KR102309763B1 - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides a compound represented by the formula (1). In addition, there is provided an organic electric device including a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, wherein the organic material layer includes a compound represented by Chemical Formula 1. When the compound represented by Formula 1 is included in the organic material layer of the organic electric device, the driving voltage may be reduced, and luminous efficiency, color purity, lifespan, and the like may be improved.

Description

Compound for organic electric device, organic electric device 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, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

In addition, the light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. can In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

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

Currently, the portable display market is a large-area display, and its size is increasing, and thus, a higher power consumption than the power consumption required by the existing portable display is required. Therefore, power consumption has become a very important factor for a portable display having a limited power supply such as a battery, and efficiency and lifespan problems must also be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan. However, the efficiency cannot be maximized simply by improving the organic material layer. This is because, when the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time. Therefore, there is a need to develop a light emitting material that has high thermal stability and can efficiently achieve charge balance in the light emitting layer.

That is, in order to sufficiently exhibit the excellent characteristics of an organic electric device, materials constituting the organic 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 layer material, etc. are stable and efficient. It should be supported by materials, but the development of stable and efficient organic layer materials for organic electric devices has not yet been sufficiently made. 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 novel compound, and to provide an organic electric device and an electronic device capable of improving luminous efficiency, lifespan, color purity, heat resistance, etc. and lowering a driving voltage by using the novel compound.

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

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

By using the compound according to an embodiment of the present invention, it is possible to achieve high luminous efficiency, low driving voltage, and high heat resistance of the device, and improve color purity and lifespan of the device.

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

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

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

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

Also, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” the other component, but also when there is another component in between. It should be understood that cases may be included. Conversely, it should be understood that when an element is said to be "on top of" another part, it means that there is no other part in the middle.

As used in this specification and the appended claims, unless otherwise indicated, the following terms have the following meanings.

As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond having 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term “haloalkyl group” or “halogenalkyl group” refers to an alkyl group substituted with halogen unless otherwise specified.

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

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

As used herein, the term “alkoxy group” or “alkyloxy group” refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

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

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R' and R" are all hydrogen in the following structures, respectively, unless otherwise specified, " A substituted fluorenyl group" or "substituted fluorenylene group" means that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a It includes the case of forming a compound as a spy together.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, the aryl group or the arylene group includes a monocyclic type, a ring conjugate, a fused multiple ring system, a spiro compound, and the like.

The term "heterocyclic group" used in the present invention includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, the number of carbon atoms each containing one or more heteroatoms It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used herein, unless otherwise specified, represents N, O, S, P or Si, and the heterocyclic group is a monocyclic group containing a heteroatom, a ring conjugate, a fused multiple ring system, a spy means a compound or the like.

In addition, the "heterocyclic group" may include a ring including _{SO 2 instead of carbon forming the ring.} For example, "heterocyclic group" includes the following compounds.

In the present specification, when naming a monovalent or divalent functional group of a parent, in some cases, it may be indicated by simply adding monovalent or divalent in front of the parent compound.

As used herein, the term "ring" includes monocyclic and polycyclic rings, and includes hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, etc., fused multiple ring systems and spiro compounds, and includes aromatic as well as non-aromatic, hydrocarbon Rings include, of course, heterocycles containing at least one heteroatom.

As used herein, the term "ring assemblies" refers to two or more ring systems (single or fused ring systems) directly connected to each other through a single bond or a double bond, and a direct connection between such rings It means that the number of linkages is one less than the total number of ring systems in this compound. In a ring aggregate, the same or different ring systems may be directly connected to each other through single or double bonds.

As used herein, the term "fused multiple ring system" refers to a fused ring type sharing at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. and a form in which at least one heterocyclic system is fused. These fused multiple ring systems may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and the spiro linkage means a connection formed by sharing only one atom in two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and they are respectively 'monospiro-', 'dispiro-', 'trispiro-', depending on the number of spiro atoms in a compound. ' It's called a compound.

Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, where The arylcarbonyl group is a carbonyl group substituted with an aryl group.

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" as used herein, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ Alkoxy group, C ₁ -C ₂₀ Alkylamine group, C ₁ -C ₂₀ Alkylthiophene group, C ₆ -C ₂₀ Arylthiophene group, C ₂ -C ₂₀ Alkenyl group, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron _{group, germanium group, and C 2} -C ₂₀ including at least one heteroatom selected from the group consisting of O, N, S, Si and P means substituted with one or more substituents selected from the group consisting of a heterocyclic group and is not limited to these substituents.

