KR102501666B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides an organic electric device and an electronic device using a compound for a hole transport layer or a light emitting auxiliary layer and a compound for a light emitting layer capable of improving luminous efficiency, stability and lifespan of the device.

Description

Compound for organic electric element, organic electric element using the 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 electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.

Lifespan and efficiency are the most problematic issues in organic electroluminescent devices, and as displays become larger, these efficiency and lifespan problems must be solved.

Efficiency, lifespan, driving voltage, etc. are related to each other. As the efficiency increases, the driving voltage relatively decreases. indicates a tendency to increase life expectancy.

However, efficiency cannot be maximized by simply improving the organic layer. This is because long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interfacial property, etc.) of the material is achieved.

In addition, in order to solve the light emitting problem in the hole transport layer in recent organic electroluminescent devices, an auxiliary light emitting layer must exist between the hole transport layer and the light emitting layer, and different light emission auxiliary layers according to each light emitting layer (R, G, B) It is time to develop the layer.

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

However, since the material used in the hole transport layer must have a low HOMO value, most of them have a low T1 value, and as a result, excitons generated in the light emitting layer are transferred to the hole transport layer, resulting in charge unbalance in the light emitting layer resulting in light emission at the interface of the hole transport layer.

When light is emitted from the interface of the hole transport layer, the color purity and efficiency of the organic electric element are lowered and the lifetime is shortened. Therefore, there is an urgent need to develop a light emitting auxiliary layer having a high T1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.

On the other hand, it delays the penetration and diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of life shortening of organic electric devices, and has stable characteristics against Joule heating generated during device operation, that is, high glass transition. It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of reducing the uniformity of the surface of the thin film when the device is driven, which is reported to have a great effect on the lifespan of the device. In addition, OLED devices are mainly formed by a deposition method, and there is a need to develop materials that can endure for a long time during deposition, that is, materials with strong heat resistance.

That is, in order to fully exhibit the excellent characteristics of organic electric devices, materials constituting the organic material layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, and light emitting auxiliary layer materials, etc. are stable and efficient. Although supporting by materials should precede, the development of stable and efficient organic material layer materials for organic electric devices has not yet been sufficiently accomplished. Therefore, the development of new materials continues to be required, and furthermore, the combination of the hole transport layer or the light emitting auxiliary layer and the light emitting layer, in detail, the combination of the light emitting auxiliary layer and the phosphorescent host, the combination of the light emitting auxiliary layer, the phosphorescent host, and the dopant Development of the same element combination is also urgently required.

KR 1020060032099 A

Embodiments of the present invention to solve the problems of the above-mentioned background art, the optimal combination of the compound for the hole transport layer or the light emitting auxiliary layer and the compound for the light emitting layer was found, and the luminous efficiency of the device when these compounds are applied to the organic electric device , it was found that the stability and lifetime can be greatly improved.

Accordingly, an object of the present invention is to provide an organic electric device and an electronic device using a combination of a compound for a hole transport layer or a light emitting auxiliary layer and a compound for a light emitting layer.

The present invention provides an organic electric device characterized in that it comprises a hole transport layer or light emitting auxiliary layer containing a compound represented by the following formula (1) and a compound represented by the following formulas (2) to (4) as a light emitting layer. .

chemical formula (1)

Formula (2) Formula (3) Formula (4)

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and the color purity and lifespan of the device can be greatly improved.

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

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

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the corresponding component is not limited by the term. When an element is described as being “connected,” “coupled to,” or “connected” to another element, that element is or may be directly connected to the other element, but there is another element between the elements. It should be understood that elements may be “connected”, “coupled” or “connected”.

As used in this specification and the appended claims, unless otherwise stated, 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.

As used herein, unless otherwise specified, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, and includes a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, and the like. A radical of a saturated aliphatic functional group, including an alkyl group, a cycloalkyl-substituted alkyl group.

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

As used herein, the term "heteroalkyl group" means that one or more of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

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

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

As used herein, the term "alkoxyl group", "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, and is limited thereto. It is not.

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" refers to an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It has a carbon number of, 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.

The terms "aryl group" and "arylene group" used herein have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group refers to a single-ring or multi-ring aromatic ring, and includes an aromatic ring formed by bonding or reacting with adjacent substituents. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

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

Also, when the prefixes are named consecutively, it means 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 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.

