WO2016167507A1 - Compound for organic electronic element, organic electronic element using same, and electronic apparatus - Google Patents

Abstract

The purpose of the present invention is to provide: a compound for high light emission efficiency, a low driving voltage, and an improved lifespan, of an element; an organic electronic element using the same; and an electronic apparatus.

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. The organic layer is often made of a multi-layer 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 element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

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

Currently, the portable display market is increasing in size with large-area displays, which requires more power consumption than that required in conventional portable displays. Therefore, power consumption has become a very important factor for a portable display having a limited power supply such as a battery, and the problem of efficiency and lifespan must also be solved.

Efficiency, lifespan, and driving voltage are related to each other, and as the efficiency increases, the driving voltage decreases relatively, and the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. The lifespan tends to increase. However, simply improving the organic material layer does not maximize the efficiency. This is because long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

That is, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting 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, a light emitting auxiliary material, Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials is continuously required, and in particular, the development of the host material of the light emitting layer is urgently required.

An object of the present invention is to provide a compound capable of improving high luminous efficiency, low driving voltage and lifetime of an element, an organic electric element using the same, and an electronic device thereof.

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.

By using the compound according to the present invention, high luminous efficiency and low driving voltage of the device can be achieved, and the life of the device can be greatly 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, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, fluorene group, spirofluorene group, spirobifluorene 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 stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or 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 It may be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

Therefore, in the present invention, the light emitting layer is formed using the compound represented by Chemical Formula 1 to optimize the energy level and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the organic layer, and thus the life of the organic electric device. And efficiency can be improved at the same time.

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.

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

<Formula 1>

In Chemical Formula 1,

R ¹ to R ⁹ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); may be selected from the group consisting of.

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; may be selected from the group consisting of, wherein 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.

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 a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.

Ar ¹ is a C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And -L'-N (R _a ) (R _b ); may be selected from the group consisting of.

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; may be selected from the group consisting of, wherein 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.

For example, when R ¹ to R ⁹ , L, Ar ¹ , L ', R _a and R _b are an aryl group or an arylene group, R ¹ to R ⁹ , L, Ar ¹ , L', R _a and R _b are Independently of each other may be a phenyl group, a biphenyl group or a phenylene group, a biphenylene group and the like.

n is an integer of 0-4.

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group each of deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; 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 ; C ₆ -C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L "-N (R _c ) (R _d ), where L", R _c and R _d are the same as defined above for L ', R _a and R _b , carbonyl group, ether group, C ₂ -C An alkoxylcarbonyl group of ₂₀ , an aryloxy group of C ₆ -C ₃₀ , -O-Si (R ^y ) ₃ , and R ^y O-Si (R ^y ) _2- (where R ^y is hydrogen, C ₆ -C ₂₀ An aryl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₈ to C ₂₀ aryl alkenyl group, a C ₇ to C ₂₀ aryl alkoxyl group, or a C ₂ to C ₂₀ alkoxyl group Carbonyl group) may be further substituted with one or more substituents selected from the group consisting of:

Here, in the case of the aryl group, the carbon number may be 6 to 60, preferably 6 to 40 carbon atoms, more preferably an aryl group having 6 to 30 carbon atoms,

When the heterocyclic group has 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably a hetero ring having 2 to 20 carbon atoms,

In the case of the arylene group, the carbon number may be 6 to 60, preferably 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms,

In the case of the alkyl group, the carbon number may be 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms.

Specifically, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formulas 2 to 4.

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

In Chemical Formulas 2 to 4,

R ¹ to R ⁹ , L and Ar ¹ are the same as R ¹ to R ⁹ , L and Ar ¹ defined in Chemical Formula 1.

More specifically, the compound represented by Formula 1 to Formula 4 may be any 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 disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and the compound represented by Chemical Formula 1 may be a hole injection layer or a hole transport layer of the organic material layer. The light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may be contained in at least one layer. In particular, the compound represented by Formula 1 may be included in the emission layer.

That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer or an electron injection layer. In particular, the compound represented by Formula 1 may be used as a material of the light emitting layer. Specifically, to provide an organic electroluminescent device comprising one of the compounds represented by Formula 2 to Formula 4 in the organic material layer, more specifically, It provides an organic electroluminescent device comprising a compound represented by the individual formulas (1-1 to 1-40, 2-1 to 2-40) in the organic material layer.

