WO2015064969A2 - Compound for organic electroluminescent device, organic electroluminescent device using same, and electronic device using said organic electroluminescent device - Google Patents

Abstract

The present invention provides a novel compound capable of improving the light-emitting efficiency, the stability, and the service life of a device, an organic electroluminescent device using same, and an electronic device using the organic electroluminescent device.

Description

Compound for organic electric element, organic electric element using same and electronic device thereof

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element 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 multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer in the organic electric device may be classified into a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material and the like according to a function.

The biggest problem for organic electric devices is life and efficiency. As the display becomes larger, these efficiency and life problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other.As the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Jouleheating generated during driving decreases, resulting in a lifetime. This tends to be higher. However, simply improving the organic layer may not maximize the efficiency. Because of the optimal combination of energy level, T ₁ value, and intrinsic properties (mobility, interfacial properties, etc.) between organic layers, long life and high efficiency can be achieved simultaneously. Because.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

However, holes move faster than electrons, and excitons generated in the emission layer are transferred to the electron transport layer, resulting in charge unbalance in the emission layer, thereby emitting light at the electron transport layer interface.

When emitting light at the electron transport layer interface, there is a problem that the color purity and efficiency of the organic electroluminescent device is deteriorated, and in particular, when the organic electroluminescent device is manufactured, high temperature stability is lowered, thereby shortening the lifespan of the organic electroluminescent device. Therefore, it is time to develop an electron transport material that has high temperature stability and high electron mobility and improves hole blocking ability with a high T1 value.

The present invention provides a compound having high electron mobility and high temperature stability, and having a more efficient hole blocking ability at a high T ₁ value, and at the same time, using the compound to improve efficiency, lifetime and color purity. And to provide an electronic device comprising the same.

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

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

According to the present invention, a compound having high electron mobility and high temperature stability and having a more efficient hole blocking ability with a high T ₁ value can be provided, and the compound can be used to improve efficiency, lifetime and color purity of the device. Can be improved.

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

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

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows:

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

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo 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.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.

As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

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

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

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

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

The prefix "aryl" or "ar" means 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 the radical substituted with an aryl group has the carbon number described herein.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group 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 an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

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

"Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a hetero ring having 2 to 60 carbon atoms, or a combination thereof. Saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. 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" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

Also, unless stated otherwise, 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 Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.

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

The organic layer may 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 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the 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 one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.

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

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and 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 or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

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

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

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

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

<Formula 1>

In Formula 1, L ¹ and L ² are each independently a single bond, an arylene group or a fluorenylene group of C ₆ to C ₆₀ . By way of example, L ¹ and L ² may be independently of each other phenyl, biphenyl, naphthyl and the like.

In Formula 1, R ³ and R ⁴ are independently of each other a C ₆ ~ C ₆₀ aryl group. For example, R ³ and R ⁴ can be phenyl, biphenyl, naphthyl, perylene and the like.

In addition, in Chemical Formula 1, R ¹ and R ² are independently selected from the following group. However, when L ¹ and L ² are a single bond, pyridine is excluded from R ¹ and R ² .

R in the group is deuterium; halogen; C ₁ ~ C ₅₀ Alkyl group; C ₆ ~ C ₆₀ Aryl group; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P, n is an integer of 0 to 4, and m is 0 to 6 Is an integer, and l is an integer of 0-5.

On the other hand, the arylene group, fluorenylene group, aryl group, heterocyclic group are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -LN (R _a ) (R _b ); C ₁ ~ C ₂₀ of the import alkylthio; C ₁ -C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; Of 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; It may be substituted with one or more substituents selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group.

Wherein L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ Heterocyclic group; It is selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.

Formula 1 may be represented by any one of the following Formulas 2-7.

<Formula 2> <Formula 3> <Formula 4>

<Formula 5> <Formula 6> <Formula 7>

In the above formula, L ¹ , L ² , R ³ , R ⁴ , R, n and m and the like may be defined as defined in formula (1).