The term "heteroalkyl" as used herein, unless otherwise specified, means an alkyl containing one or more heteroatoms. As used herein, the term "heteroaryl group" or "heteroarylene group" refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is limited thereto It does not, and includes at least one of a single ring and a multi-ring, and may be formed by combining adjacent functional groups.

As used herein, the term "heterocyclic group" includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group, unless otherwise specified. Contains an aromatic ring. It may also be formed by combining adjacent functional groups.

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

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

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

Unless otherwise specified, the term "ring" used herein refers to a fused ring composed of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

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

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

Unless otherwise specified, the term "ether" as used herein is represented by -R-O-R', wherein R or R' are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a carbon atom of 6 to 30 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.

In addition, unless explicitly stated otherwise, “substituted” in the term “substituted or unsubstituted” as used herein means 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 group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, deuterium-substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ ~ C ₂₀ means substituted with one or more substituents selected from the group consisting of heterocyclic groups, but is not limited to these substituents.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponential definition of the following chemical formula.

Here, when a is an integer of 0, substituent R ¹ does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is combined 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 indicating the hydrogen bonded to the carbon forming the benzene ring. is omitted.

Hereinafter, a compound according to an aspect of the present invention and an organic electric device including the same will be described.

According to a specific example of the present invention, in the organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the organic material layer is between the first electrode and the light emitting layer. It includes a light emitting auxiliary layer formed, a hole transport layer formed between the first electrode and the light emitting auxiliary layer, and a light emitting layer, wherein the light emitting layer includes a host and a dopant material, respectively, and the hole transport layer or the light emitting auxiliary layer has the following chemical formula (1) ), and the light emitting layer provides an organic electric device including at least one of the compounds represented by the following formulas (2) to (4).

chemical formula (1)

Formula (2) Formula (3) Formula (4)

{In the above formulas (1) to (4),

1) Ar ^{1 , 2, 3, 4} are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of, (Where L' is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorenylene group; C ₃ ~ C ₆₀ It is selected from the group consisting of an aliphatic ring and a C ₆ ~ C ₆₀ fused ring group of an aromatic ring; and a C ₂ ~ C ₆₀ heterocyclic group; wherein R _a and R _b are independently of each other C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; and C containing at least one heteroatom of O, N, S, Si and P ₂ ~ C ₆₀ heterocyclic group; selected from the group consisting of)

2) a, b, d, e, h, i, k are integers from 0 to 4, c, f, g are integers from 0 to 3, j is an integer from 0 to 2, and R ^{1 to 23} are independent of each other as hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); or adjacent R ¹ , adjacent R ² , adjacent R ³ , adjacent R ⁴ , adjacent R ⁵ , neighboring R ⁶ , neighboring R ⁷ , neighboring R ⁸ , neighboring R ⁹ , neighboring R ¹⁰ , neighboring R ¹¹ , neighboring R ¹² , neighboring R ¹³ , neighboring R ¹⁴ , neighboring R ¹⁵ , neighboring R ¹⁶ , neighboring R ¹⁷ , neighboring R ¹⁸ , neighboring R ¹⁹ , neighboring R ²⁰ , neighboring R ²¹ , neighboring One R ²² and adjacent R ²³ may bond to each other to form a ring,

3) L ^{1 to 5} are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₂ ~C ₆₀ divalent heterocyclic group; A divalent fused ring group of C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring; And it is selected from the group consisting of a divalent aliphatic hydrocarbon group,

4) X and Y are directly bonded independently of each other; S, O, NR', CR'R” or SiR'R”, W is S, O, NR', CR'R” or SiR'R”;

R' and R” are hydrogen; C ₆ ~ C ₆₀ aryl group; C ₃ ~ C ₆₀ heterocyclic group; It is selected from the group consisting of; C ₁ ~ C ₅₀ Alkyl group, and can be combined with each other to form a spyro compound;

5) l and m are integers from 0 to 1, l + m is 1 or more, and when l and m are 0, it means a direct bond,

6) Z ^1-16 are each independently CR or N, R is hydrogen, C ₆ ~ C ₆₀ aryl group; O, N, S, Si, P containing at least one heteroatom C ₃ ~ C ₆₀ heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₆ ~ C ₆₀ Arylamine group; It is selected from the group consisting of a fluorene group, and can form a ring by bonding with a neighboring group.}

As a specific embodiment, the present invention provides an organic electric device characterized in that the compound represented by Chemical Formula (1) is a compound represented by Chemical Formula (5) or (6) below.