In another embodiment, the compound is contained alone or in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer, Provided is an organic electroluminescent device characterized in that a compound is contained in a combination of two or more different from each other, or the compound is contained in a combination of two or more. In other words, each of the layers may include a compound corresponding to Formula 1 to Formula 4 alone, may include a mixture of two or more compounds of Formula 1 to Formula 4, the compound of claims 1 to 3, Mixtures with compounds that do not correspond to the invention may be included. Herein, the compound not corresponding to the present invention may be a single compound or two or more compounds. In this case, when the compound is contained in a combination of two or more kinds of other compounds, the other compound may be a known compound of each organic material layer, or a compound to be developed in the future. In this case, the compound contained in the organic material layer may be made only of the same kind of compound, but may be a mixture of two or more kinds of the compound represented by the formula (1).

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.

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 ]

Compound represented by Formula 1 according to the present invention (Product) is prepared by reacting Sub 1 with Sub 2, as shown in Scheme 1.

<Scheme 1>

I. Synthesis Example of Sub 1

Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.

<Scheme 2>

1. Synthesis Example of Sub 1 (1)

<Scheme 3>

Sub 1-3 Synthesis

Sub1-1 (89 g, 500 mmol), sub1-2 (70 g, 750 mmol), Cu (OAc) 2 (40 g, 200 mmol), 10 mol% PdCl ₂ (9 g, 5) mmol), DMF (700 mL) was added to the mixture, and the reaction was performed at 100 ° C. for 12 hours. After the reaction was completed, the mixture was extracted using diethyl ether, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was subjected to silicagel column (methylene chloride: hexane = 1: 5) to give 2- (4-bromophenyl) -3-phenyl-1H-indole (Sub1-3). (78 g, 58%)

Sub 1-5 synthesis

Sub1-3 (300 mmol), sub1-4 (550 mmol), Pd (OAc) ₂ (30 mmol), PPh ₃ (60 mmol), tBuONa (360 mmol) and p-xylene (700 mL) were added and dissolved, and the reaction was performed at 130 ° C. for 24 hours. When the reaction is complete, cooled to room _{temperature, Pd (OAc) 2 (15} mmol), PCy 3 · HBF 4 (30 mmol), DBU (600 mmol), into an additional DMA (700 mL) at 145 ℃ dissolved The reaction proceeds for 12 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, 500 mL of ethyl acetate was added and the mixture was heated and dissolved at 50 ° C. Extract with ethyl acetate, water and brine and dry the organic layer with MgSO ₄ . The obtained organic layer was subjected to silica gel column (ethyl acetate: hexane = 1: 10) to 8-Bromo-5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinoline (Sub1-5) Got.

Sub 1 (1) Synthesis

8-Bromo-5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinoline (Sub1-5) (100 mmol) was dissolved in THF (600 mL) in a round bottom flask. After this time the temperature is lowered to -78 ° C and n-BuLi (150 mmol) is slowly dropped. Triisopropylborate (200 mmol) was added thereto, and the reaction was performed at room temperature for 24 hours. After the reaction was completed, an aqueous solution of HCl was added, and the resulting solid was filtered to form (5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinolin-8-yl) boronic acid ( Sub1 (1)) was obtained.

2. Synthesis Example of Sub 1 (2)

<Scheme 4>

Sub 1-8 synthesis

Sub1-7 (89 g, 500 mmol), sub1-2 (70 g, 750 mmol), Cu (OAc) ₂ (40 g, 200 mmol), 10 mol% PdCl ₂ (9 g, 5) mmol), DMF (700 mL) was added to the mixture, and the reaction was performed at 100 ° C. for 12 hours. After the reaction was completed, the mixture was extracted using diethyl ether, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was subjected to silicagel column (methylene chloride: hexane = 1: 5) to obtain 2- (3-bromophenyl) -3-phenyl-1H-indole (Sub1-8). (67 g, 50%)

Sub 1-9 Synthesis

Sub1-8 (300 mmol), sub1-4 (550 mmol), Pd (OAc) _{2 in a} 2L round bottom flask (30 mmol), PPh ₃ (60 mmol), tBuONa (360 mmol) and p-xylene (700 mL) were added and dissolved, and the reaction was performed at 130 ° C. for 24 hours. When the reaction is complete, cooled to room _{temperature, Pd (OAc) 2 (15} mmol), PCy 3 · HBF 4 (30 mmol), DBU (600 mmol), into an additional DMA (700 mL) at 145 ℃ dissolved The reaction proceeds for 12 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, 500 mL of ethyl acetate was added and the mixture was heated and dissolved at 50 ° C. Extract with ethyl acetate, water and brine and dry the organic layer with MgSO ₄ . The obtained organic layer was subjected to silicagel column (ethyl acetate: hexane = 1: 10) to obtain 7-Bromo-5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinoline (Sub1-9) Got.