In addition, unless there is an explicit explanation, the formula used in the present invention is the same as the definition of the substituent by the exponential definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the 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 , an organic electric device 100 according to the present invention includes a first electrode 120 , a second electrode 180 , and a first electrode 110 and a second electrode 180 formed on a substrate 110 . ), an organic layer containing the compound according to the present invention is provided. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . At this time, at least one of these layers may be omitted, or a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, etc. may be further included, and the electron transport layer 160 and the like serve as a hole blocking layer. you might be able to

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 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 is a hole injection layer 130 , a hole transport layer 140 , an electron transport layer 160 , an electron injection layer 170 , a light emitting layer 150 , a light efficiency improving layer, a light emitting auxiliary layer, etc. may be used as a material for, and preferably, the compound of the present invention may be used as a host material of the light emitting layer 150 .

On the other hand, even with the same core, the band gap, electrical properties, interface properties, etc. may vary depending on which position the substituent is bonded to, so the selection of the core and the combination of the sub-substituents bonded thereto are very important, especially When the energy level between each organic material layer, the T ₁ value, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form the anode 120, and the hole injection layer 130 thereon. , after forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160, and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon. have. In addition, a light emitting auxiliary layer 151 may be additionally formed between the hole transport layer 140 and the light emitting layer 150 .

In addition, the organic layer is a solution process or a solvent process using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, a doctor blading process, It can be manufactured with a smaller number of layers by a method such as a screen printing process or a thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

The organic electric device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

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

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

Another embodiment of the present invention may include a display device including the organic electric device 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/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 control, a navigation system, a game machine, various TVs, and various computers.

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

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

<Formula 1>

In Formula 1, each symbol is defined as follows.

Y ¹ and Y ² are each independently N(Ar ² ), m and n are each an integer of 0 or 1, provided that at least one of m and n is 1. if m is "0" is Y ² is present is the carbon bonded to both Y ² without the mediation of Y ² do not bond directly. Similarly, when n is “0”, Y ¹ does not exist, so both carbons are directly bonded. Preferably, at least one of m and n may be 0 and the other may be 1.

Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; _{C 2} -C ₆₀ A heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} and -L′-N(R ^a )(R ^b ); may be selected from the group consisting of.

Preferably, Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; Or O, N, S, Si and P containing at least one heteroatom C ₂ -C ₆₀ A heterocyclic group; may be.

Specifically, Ar ¹ and Ar ² are each independently a phenyl group unsubstituted or substituted with a naphthyl group, a pyrimidinyl group, a triazinyl group, or a benzo[ d]thiazole; biphenyl group; a naphthyl group unsubstituted or substituted with phenyl; phenyl-substituted or unsubstituted trizinyl group; a phenyl-substituted or unsubstituted pimiridinyl group; monovalent benzo[d ]thiazole unsubstituted or substituted with a phenyl group or a pyridyl group; monovalent benzo[d ]imidazole substituted or unsubstituted with a phenyl group; etc. can be

Z ¹ to Z ⁸ are each independently C(Ar ³ ) or N. Here, Ar ³ is hydrogen, a C ₆ -C ₆₀ aryl group; fluorenyl group; _{C 2} -C ₆₀ A heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} And _{-L'-N (R a) (} R b); is selected from the group consisting of, can be selectively coupled to each other in the neighborhood between the Ar ³ to form a ring.

Meanwhile, when Ar ¹ to Ar ³ are -L′-N(R _a )(R _b ), L′ is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} and a C ₂ -C ₆₀ heterocyclic group; selected from the group consisting of, wherein R ^a and R ^b are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring; and a C 2} -C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; may be selected from the group consisting of.