Formula (5) Formula (6)

(In Formulas (5) and (6), ^{R 1-8} , a, b, c, d, e, f, g, h, Ar ^1-2 , L ^1-3 are defined in Formula (1) above as has been done.)

In addition, the present invention provides an organic electric device characterized in that the compound represented by Chemical Formula (2) is a compound represented by any one of Chemical Formulas (7) to (12) below.

Formula (7) Formula (8) Formula (9)

Formula (10) Formula (11) Formula (12)

(In Formulas (7) to (12), R ^{9 to 11} , i, j, k, Ar ³ , L ⁴ , X, and Y are as defined in Formula 1 above.)

In addition, the present invention provides an organic electric device characterized in that the compound represented by Chemical Formula (3) is a compound represented by any one of Chemical Formulas (13) to (16) below.

Formula (13) Formula (14)

Formula (15) Formula (16)

(In Formulas (13) to (16), Z ^1-16 , Ar ⁴ , L ⁵ , R'. R” is as defined in Formula 1 above.)

In addition, the present invention provides an organic electric device characterized in that the compound represented by the above formula (4) is represented by the following formula (17).

Formula (17)

{In the formula (17),

1) R ^{12,13,14,15,16,17,22,23} are as defined in Formula 1 above,

2) R ²⁴ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of, n is an integer from 0 to 4, adjacent R ²⁴ may bond to each other to form a ring,

3) L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₂ ~C ₆₀ divalent heterocyclic group; A divalent fused ring group of C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring; And it is selected from the group consisting of a divalent aliphatic hydrocarbon group,

4) T is S, O, NR', CR'R” or SiR'R, and R', R” are as defined in Formula 1 above.}

In addition, the present invention provides an organic electric device characterized in that the compound represented by the formula (1), formula (5) or (6) is selected from among the compounds represented by the following.

In addition, the present invention provides an organic electric device characterized in that the compounds represented by Formula (2) or Formulas (7) to (12) are represented by any one of the compounds shown below.

In addition, the present invention provides an organic electric device characterized in that the compound represented by Chemical Formula (3) or Chemical Formulas (13) to (16) is any one of the compounds represented by the following.

In addition, the present invention provides an organic electric device characterized in that the compound represented by the formula (4) or formula (17) is a compound represented by any one of the following.

In another aspect, the present invention provides an organic electric device including a compound represented by the following formula (18) as a dopant in the light emitting layer.

Formula (18)

(In the above formula (18),

1) R ²⁵ to R ³² are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; O, N, S, Si, P containing at least one heteroatom C ₃ ~ C ₆₀ heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₁ ~ C ₅₀ alkoxy group; C ₂ ~ C ₂₀ alkenyl group; -L'-N(R _a )(R _b ); Is selected from the group consisting of, or R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² are can combine with each other to form a ring,

2) L is an integer from 1 to 3

3) A is an independent ligand represented by the following formula (18-1) or formula (18-2), having a covalent bond with C, a coordination bond with N, a covalent bond with O, or a coordination bond with another O As a result, it forms a complex with Ir,

Formula (18-1) Formula (18-2)

4) R ³³ and R ³⁴ are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; O, N, S, Si, P containing at least one heteroatom C ₃ ~ C ₆₀ heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₁ ~ C ₅₀ alkoxy group; C ₂ ~ C ₂₀ alkenyl group; -L'-N (R _a ) (R _b ); It is selected from the group consisting of.)

In addition, the present invention provides an organic electric device characterized in that the compound represented by the formula (18) is any one of the compounds represented below.

_

Referring to FIG. 1, the organic electric element 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 and a second electrode formed on a substrate 110. An organic material layer containing the compound represented by Chemical Formula 1 is provided between (180). In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), 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, other layers except for the light emitting layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and an electron transport layer 160 may serve as a hole blocking layer.