Sub 1 (2) Synthesis

7-Bromo-5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinoline (Sub1-9) (100 mmol) was dissolved in THF (600 mL) in a round bottom flask. After this time the temperature is lowered to -78 ° C and n-BuLi (150 mmol) is slowly dropped. Triisopropylborate (200 mmol) was added thereto, and the reaction was performed at room temperature for 24 hours. When the reaction is completed, an aqueous solution of HCl is added, and the resulting solid is filtered to form (5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinolin-7-yl) boronic acid ( Sub1 (2)) was obtained.

An example of Sub 1 is as follows, but is not limited thereto.

TABLE 1

Π. Example of Sub 2

Examples of Ar ₁ -LX (X = Br, Cl, F) of Sub 2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

TABLE 2

III. Final Product of  synthesis

Sub 1 compound (1 equiv), Sub 2 compound (1.1 equiv), Pd (PPh ₃ ) ₄ (0.03 ~ 0.05 equiv), K ₂ CO ₃ (3 equiv), THF (3 mL / 1 mmol) , Dissolve in water (1.5 mL / 1 mmol) and heat to reflux at 80 ℃ ~ 90 ℃. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product.

1.1 Synthesis Example 1-8

Scheme 5

(5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinolin-8-yl) boronic acid (8.87 g, 20 mmol) and 2-chloro-4 in a round bottom flask , 6-diphenyl-1,3,5-triazine (5.89 g, 22 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), K ₂ CO ₃ (8.29 g, 60 mmol), THF (200 mL ), Add water (100 mL) to dissolve and heat to reflux at 80 ℃ ~ 90 ℃. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was dissolved in 1,2-dichlorobenzne, and silicagel filtered. The filtrate was concentrated and recrystallized to obtain product 1-8. (9.46 g, 75%)

2. Synthesis Example of 1-13

<Scheme 6>

(5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinolin-8-yl) boronic acid (8.87 g, 20 mmol) and 2-chloro-4 in a round bottom flask -phenylbenzo [h] quinazoline (6.4 g, 22 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), K ₂ CO ₃ (8.29 g, 60 mmol), THF (200 mL), water (100 mL ) And melt and heat it to reflux at 80 ℃ ~ 90 ℃. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was dissolved in 1,2-dichlorobenzne and silicagel filtered. The filtrate was concentrated and recrystallized to obtain product 1-13. (10.5 g, 80%)

3. Synthesis Example of 1-35

Scheme 7

(5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinolin-8-yl) boronic acid (4.43 g, 10 mmol), 2- (3- bromophenyl) -4,6-diphenylpyrimidine (4.3 g, 11 mmol), Pd (PPh ₃ ) ₄ (0.35 g, 0.3 mmol), K ₂ CO ₃ (4.15 g, 30 mmol), THF (200 mL), water ( 100 mL) is dissolved and heated to reflux at 80 ℃ ~ 90 ℃. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was dissolved in Toluene, silicagel filtered, and the filtrate was concentrated and recrystallized to obtain a product 1-35. (5.8 g, 82%)

4. Synthesis Example of 2-4

Scheme 8

(5-phenylbenzo [4,5] thieno [2,3-c] indolo [2,1-a] isoquinolin-7-yl) boronic acid (4.43 g, 10 mmol), 2- (4- bromophenyl) pyridine (2.6 g, 11 mmol), Pd (PPh ₃ ) ₄ (0.35 g, 0.3 mmol), K ₂ CO ₃ (4.15 g, 30 mmol), THF (200 mL), water (100 mL) After melting, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was dissolved in Toluene, and silicagel filtered. The filtrate was concentrated and recrystallized to obtain a product 2-4. (4.37 g, 79%)

TABLE 3

On the other hand, in the above described an exemplary synthesis example of the present invention represented by the formula (1), these are all Buchwald-Hartwig cross coupling reaction, PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70, 5014.) , Miyaura boration reaction and Suzuki cross-coupling reaction and the like, in addition to the substituents specified in the specific synthesis examples, the reaction proceeds even if other substituents (R ¹ to R ⁹ , Ar ¹ , L and other substituents) defined in Formula 1 are combined. Those skilled in the art will readily understand.

Manufacturing Evaluation of Organic Electrical Device

[ Example  One] Red organic light emitting diode  Production and test (phosphorescent host)

An organic light emitting diode was manufactured according to a conventional method using a compound obtained through synthesis as a light emitting host material of a light emitting layer. First, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ¹ on the ITO layer (anode) formed on the glass substrate. -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a hole injection layer having a thickness of 60 nm, and then 4,4-bis [N- (1) as a hole transport compound on the hole injection layer. -Naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Compound 1-1 of the present invention was used as a host on the hole transport layer, and a dopant material was doped with (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] at a 95: 5 weight ratio. A light emitting layer was deposited to a thickness of 30 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 with a holding layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a transport layer to a thickness of 40 nm. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting diode.