Specifically, Formula 1 to Formula 7 may be one of the following compounds.

In another embodiment, the present invention provides a compound for an organic electric device represented by Chemical Formula 1.

In another embodiment, the present invention provides an organic electric device containing the compound represented by the formula (1).

In this case, the organic electric element includes a first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 may be included in the electron transport layer of the organic material layer. That is, the compound represented by Formula 1 may be used as the electron transport layer material. Specifically, to provide an organic electroluminescent device comprising one of the compounds represented by Formula 2 to Formula 7 in the organic material layer, more specifically, the present invention provides an organic electroluminescent device comprising a compound represented by the respective formula in the organic material layer To provide.

In another embodiment of the present invention, the present invention may include at least a light emitting auxiliary layer in the organic material layer.

In still another embodiment of the present invention, the present invention provides a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric element further comprising.

In still another embodiment of the present invention, the present invention provides a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric element further comprising.

In still another embodiment of the present invention, the present invention provides an organic electroluminescent device is formed by any one of the organic coating layer, spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process and roll-to-roll process do.

In another embodiment of the present invention, the present invention provides a display device including an organic electric element including the organic material layer; And a controller for driving the display device.

In another embodiment of the present invention, the organic electroluminescent device according to the present invention is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination It can be one.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

Synthesis Example

The compound represented by Chemical Formula 1 according to the present invention is prepared by reacting Sub 1 and Sub 2 as in Scheme 1 below, but is not limited thereto.

<Scheme 1>

The compound according to the present invention may be prepared by reacting Sub 1 and Sub 2 as in Scheme 1 below.

Synthesis Example of Sub 1

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

Sub 1-1 Synthesis

4,7-dibromo-1,10-phenanthroline (6.8 g, 20 mmol) was dissolved in DMF in a round bottom flask, Bis (pinacolato) diboron (5.6 g, 22 mmol), Pd (dppf) Cl ₂ (0.03 equiv) , KOAc (3 equiv) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by 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 purified by silicagel column and recrystallization to obtain 4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1, 7.4 g of 10-phenanthroline was obtained. (Yield 86%)

Sub 1-3 Synthesis

4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,10-phenanthroline (1 equivalent), Sub 1-2 (1 equivalent), Pd ( PPh ₃ ) ₄ (0.03 equiv) and K ₂ CO ₃ (3 equiv) were dissolved in anhydrous THF and a small amount of water and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the resulting product was concentrated by organic solvent was separated by silicagel column to obtain the desired Sub 1-3.

[Synthesis example of Sub 1-3-1]

4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,10-phenanthroline (8.4 g, 20 mmol) and 2- (4-bromophenyl) pyridine (4.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.03 equiv) and K ₂ CO ₃ (3 equiv) were dissolved in anhydrous THF and a small amount of water and then refluxed for 24 h. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by silicagel column to the desired 4- (4- (pyridin-2-yl) phenyl) -7- (4,4 7.3 g of, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,10-phenanthroline were obtained. (Yield 80%)

Sub 1-5 Synthesis

Sub 1-3 (1 equiv), Sub 1-4 (1 equiv), Pd (PPh ₃ ) ₄ (0.03 equiv) and K ₂ CO ₃ (3 equiv) are dissolved in anhydrous THF and a small amount of water, followed by 24 It was refluxed for hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by a silicagel column to obtain the desired Sub 1-5.