In addition, although not shown, the organic electric element according to the present invention may further include a protective layer formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

On the other hand, even in the same core, since the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is attached to which position, the selection of the core and the combination of sub-substituents bonded thereto are also very important. It is important, especially when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved, long life and high efficiency can be achieved at the same time.

An organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and After forming an organic material layer including the electron injection layer 170, it can be manufactured by depositing a material that can be used as a cathode thereon.

In addition, the present invention further includes a light efficiency improvement layer formed on at least one of one side opposite to the organic material layer among one side surface of the first electrode in the organic electric device or one side opposite to the organic material layer among one side surface of the second electrode. It provides an organic electric element that does.

In the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process, and the organic material layer includes the compound as an electron transport material. It provides an organic electric element characterized in that.

As another specific example, the present invention provides an organic electric device characterized in that a compound of the same type or a different type of the compound represented by the formula (1) is mixed and used in the organic material layer.

In addition, the present invention provides a hole transport layer or light emitting auxiliary layer composition containing the compound represented by Formula (1), and provides an organic electric device including the hole transport layer or light emitting auxiliary layer.

In addition, the present invention is a display device including the organic electric element; and a controller for driving the display device.

In another aspect, the present invention provides an electronic device characterized in that the organic electric device is at least one of an organic light emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for monochromatic or white lighting. At this time, 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 device, a game machine, various TVs, and various computers.

Hereinafter, synthetic examples of the compounds represented by the above formulas (1) to (4) and (18) of the present invention and manufacturing examples of the organic electric device of the present invention will be described in detail with examples, but the present invention It is not limited to the following examples.

[ synthesis example One]

The final product represented by Chemical Formula (1) according to the present invention is prepared by reacting Sub 1 with Sub 2 as shown in Scheme 1 below.

<Scheme 1>

Sub 1 synthesis Example (L ^One this single bond if not )

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

<Scheme 2>

Sub 1(6) Synthesis example

Synthesis of Sub 1-2-1

After dissolving Sub 1-1-1 (55.3g, 140 mmol) in DMF 980mL, bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol) ) were added in order and after stirring for 24 hours, the resulting compound was separated over a silicagel column and recrystallization to obtain 45.8 g (74%) of the borate compound Sub 1-2-1.

Synthesis of Sub 1(6)

Sub 1-2-1 (35.4 g, 80 mmol), THF 360 mL, Sub 1-3-1 (23.8 g, 84 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water were added, followed by stirring and refluxing. After the reaction was completed, extraction was performed with ether and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 28.7 g (76%) of the product.

Sub 1(8) Synthesis example

Synthesis of Sub 1-2-2

After dissolving Sub 1-1-2 (55.3g, 140 mmol) in DMF 980mL, bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol) ) were added in order and after stirring for 24 hours, the resulting compound was separated over a silicagel column and recrystallization to obtain 46.4 g (75%) of the borate compound Sub 1-2-2.

Synthesis of Sub 1(8)

Sub 1-2-1 (35.4 g, 80 mmol), THF 360 mL, Sub 1-3-2 (32.7 g, 84 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water are added, followed by stirring to reflux. After the reaction was completed, extraction was performed with ether and water, the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 33.3 g (72%) of the product.

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

compound FD-MS compound FD-MS Sub 1(1) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(2) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(3) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(4) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(5) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(6) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(7) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(8) m/z=576.05 (C ₃₇ H ₂₁ BrS=577.54) Sub 1(9) m/z=471.06 (C ₃₀ H ₁₈ BrN=472.39) Sub 1(10) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40) Sub 1(11) m/z = 546.10 (C ₃₇ H ₂₃ Br = 547.50) Sub 1(12) m/z=470.07 (C ₃₁ H ₁₉ Br=471.40)

Sub 2 synthesis example

Sub 3 of Reaction Scheme 1 may be synthesized by the reaction pathway of Reaction Scheme 3 below, but is not limited thereto.

<Scheme 3>

Synthesis example of Sub 2(1)

After dissolving Sub 2-2-1 (7.7g, 24mmol) in toluene, Sub 2-1-1 (5.2g, 20mmol), Pd ₂ (dba) ₃ (0.5g, 0.6mmol), P (t-Bu ) ₃ (0.2g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (300 mL) were added, followed by stirring and refluxing at 100℃ for 24 hours. After the reaction was completed, extraction was performed with ether and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 6.8 g of the final compound (yield: 68%).

