. Reaction termination was confirmed by LC and TLC. After the completion of the reaction, the resulting precipitate was filtered and the filtered precipitate was purified by Soxhlet purification with chloroform (CHCl ₃ ) to give compound 2-1-3 (3.34 g, 60.9%).

MS: [M + H] = 789

< Experimental Example  1>

The glass substrate coated with ITO (indium tin oxide) to a thickness of 1,500 kPa was put in distilled water in which detergent was dissolved and ultrasonically washed. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (400 kPa), which is a material for transporting holes, was vacuum deposited thereon, and the host H1 and the dopant D1 compound were vacuum deposited to a thickness of 300 kPa as a light emitting layer.

Compound 1-1-1 prepared in Preparation Example 1 was vacuum deposited on the emission layer to a thickness of 200 kPa to form an electron injection and transport layer. A cathode was formed by sequentially depositing 12 Å thick lithium fluoride (LiF) and 2,000 Å thick aluminum on the electron injection and transport layer. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7 Å / sec.

< Comparative example  1>

Except for using Alq ₃ in the electron transport layer in Experimental Example 1 was the same experiment.

< Experimental Example  2>

Except for using the compound 1-1-4 prepared in Preparation Example 5 in the electron transport layer in Experimental Example 1 was the same experiment.

< Experimental Example  3>

Except for using the compound 1-1-5 prepared in Preparation Example 6 in the electron transport layer in Experimental Example 1 was the same.

< Experimental Example  4>

Except for using the compound 1-1-6 prepared in Preparation Example 7 in the electron transport layer in Experimental Example 1 was the same.

< Experimental Example  5>

Except for using the compound 1-1-7 prepared in Preparation Example 8 in the electron transport layer in Experimental Example 1 was the same experiment.

[Table 1]

From the results of Table 1, it can be seen that when the organic material layer of the organic electronic device is formed using the compound according to the present invention, excellent characteristics such as efficiency increase, driving voltage drop, and stability increase are exhibited.

Claims (13)

Compound represented by the following formula (1) or formula (2):
[Formula 1]

(2)

In Chemical Formulas 1 and 2,
Ar1, Ar2, Ar4 and Ar5 are each independently deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and An arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of nitrile groups; And one or more substituents selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and nitrile groups It is selected from the group consisting of a hetero arylene group substituted or unsubstituted with a hetero atom containing O, N or S,
Ar3 is hydrogen; heavy hydrogen; One or more substituents selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and nitrile groups Substituted or unsubstituted aryl group; And one or more substituents selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, arylamine, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, fluorenyl and nitrile groups It is selected from the group consisting of a heteroaryl group which is unsubstituted or substituted with a hetero atom containing O, N or S as a hetero atom. The compound of claim 1, wherein Ar 1 in Formula 1 is selected from the group consisting of the following structural formulas:

The compound of claim 1, wherein Ar 2 in Formula 1 is selected from the group consisting of the following structural formulas:

The compound of claim 1, wherein Ar 3 of Chemical Formula 1 is selected from the group consisting of the following structural formulas:

In the above structural formula, each X is independently N, S or O, and CY represents an aryl group or a heteroaryl group. The compound of claim 1, wherein Ar 4 in Formula 2 is selected from the group consisting of the following structural formulas:

In the above structural formula, CY represents an aryl group or a heteroaryl group. The compound of claim 1, wherein Ar 5 in Formula 2 is selected from the group consisting of the following structural formulas:

The compound according to claim 1, wherein the compound represented by Chemical Formula 1 or Chemical Formula 2 is any one selected from the group consisting of the following structural formulas:

An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 7. An organic electronic device comprising the compound of formula (1) or (2) described. The method according to claim 8, wherein the organic layer comprises at least one layer of the electron injection layer and the electron transport layer, the organic electron, characterized in that at least one layer of the electron injection layer and the electron transport layer comprises the compound of Formula 1 or 2 device. The organic electronic device according to claim 8, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound of Formula 1 or 2. The method according to claim 8, wherein the organic layer comprises a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, one layer of the layer comprises the compound of Formula 1 or An organic electronic device, characterized in that. The organic electronic device of claim 8, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor. The method according to claim 8, wherein the organic layer comprises an electron transport layer comprising the compound of Formula 1, the electron transport layer is selected from the group consisting of alkali metal, alkali metal compound, alkaline earth metal or alkaline earth metal compound and combinations thereof An organic electronic device, further comprising a dopant.

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