[Synthesis example of Sub 1-5-1]

4- (4- (pyridin-2-yl) phenyl) -7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,10-phenanthroline (9.2g, 20 mmol), 2- (4-bromophenyl) pyridine (4.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.03 equiv) and K ₂ CO ₃ (3 equiv) were dissolved in anhydrous THF and a small amount of water. Then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by silicagel column to the desired 4,7-bis (4- (pyridin-2-yl) phenyl) -1,10 7.6 g of -phenanthroline was obtained. (Yield 78%)

Sub 1 synthesis example

Dissolve 7-bis (4- (pyridin-2-yl) phenyl) -1,10-phenanthroline (1 equivalent) obtained in the above synthesis in THF, lower the temperature of the reaction to -78 ° C, and n-BuLi (2.5 M in hexane) (1.1 equiv) was slowly added dropwise and the reaction stirred for 30 min. Then the temperature of the reaction was lowered to -78 ° C and bromobenzene (1.5 equiv) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organics were purified by silicagel column and recrystallization with 2-phenyl-4,7-bis (4- (pyridin-2-yl) phenyl) -1,10-phenanthroline was obtained.

[(Synthesis example of Sub 1 (1))]

Dissolve 7-bis (4- (pyridin-2-yl) phenyl) -1,10-phenanthroline (9.7 g, 20 mmol) in THF, lower the temperature of the reaction to -78 ° C, n-BuLi (2.5 M in hexane) (1.1 equiv) was slowly added dropwise and the reaction stirred for 30 min. Then, the temperature of the reactant was lowered to -78 ° C and bromobenzene (4.7 g, 30 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organics were purified by silicagel column and recrystallization with 2-phenyl-4,7-bis (4- (pyridin-2-yl) 8.4g of phenyl) -1,10-phenanthroline were obtained. (Yield: 75%)

[(Synthesis example of Sub 1 (19)]]

Dissolve 4,7-di (isoquinolin-3-yl) -1,10-phenanthroline (8.7 g, 20 mmol) in THF, lower the temperature of the reaction to -78 ° C, n-BuLi (2.5 M in hexane) ( 1.1 eq) was slowly added dropwise and the reaction stirred for 30 min. Then the temperature of the reaction was lowered to -78 ° C. and 4-bromo-1,1'-biphenyl (7.0 g, 30 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resultant organics were purified by silicagel column and recrystallization with 2-([1,1'-biphenyl] -4-yl) -4, 9.2 g of 7-di (isoquinolin-3-yl) -1,10-phenanthroline was obtained. (Yield 78%)

Sub 1 is not limited to the following compounds, but may be the following compounds, the following compounds may be synthesized using the reaction mechanism used in the reaction. On the other hand, FD-MS values for the following compounds are shown in Table 1.

TABLE 1

Example of Sub 2

Examples of Sub 2 are as follows, but are not limited thereto, FD-MS for the following compounds are shown in Table 2.

TABLE 2

Synthesis of Product

Sub 1 (1 equiv) was dissolved in THF, the temperature of the reaction was lowered to −78 ° C., n-BuLi (2.5 M in hexane) (1.1 equiv) was slowly added dropwise, and the reaction stirred for 30 min. Then again the temperature of the reaction was lowered to -78 ° C and Sub 2 (1.2 equiv) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain a product.

Synthesis Example of 1-1

Dissolve 2-phenyl-4,7-bis (4- (pyridin-2-yl) phenyl) -1,10-phenanthroline (11.3 g, 20 mmol) in THF, lower the temperature of the reaction to -78 ° C, n-BuLi (2.5 M in hexane) (1.1 equiv) was slowly added dropwise and the reaction stirred for 30 min. Then the temperature of the reaction was lowered to -78 ° C. and bromobenzene (3.8 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 4.7 g of product. (Yield 64%)

Synthesis Example of 2-1

Dissolve 2-phenyl-4,7-di (quinolin-2-yl) -1,10-phenanthroline (10.2 g, 20 mmol) in THF, lower the temperature of the reaction to -78 ° C, n-BuLi (2.5 M in hexane) (1.1 equiv) was slowly added dropwise and the reaction stirred for 30 min. Then the temperature of the reaction was lowered to -78 ° C. and bromobenzene (3.8 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain Product 7.9g. (Yield 67%)