Synthesis example of Sub 2 (18)

After dissolving Sub 2-2-2 (11.5g, 24mmol) in toluene, Sub 2-1-2 (6.7g, 20mmol) was synthesized using the above Sub 2(1) synthesis method to obtain 11.1g of the final compound (yield: 76 %) was obtained.

Synthesis example of Sub 2(1)

After dissolving Sub 2-1-1 (6.2g, 24mmol) in toluene, the final compound 9.1g (yield: 76 %) was obtained.

An example of Sub 2 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub 2(1) m/z=499.20 (C ₃₆ H ₂₅ N ₃ =499.62) Sub 2(2) m/z=549.22 (C ₄₀ H ₂₇ N ₃ =549.68) Sub 2(3) m/z=549.22 (C ₄₀ H ₂₇ N ₃ =549.68) Sub 2(4) m/z=575.24 (C ₄₂ H ₂₉ N ₃ =575.72) Sub 2(5) m/z=651.27 (C ₄₈ H ₃₃ N ₃ =651.81) Sub 2(6) m/z=599.24 (C ₄₄ H ₂₉ N ₃ =599.74) Sub 2(7) m/z=649.25 (C ₄₈ H ₃₁ N ₃ =649.80) Sub 2(8) m/z=654.25 (C ₄₅ H ₃₀ N ₆ =654.78) Sub 2(9) m/z=627.24 (C ₄₄ H ₂₉ N ₅ =627.75) Sub 2(10) m/z = 615.27 (C ₄₅ H ₃₃ N ₃ =615.78) Sub 2(11) m/z=605.19 (C ₄₂ H ₂₇ N ₃ S=605.76) Sub 2(12) m/z = 664.26 (C ₄₈ H ₃₂ N ₄ =664.814) Sub 2(13) m/z=574.24 (C ₄₂ H ₂₉ N ₃ =575.72) Sub 2(14) m/z=625.25 (C ₄₆ H ₃₁ N ₃ =625.78) Sub 2(15) m/z=731.24 (C ₅₂ H ₃₃ N ₃ S=731.92) Sub 2(16) m/z = 727.30 (C ₅₄ H ₃₇ N ₃ =727.91) Sub 2(17) m/z = 725.28 (C ₅₄ H ₃₅ N ₃ =725.90) Sub 2(18) m/z = 730.28 (C ₅₁ H ₃₄ N ₆ =730.88) Sub 2(19) m/z = 677.26 (C ₄₈ H ₃₁ N ₅ =677.81) Sub 2(20) m/z=665.28 (C ₄₉ H ₃₅ N ₃ =665.84) Sub 2(21) m/z=499.20 (C ₃₆ H ₂₅ N ₃ =499.62) Sub 2(22) m/z=549.22 (C ₄₀ H ₂₇ N ₃ =549.68) Sub 2(23) m/z=549.22 (C ₄₀ H ₂₇ N ₃ =549.68) Sub 2(24) m/z=575.24 (C ₄₂ H ₂₉ N ₃ =575.72)

Example of Final Products synthesis

Synthesis example of 1-4

After dissolving Sub 1(13) (9.5g, 24mmol) in toluene, Sub 2(24) (11.5g, 20mmol) was added and Pd ₂ (dba) ₃ (0.5g, 0.6mmol), P(t-Bu ) ₃ (0.2g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (300 mL) were added, followed by stirring and refluxing at 100℃ for 24 hours. After the reaction was completed, extraction was performed with ether and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 16.2 g of the final compound (yield: 76%).

Synthesis example of 2-8

After dissolving Sub 1(14) (9.5g, 24mmol) in toluene, Sub 2(25) (13.1g, 20mmol) was added and 16.7g of the final compound (yield: 72%) was obtained using the synthesis method of 1-4 above. got it

Synthesis example of 3-14

After dissolving Sub 1(15) (9.5g, 24mmol) in toluene, Sub 2(26) (12.5g, 20mmol) was added and 16.7g of the final compound (yield: 74%) was obtained using the synthesis method of 1-4 above. got it

Synthesis example of 4-1

After dissolving Sub 1(16) (9.5g, 24mmol) in toluene, Sub 2(21) (10.0g, 20mmol) was added and final compound 15.2 (yield: 78%) was obtained using the synthesis method of 1-4 above. .