When each of the above symbols is an aryl group, a fluorenyl group, a fused ring group, a hetero group, an arylene group or a fluorenylene group, each of these is deuterium, a halogen, a silane group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group group, an alkylthio import of _{C 1 -C 20, C 1 -C} 20 alkynyl group, the alkoxy group, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ of a C ₆ - C ₂₀ Aryl group, C ₆ -C _{20 Aryl group substituted with deuterium, fluorenyl group, C 2} -C ₂₀ containing at least one heteroatom selected from the group consisting of O, N, S, Si and P of a heterocyclic group, a C ₃ -C ₂₀ cycloalkyl group, a C ₇ -C ₂₀ arylalkyl group, a C ₈ -C ₂₀ arylalkenyl group, an arylamine group and a heteroarylamine group with one or more substituents selected from the group consisting of may be substituted.

Preferably, Chemical Formula 1 may be represented by Chemical Formula 2 or Chemical Formula 3 below.

<Formula 2> <Formula 3>

In Formula 2 or Formula 3, Y ¹ , Y ² , Z ¹ to Z ⁸ and Ar ¹ are as defined in Formula 1.

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

In another embodiment, the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer formed with the first electrode and the second electrode, wherein the organic material layer includes a hole injection layer, a hole transport layer, and a light emitting auxiliary layer. and at least one of the light-emitting layers, wherein the compound is included in at least one of these organic layers, preferably in the light-emitting layer.

The compound included in the organic material layer may be one single compound or a mixture of two or more represented by Chemical Formulas 1 to 6. In addition, the organic material layer may include at least one compound among Compound 1-1 to Compound 1-100.

In addition, a light efficiency improving layer may be further formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer, and the organic material layer is a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip It may be formed by a coating process or a roll-to-roll process.

In another embodiment, the present invention includes a display device including an organic electric element containing the compound, and a control unit for driving the display apparatus, wherein the organic electric element is an organic electroluminescent element, an organic solar cell, It may be at least one of an organophotoreceptor, an organic transistor, and a device for monochromatic or white illumination.

Hereinafter, the synthesis example of the compound represented by Formula 1 used in the organic material layer of the present invention and the preparation example of the organic electric device will be described in detail with reference to Examples, but the scope of the present invention is limited to the following examples it is not

Synthesis example

The compound (Product) represented by Formula 1 according to the present invention may be prepared by reacting Core 1 or Core 2 with Sub 1 as shown in Scheme 1 below. Scheme 1 below is only an example of a reaction scheme in which the compound of the present invention is produced, and the scope of the present invention is not limited thereby. In the following formula, each symbol is as defined in formula (1), and X is a halogen compound.

<Scheme 1>

Synthesis example of Core 1

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

<Scheme 2>

Synthesis example of Core 1(1)

(1) Synthesis of compound 1-2

Compound 1-1 (100 g, 380.01 mmol), 2-chloroaniline (48.47 g, 380.01 mmol), Pd(oAc) ₂ (2.55 g, 11.40 mmol), P(t-Bu) ₃ (4.61 g) in a round-bottom flask , 22.80 mol), NaOt-Bu (109.59 g, 1140.30 mmol) and Toluene (1200 mL) were added and stirred at 75° C. for 8 hours. After extraction with methylene chloride and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain compound 1-2 (76.52 g). (Yield: 65%)

(2) Synthesis of compound 1-3

Compound 1-2 (70 g, 225.59 mmol), Pd(oAc) ₂ (1.52 g, 6.77 mmol), Tri-ter-butylphosphonium tetrafluoro borate (6.55 g, 22.55 mmol) , K ₂ CO ₃ (88.26 g) in a round-bottom flask , 677.85 mmol) and DMA (750 mL) were added and refluxed for 12 hours. After extraction with methylene chloride and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain compound 1-3 (30.88 g). (Yield: 50%)

(3) Synthesis of compound 1-4

Compound 1-3 (30 g, 109.74 mmol), iodobenzene (55.97 g, 274.37 mmol), Pd ₂ (dba) ₃ (3.01 g, 3.29 mmol), P(t-Bu) ₃ (1.33 g, 6.58 mmol), NaOt-Bu (31.64 g, 329.22 mmol) and Toluene (360 mL) were added, and the reaction was carried out at 100 °C. 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} and concentrated, and the obtained organic material was recrystallized using silicagel column to obtain compound 1-4 (26.84 g). (Yield: 70%)