[ Example  2] to [ Example  80] Red organic light emitting element Phosphorescent Host

The above examples were used as phosphorescent host material of the light emitting layer instead of compound 1-1 of the present invention, but one of compounds 1-2 to 1-40 and 2-1 to 2-40 of the present invention shown in Table 4 below. An organic electroluminescent device was manufactured in the same manner as in 1.

[ Comparative example  One]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A was used instead of Compound 1-1 of the present invention as a phosphorescent host material of the emission layer.

Comparative Compound A

[ Comparative example  2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound B was used instead of Compound 1-1 of the present invention as a phosphorescent host material of the emission layer.

Comparative Compound B

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement results were obtained at a luminance of 2500 cd / m2. The T95 life was measured using a life measurement instrument manufactured by McScience. Table 4 shows the results of device fabrication and evaluation.

TABLE 4

As can be seen from the results of Table 4, the organic electroluminescent device using the organic electroluminescent device material of the present invention as a phosphorescent host can significantly improve efficiency, driving voltage and lifetime.

In other words, the invention compound having a six-membered heterocycle in which S and N are substituted as the comparative compound A, which is generally used as a host material, and the comparative compound B, which is Bebq ₂ , showed the best device results.

This is because the comparative compounds A and B have only excellent stability to electrons, while the invention compound whose heterocyclic ring is substituted with S and N has excellent stability to holes as well as electrons, thus reducing deterioration in the device. It is presumed to increase the stability and to play a more suitable role as a red host while having an appropriate T1 value, resulting in the best device results.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics were described in terms of the light emitting layer. However, materials used as the light emitting layer typically include organic electron devices such as the above-described electron transport layer, electron injection layer, hole injection layer, hole transport layer, and light emitting auxiliary layer. It can be used in combination with a single or other material as an organic layer of. Therefore, the compounds of the present invention can be used in combination with a single or other materials in addition to the light emitting layer, for example, an organic material layer, for example, an electron transport layer, an electron injection layer, a hole injection layer, a hole transport layer and a light emitting auxiliary layer.

The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications can be made without departing from the essential features 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 scope of protection of the present invention should be interpreted by the following claims, and all descriptions within the equivalent scope should be construed 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 US Patent Act No. 10-2015-0052576, filed April 14, 2015 with Korea. All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason as for the above-mentioned countries, all the contents are incorporated into this patent application by reference.

Claims (9)

A compound represented by the following formula (1). <Formula 1>

In Chemical Formula 1, R ¹ to R ⁹ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); 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 a C ₂ ~ C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and Ar ¹ is a C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And -L'-N (R _a ) (R _b ); 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, and n is an integer from 0 to 4, The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group each of deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; 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 ; C ₆ -C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L "-N (R _c ) (R _d ), where L", R _c and R _d are the same as defined above for L ', R _a and R _b , carbonyl group, ether group, C ₂ -C An alkoxylcarbonyl group of ₂₀ , an aryloxy group of C ₆ -C ₃₀ , -O-Si (R ^y ) ₃ , and R ^y O-Si (R ^y ) _2- (where R ^y is hydrogen, C ₆ -C ₂₀ An aryl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₈ to C ₂₀ aryl alkenyl group, a C ₇ to C ₂₀ aryl alkoxyl group, or a C ₂ to C ₂₀ alkoxyl group Carbonyl group) may be further substituted with one or more substituents selected from the group consisting of: The method of claim 1, The compound represented by Formula 1 is represented by the following formula.        <Formula 2> <Formula 3> <Formula 4>

(In Formulas 2 to 4, wherein R ¹ to R ⁹ , L and Ar ¹ are the same as defined in claim ¹ ) The method of claim 1, Compound which is one of the following compounds.

A first electrode; Second electrode; And And an organic material layer disposed between the first electrode and the second electrode and containing the compound of any one of claims 1 to 3. The method of claim 4, wherein The organic material layer comprises an emission layer, the organic electroluminescent device, characterized in that the compound is contained alone or in a mixture in the emission layer. The method of claim 4, wherein And an optical efficiency improving layer formed on at least one surface of the first and second electrodes opposite to the organic material layer. 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. Claim 4 display device comprising the organic electroluminescent element; And And a controller for driving the display device. The method of claim 8, The organic electronic device is an electronic device, characterized in that one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a device for monochrome or white illumination.

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