Synthesis Example of 3-18

Dissolve 4,7-bis (4- (isoquinolin-3-yl) phenyl) -2-phenyl-1,10-phenanthroline (13.2 g, 20 mmol) in THF, lower the temperature of the reaction to -78 ° C, n-BuLi (2.5 M in hexane) (1.1 equiv) was slowly added dropwise and the reaction stirred for 30 min. Then, the temperature of the reactant was lowered to -78 ° C and bromobenzene (3.8 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organics were purified by silicagel column and recrystallized to obtain 9.2 g of product. (Yield 62%)

Synthesis Example of 4-7

4- (isoquinolin-3-yl) -2- (naphthalen-2-yl) -7- (4- (pyridin-2-yl) phenyl) -1,10-phenanthroline (11.7 g, 20 mmol) in THF After dissolving, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 equiv) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ° C and 1-bromonaphthalene (5.0 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain Product 7.9g. (Yield 56%)

Synthesis Example of 5-11

2-([1,1'-biphenyl] -4-yl) -7- (4- (pyridin-2-yl) phenyl) -4- (quinolin-3-yl) -1,10-phenanthroline (12.3g , 20 mmol) was dissolved in THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 equiv) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ° C. and 2-bromonaphthalene (5.0 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 8.1 g of product. (Yield 55%)

6-16 Synthesis Example

Dissolve 4- (isoquinolin-3-yl) -2-phenyl-7- (quinolin-3-yl) -1,10-phenanthroline (10.2, 20 mmol) in THF, lower the temperature of the reaction to -78 ° C , n-BuLi (2.5M in hexane) (1.1 equiv) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ° C. and bromobenzene (3.8 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain Product 7.0g. (Yield 60%)

Synthesis Example of 7-4

2-phenyl-4- (pyrido [3,2-d] pyrimidin-2-yl) -7- (pyrido [4,3-d] pyrimidin-2-yl) -1,10-phenanthroline (10.3 g, 20 mmol) was dissolved in THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 equiv) was slowly added dropwise, and the reaction stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ° C. and bromobenzene (3.8 g, 24 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 6.6 g of product. (Yield 56%)

FD-MS for the compounds 1-1 to 7-8 prepared by the same method as in Table 3 below.

TABLE 3

Manufacturing Evaluation of Organic Electrical Device

Example 1 Green Organic Electroluminescent Device

First, 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) is vacuum deposited to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate. After forming the injection layer, 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. Formed. Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] is used as the host material on the hole transport layer, and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as the dopant material is 95: A light emitting layer having a thickness of 30 nm was deposited by doping at a weight ratio of 5 nm. Subsequently, (1,1 'bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm on the light emitting layer by hole blocking. A layer was formed, and the compound (1-1) of the present invention was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, which is a halogenated alkali metal, was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form an organic electroluminescent device.

[Example 2] to [Example 128]: green organic electroluminescent element

An organic electroluminescent device was manufactured according to the same method as Example 1 except for using the compounds 1-2 to 7-8 of the present invention shown in Table 4 instead of the compound 1-1 of the present invention as an electron transport layer material.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example I, except that Comparative Compound 1 was used instead of the compound according to the present invention as an electron transport layer material.

<Comparative Compound 1>

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example I, except that Comparative Compound 2 was used instead of the compound according to the present invention as an electron transport layer material.

Comparative Compound 2

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example I, except that Comparative Compound 3 was used instead of the compound according to the present invention as an electron transport layer material.

Comparative Compound 3

[Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example I, except that Comparative Compound 4 was used instead of the compound according to the present invention as an electron transport layer material.

Comparative Compound 4

Characteristics of electroluminescence (EL) by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared according to Examples 1 to 128 and Comparative Examples 1 to 4 of the present invention The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 5000 cd / m ² reference luminance. The measurement results are shown in Table 4 below.