(5) Synthesis of compound 1-5

In a round-bottom flask, compound 1-4 (25 g, 74.54 mmol) _{was dissolved in CH 2} Cl ₂ , and Br ₂ (11.37 g, 74.54 mmol) was slowly added dropwise, and the reaction mixture was stirred for 10 hours. After completion of the reaction, Br ₂ is removed with an aqueous sodium thiosulfate solution. After extraction with ethyl acetate and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain Compound 1-5 (16.85 g). (Yield: 55%)

(6) Synthesis of compound 1-6

Compound 1-5 (15 g, 35.01 mmol), 2-nitrophenyl boronic acid (7.01 g, 42.02 mmol), Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (14.51 g) in a round-bottom flask , 105.03 mmol), THF (120 mL) and H ₂ O (50 mL) were added, and the reaction mixture was refluxed for 10 hours. 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} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain Compound 1-6 (10.75 g). (Yield: 65%)

(7) Core 1(1) synthesis

Compound 1-6 (10 g, 22.80 mmol), PPh ₃ (17.94 g, 68.40 mmol), and O-DCB (75 mL) were refluxed in a round bottom flask for 12 hours. After completion of the reaction, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized using silicagel column to obtain Core 1 (1) (6.03 g). (Yield: 65%)

Synthesis example of Core 1(2)

(1) Synthesis of compound 1-7

Compound 1-1 (100 g, 380.01 mmol), 2-chloropyridin-3-amine (48.85 g, 380.01 mmol), Pd(oAc) ₂ (2.55 g, 11.40 mmol), P(t-Bu) in a round-bottom flask ₃ (4.61 g, 22.80 mmol), NaOt-Bu (109.59 g, 1140.30 mmol) and Toluene (1200 mL) were added and stirred at 75° C. for 8 hours. After extraction with methylene chloride and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain compound 1-7 (57.15 g). (Yield: 50%)

(2) Synthesis of compound l-8

Compound 1-7 (70 g, 225.59 mmol), Pd(oAc) ₂ (1.52 g, 6.77 mmol), Tri-ter-butylphosphonium tetrafluoro borate (6.55 g, 22.55 mmol) , K ₂ CO ₃ (88.26 g) in a round-bottom flask , 677.85 mmol) and DMA (750 mL) were added and refluxed for 12 hours. After extraction with methylene chloride and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain compound 1-8 (24.71 g). (Yield: 40%)

(3) Synthesis of compound 1-9

Compound 1-8 (30 g, 109.74 mmol), iodobenzene (55.97 g, 274.37 mmol), Pd ₂ (dba) ₃ (3.01 g, 3.29 mmol), P(t-Bu) ₃ (1.33 g, 6.58 mmol), NaOt-Bu (31.64 g, 329.22 mmol) and Toluene (360 mL) were added, and the reaction was carried out at 100 °C. When the reaction was completed, the reaction was _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the fished organic material was recrystallized by silicagel column to obtain compound 1-9 (24.83 g). (Yield: 65%)

(4) Synthesis of compound 1-10

In a round-bottom flask, compound 1-9 (25 g, 71.54 mmol) _{was dissolved in CH 2} Cl ₂ , and Br ₂ (11.37 g, 74.54 mmol) was slowly added dropwise, and the reaction mixture was stirred for 10 hours. After completion of the reaction, Br ₂ is removed with an aqueous sodium thiosulfate solution. After extraction with ethyl acetate and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain Compound 1-10 (15.32 g). (Yield: 50%)

(5) Synthesis of compound 1-11

Compound 1-10 (15 g, 35.01 mmol), 2-nitrophenyl boronic acid (7.01 g, 42.02 mmol), Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol) and K ₂ CO ₃ (14.51 g) in a round-bottom flask , 105.03 mmol), THF (120 mL) and H ₂ O (50 mL) were added, and the reaction mixture was refluxed for 10 hours. 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} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain Compound 1-11 (10.09 g). (Yield: 61%)

(6) Core 1(2) synthesis

Compound 1-11 (10 g, 21.16 mmol), PPh ₃ (17.94 g, 68.40 mmol) and O-DCB (75 mL) were added to a round-bottom flask and refluxed for 12 hours. After completion of the reaction, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was recrystallized using silicagel column to obtain Core 1(2) (4.64 g). (Yield: 50%)

Synthesis example of Core 2

Core 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3 below, but is not limited thereto.

<Scheme 3>

Synthesis example of Core 2(1)

(1) Synthesis of compound 2-1

Compound 1-50 (36.5 g, 85.16 mmol), 2-chloroaniline (10.86 g, 85.16 mmol), Pd(oAc) ₂ (0.57 g, 2.55 mmol), P(t-Bu) ₃ (1.03 g) in a round-bottom flask , 5.11), NaOt-Bu (24.55 g, 255.07 mmol) and Toluene (283 mL) were added and stirred at 75° C. for 8 hours. After extraction with methylene chloride and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain compound 2-1 (25.6 g). (Yield: 63%)

(2) Core 2(1) synthesis

_{Compound 2-1 (23.8 g, 49.88 mmol), PPh 3} (39.25 g, 149.65 mmol), and O-DCB (170 mL) were refluxed in a round bottom flask for 12 hours. After completion of the reaction, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain Core 2(1) (13.12g). (Yield: 60%)

Synthesis example of Core 2(2)

(1) Synthesis of compound 2-2

Compound 1-5 (36.5 g, 85.16 mmol), 2-chloropyridin-3-amine (10.94 g, 85.16 mmol), Pd(oAc) ₂ (0.57 g, 2.55 mmol), P(t-Bu) in a round bottom flask ₃ (1.03 g, 5.11), NaOt-Bu (24.55 g, 255.07 mmol) and Toluene (283 mL) were added and stirred at 75° C. for 8 hours. After extraction with methylene chloride and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized by silicagel column to obtain compound 2-2 (24.8 g). (Yield: 61%)

(2) Core 2(2) synthesis

Compound 2-2 (23.8 _{g, 49.88 mmol), PPh 3} (39.25 g, 149.65 mmol) and O-DCB (170 mL) were added to a round-bottom flask and refluxed for 12 hours. After completion of the reaction, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain Core 2 (2) (12.71 g). (Yield: 58%)

Synthesis example of Sub 1

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

(1) Synthesis of compound C

In a round-bottom flask, 1 equivalent of Compound A, 1 equivalent of Compound B , Pd(pph ₃ ) ₄ 0.03 equivalents K ₂ CO ₃ 3 equivalents, THF (0.1 mol), H ₂ O (0.3 mol mL) were added, and then reacted at 80 ° C. proceed with Upon 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 organic material was recrystallized by silicagel column to obtain compound C. (Yield: 45%)

(2) Synthesis of compound F

Compound D 1 equivalent, E 1 equivalent, Pd(pph ₃ ) ₄ 0.03 equivalent K ₂ CO ₃ 3 equivalents, THF (0.1 mol) and H ₂ O (0.3 mol mL) were put in a round-bottom flask, and the reaction was carried out at 80 ° C. proceed Upon completion of the reaction, _{extraction was performed with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized using silicagel column to obtain compound F. (Yield: 30%)

Examples of Sub 1 are as follows, but not limited thereto

[Table 1]

Final compound synthesis

Compound 1-4 Synthesis Example

In a round-bottom flask, Core 1(1) (6 g, 13.68 mmol), 4-bromo-1,1'-biphenyl (7.97 g, 34.20 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.41 mmol), P (t-Bu) ₃ (0.16 g, 0.82 mmol), NaOt-Bu (3.98 g, 41.49 mmol) and Toluene (50 mL) were added, and then the reaction was proceeded at 100 °C. When the reaction was completed, the organic layer was extracted with _{CH 2} Cl _{2 and water, dried over MgSO 4} , concentrated, and the fished organic material was recrystallized using silicagel column to obtain the final compound 1-4 (5.25 g). (Yield: 65%)

Compound 1-6 Synthesis Example

Core1 compound (6 g, 11.65 mmol), 4-bromo-1,1'-biphenyl (3.26 g, 13.99 mmol), Pd ₂ (dba) ₃ (0.32 g, 0.34 mmol), P(t-) in a round-bottom flask Bu) ₃ (0.14 g, 0.69 mmol), NaOt-Bu (3.36 g, 34.97 mmol) and Toluene (50 mL) were added, and then the final compound 1-6 (4.74 g) was obtained by the synthesis method of 1-4. (Yield: 61%)

Compound 1-8 Synthesis Example

Compound 1-8 (4.50 g) was obtained by the same synthesis except that 3-bromo-1,1'-biphenyl was used instead of 4-bromo-1,1'-biphenyl in Synthesis Example of Compound 1-6. (58%)