TABLE 4

As can be seen from the results of Table 4, the organic electroluminescent device (OLED) using the compounds of the present invention is used as an electron transport layer material, the driving voltage and high efficiency and high lifespan than the comparative compound 1 of Alq ₃ widely used conventionally Indicated. This is the case of the compounds of the hand, indicate the dopant T ₁ value (2.0 eV) of the Alq ₃ is significantly lower T ₁ values using as an electron transporting layer than the Ir (ppy) ₃ of the T ₁ value (2.4 eV) used in the light emitting layer invention, It exhibits a T ₁ value (2.5 ev to 2.6 ev) that is generally higher than the T ₁ value of Ir (ppy) ₃ (2.4 eV), thereby improving hole blocking ability as well as excitons in the light emitting layer. This is because the relative probability of staying well increases.

In addition, comparing the results of the organic electroluminescent devices of the compounds of Comparative Compounds 2, 3, and 4 with the compounds of the present invention, the use of the compounds of the present invention resulted in a significant improvement in relatively low driving voltage, efficiency and lifetime. It was confirmed that it was shown. The characteristics vary depending on the position and type of the substituents of the core, and the compound of the present invention has better device characteristics than that of Comparative Compound 2, Comparative Compound 3 and Comparative Compound 4. It can be explained that the charge balance of the electron is well achieved to improve the performance of the device.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics were described in terms of the light emitting layer (phosphorescent host). As an organic material layer of the organic electric element, such as a light emitting auxiliary layer, it can be used in a single or mixed with other materials. Therefore, the above-described compounds of the present invention may be used in combination with a single or other material in addition to the light emitting layer (phosphorescent host), for example, an organic material layer, for example, an electron transport layer, an electron injection layer, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and the like. .

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority under No. 119 (a) (35 USC § 119 (a)) of the Patent Application No. 10-2013-0128911, filed in Korea on October 29, 2013. All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (10)

1. A compound represented by the following formula (1).

   <Formula 1>

   

   [In Formula 1, L ¹ and L ² are independently of each other, a single bond, a C ₆ ~ C ₆₀ arylene group or a fluorenylene group, R ³ and R ⁴ are independently of each other C ₆ ~ C ₆₀ aryl Gigi,

   R ¹ and R ² are independently selected from the following groups,

   

   

   (Except pyridine in R ¹ and R ² when L ¹ and L ² are a single bond, in which R is deuterium; halogen; C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P, n is an integer of 0 to 4, and m is 0 to 6 Is an integer between and l is an integer from 0 to 5)

   The arylene group, the fluorenylene group, the aryl group, and the heterocyclic group are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -LN (R _a ) (R _b ); C ₁ ~ C ₂₀ of the import alkylthio; C ₁ -C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; Of 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; It may be substituted with one or more substituents selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group,

   L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ Heterocyclic group; It is selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ ~ C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.]
2. The method of claim 1,

   Compound represented by any one of the following formulas (2) to (7).

   <Formula 2> <Formula 3> <Formula 4>

   

   <Formula 5> <Formula 6> <Formula 7>

   

   (In the above formula, L ¹ , L ² , R ³ , R ⁴ , R, n and m are the same as defined in claim 1)
3. The method of claim 1,

   Compound which is one of the following compounds.

   

   

   

   

   

   
4. A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode.

   An organic electric device, characterized in that the compound according to claim 1 or 2 is contained in the organic material layer.
5. The method of claim 4, wherein

   The compound is an organic electric device, characterized in that contained in the electron transport layer of the organic material layer.
6. The method of claim 4, wherein

   The organic material layer further comprises an emission layer, and an emission auxiliary layer formed between the emission layer and the first electrode or the emission layer and the second electrode.
7. The method of claim 4, wherein

   And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
8. The method of claim 4, wherein

   The organic material layer is formed 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.
9. Claim 4 display device comprising the organic electroluminescent element; And

   And a controller for driving the display device.
10. The method of claim 10,

    The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.

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