Compound 1-10 Synthesis Example

In a round-bottom flask, Core 1(1) (6 g, 13.68 mmol), 2-bromonaphthalene (7.97 g, 3.39 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.41 mmol), P(t-Bu) ₃ ( After adding 0.16 g, 0.82 mmol), NaOt-Bu (3.98 g, 41.49 mmol) and Toluene (50 mL), the final compound 1-10 (4.63 g) was obtained by the synthesis of compound 1-4. (Yield: 60%)

Compound 1-40 Synthesis Example

In a round-bottom flask, Core 1(1) (4.6 g, 10.48 mmol), 2-chlorobenzo[d]thiazole (2.13 g, 12.58 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), P(t- Bu) ₃ (0.12 g, 0.62 mmol), NaOt-Bu (3.02 g, 31.44 mmol) and Toluene (35 mL) were added, and then the final compound 1-40 (2.40 g) was obtained by the synthesis method of 1-4. (Yield: 40%)

Compound 1-48 Synthesis Example

Compound 1-48 (4.32 g) was obtained by the same synthesis except that 2-chloro-1-phenyl-1H-benzo[d]imidazole was used instead of 2-chlorobenzo[d]thiazole in the synthesis of compound 1-40. (60%)

Compound 1-54 Synthesis Example

In a round-bottom flask, Core 2(1) (6 g, 13.68 mmol), 4-bromo-1,1'-biphenyl (7.97 g, 34.20 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.41 mmol), P (t-Bu) ₃ (0.16 g, 0.82 mmol), NaOt-Bu (3.98 g, 41.49 mmol), and Toluene (50 mL) were added to the above compound The final compound 1-54 (5.25 g) was obtained by the synthesis method of 1-4. (Yield: 65%)

Compound 1-76 Synthesis Example

Core 2 compound (6 g, 13.65 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.48 g, 20.47 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.40 mmol), P(t-Bu) ₃ (0.16 g, 0.81 mmol), NaOt-Bu (3.93 g, 40.95 mmol), and Toluene (50 mL) were added, followed by the synthesis of 1-4 above to final compound 1-76 (4.12 g) was obtained. (Yield: 45%)

Compound 1-81 Synthesis Example

In the synthesis of compound 1-76, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. compound 1-81 (6.79 g) was obtained. (50%)

FD-MS values for compounds 1-1 to 1-100 synthesized by the above synthesis examples are shown in Table 2 below.

[Table 2]

Manufacturing evaluation of organic electric devices

[Example 1] Green organic light emitting device (phosphorescent host)

First, on an ITO layer (anode) formed on an organic substrate, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -phenylbenzene-1,4-diamine (hereinafter abbreviated as “2-TNATA”) was vacuum-deposited to a thickness of 60 nm to form a hole injection layer, and then 4,4-bis[ N -( 1-naphthyl) -N -phenylamino]biphenyl (hereinafter abbreviated as "-NPD") was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Then, the hole transport layer was doped with compound 1-1 of the present invention as a host and Ir(ppy) ₃ [tris(2-phenylpyridine)-iridium] as a dopant at a weight of 95:5 to form a light emitting layer with a thickness of 30 nm. formed. Then, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum (hereinafter abbreviated as “BAlq”) was vacuum-deposited on the light emitting layer to a thickness of 10 nm. A hole blocking layer was formed, and tris(8-quinolinol)aluminum (hereinafter _{abbreviated as “Alq 3} ”) was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 2] to [Example 100] Green organic light emitting device (phosphorescent host)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that compounds 1-2 to 1-100 of the present invention described in Table 2 below were used instead of compound 1-1 of the present invention as a hole transport layer material. .

[Comparative Example 1] to [Comparative Example 4] Green organic light emitting device (phosphorescent host)

In Comparative Examples 1 to 4, an organic electroluminescent device was prepared in the same manner as in Example 1, except that the following Comparative Compounds A to D were used instead of Compound 1-1 of the present invention as hosts.

By applying a forward bias DC voltage to the organic electroluminescent devices of Examples and Comparative Examples prepared as described above, electroluminescence (EL) characteristics were measured with a PR-650 manufactured by photoresearch, and McScience at 5000cd/m ² standard luminance T95 lifetime was measured through the lifetime measuring equipment manufactured by the company. The measurement results are shown in Table 3 below.

[Table 3]

As can be seen from the results of Table 3, the organic electroluminescent device using the compound of the present invention as a phosphorescent host has improved luminous efficiency and lifetime, and lowered driving voltage.

Looking at the results of applying the comparative compounds B to D and the compound of the present invention, the device characteristics were different depending on the type of hetero atom and the position where the rings were fused, despite the similar parent nucleus (compound form in which seven rings were fused). You can see that it changes.

Comparing the device characteristics measurement results of Comparative Example 2 and Comparative Example 3, which have the same fused structure but differ only in the type of hetero atom, it is found that the device using Comparative Compound C containing N and S heteroatoms has better characteristics. can be checked In addition, when comparing the device characteristics results of Comparative Examples 3 and 4, and the compounds of the present invention having the same type of hetero element but different fused positions, completely different device results are derived only with different fused positions. Able to know.

This is because the energy level of the compound varies depending on the type of element of the heterocyclic ring and the fusion position of the ring. It is judged that the best result was derived because the charge balancing in the light emitting layer of

That is, this suggests that even if the parent nucleus is similar, the physical properties of the compound and the result of the device may be significantly different depending on the type of hetero element in the hetero ring and the fusion position.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit 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 construed by the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

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

Claims (9)

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

In Formula 1,
Y ¹ and Y ² are each independently N(Ar ² ), m and n are each an integer of 0 or 1, provided that at least one of m and n is 1,
Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; _{C 2} -C ₆₀ A heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} and -L'-N(R ^a )(R ^b );
Z ¹ to Z ⁸ are each independently C(Ar ³ ) or N, Ar ³ is hydrogen, C ₆ -C ₆₀ An aryl group; fluorenyl group; _{C 2} -C ₆₀ A heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} And -L'-N(R _a )(R _b ); is selected from the group consisting of, and optionally adjacent Ar ³ may be bonded to each other to form a ring,
The L' is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} And C ₂ -C ₆₀ A heterocyclic group is selected from the group consisting of;
wherein R ^a and R ^b are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} And O, N, S, Si and P containing at least one heteroatom C ₂ -C ₆₀ A heterocyclic group; is selected from the group consisting of,
The aryl group, fluorenyl group, fused ring group, hetero group, arylene group and fluorenylene group are deuterium, halogen, silane group, siloxane group, boron group, germanium group, cyano group, nitro group, C ₁ -C ₂₀ of alkylthio come, as alkynyl group, an aryl group, a C ₆ -C ₂₀ heavy hydrogen of C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ of the Substituted C ₆ -C ₂₀ A heterocyclic group containing at least one heteroatom selected from the group consisting of an aryl group, a fluorenyl group, O, N, S, Si and P, C ₂ -C ₂₀ heterocyclic group, C ₃ - It may be further substituted with one or more substituents selected from the group consisting of a C ₂₀ cycloalkyl group, a C ₇ -C ₂₀ arylalkyl group, a C ₈ -C _{20 arylalkenyl group, an arylamine group, and a heteroarylamine group.} The method of claim 1,
Formula 1 is a compound, characterized in that represented by Formula 2 or Formula 3 below:
<Formula 2><Formula3>

In Formula 2 or Formula 3, Y ¹ , Y ² , Z ¹ to Z ⁸ and Ar ¹ are as defined in claim 1. The method of claim 1,
Formula 1 is a compound, characterized in that one of the following compounds:

. a first electrode; a second electrode; and an organic material layer formed with the first electrode and the second electrode,
The organic material layer is an organic electric device comprising the compound of any one of claims 1 to 3. 5. The method of claim 4,
An organic electric device comprising at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer of the organic material layer, and comprising one single compound or two or more compounds. 5. The method of claim 4,
The organic electric device further comprising a light efficiency improving layer formed on at least one surface opposite to the organic material layer of one surface of the first electrode and the second electrode. 5. The method of claim 4,
The organic material layer is an organic electric device, characterized in that 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. A display device comprising the organic electric device of claim 4; and
An electronic device comprising a; a control unit for driving the display device. 9. The method of claim 8,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and an electronic device, characterized in that at least one of a single color or white lighting device.

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