Synthesis example of 5-4

After dissolving Sub 1(16) (9.5g, 24mmol) in toluene, Sub 2(27) (11.5g, 20mmol) was added and 15.8g of the final compound (yield: 74%) was obtained using the synthesis method of 1-4 above. got it

Synthesis example of 6-8

After dissolving Sub 1(16) (9.5g, 24mmol) in toluene, Sub 2(28) (13.1g, 20mmol) was added and 17.7g of the final compound (yield: 76%) was obtained using the synthesis method of 1-4 above. got it

Synthesis example of 7-14

After dissolving Sub 1(16) (9.5g, 24mmol) in toluene, Sub 2(29) (12.5g, 20mmol) was added and 16.9g of the final compound (yield: 75%) was obtained using the synthesis method of 1-4 above. got it

Synthesis example of 8-1

After dissolving Sub 1(16) (9.5g, 24mmol) in toluene, Sub 2(30) (10.0g, 20mmol) was added and 15.0 (yield: 77%) of the final compound was obtained using the synthesis method of 1-4 above. got it

compound FD-MS compound FD-MS 1-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 1-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 1-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 1-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 1-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 1-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 1-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 1-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 1-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 1-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 1-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 1-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 1-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 1-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 1-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 1-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 1-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 1-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 1-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 1-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 1-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 1-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 1-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 1-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 1-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 1-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 1-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 1-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 2-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 2-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 2-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 2-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 2-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 2-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 2-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 2-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 2-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 2-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 2-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 2-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 2-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 2-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 2-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 2-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 2-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 2-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 2-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 2-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 2-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 2-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 2-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 2-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 2-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 2-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 2-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 2-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 3-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 3-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 3-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 3-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 3-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 3-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 3-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 3-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 3-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 3-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 3-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 3-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 3-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 3-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 3-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 3-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 3-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 3-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 3-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 3-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 3-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 3-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 3-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 3-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 3-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 3-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 3-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 3-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 4-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 4-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 4-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 4-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 4-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 4-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 4-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 4-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 4-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 4-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 4-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 4-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 4-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 4-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 4-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 4-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 4-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 4-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 4-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 4-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 4-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 4-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 4-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 4-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 4-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 4-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 4-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 4-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 5-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 5-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 5-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 5-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 5-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 5-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 5-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 5-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 5-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 5-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 5-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 5-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 5-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 5-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 5-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 5-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 5-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 5-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 5-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 5-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 5-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 5-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 5-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 5-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 5-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 5-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 5-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 5-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 6-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 6-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 6-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 6-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 6-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 6-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 6-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 6-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 6-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 6-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 6-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 6-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 6-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 6-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 6-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 6-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 6-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 6-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 6-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 6-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 6-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 6-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 6-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 6-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 6-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 6-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 6-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 6-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 7-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 7-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 7-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 7-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 7-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 7-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 7-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 7-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 7-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 7-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 7-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 7-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 7-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 7-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 7-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 7-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 7-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 7-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 7-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 7-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 7-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 7-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 7-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 7-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 7-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 7-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 7-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 7-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29) 8-1 m/z = 813.31 (C ₆₁ H ₃₉ N ₃ =814.00) 8-2 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 8-3 m/z = 864.33 (C ₆₅ H ₄₁ N ₃ =864.06) 8-4 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 8-5 m/z = 965.38 (C ₇₃ H ₄₇ N ₃ =966.20) 8-6 m/z = 913.35 (C ₆₉ H ₄₃ N ₃ =914.12) 8-7 m/z = 963.36 (C ₇₃ H ₄₅ N ₃ =964.18) 8-8 m/z = 968.36 (C ₇₀ H ₄₄ N ₆ =969.16) 8-9 m/z = 941.35 (C ₆₉ H ₄₃ N ₅ =942.14) 8-10 m/z = 929.38 (C ₆₉ H ₄₃ N ₅ =942.14) 8-11 m/z=919.30 (C ₆₇ H ₄₁ N ₃ S=920.15) 8-12 m/z = 978.37 (C ₇₃ H ₄₆ N ₄ =979.20) 8-13 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 8-14 m/z=939.36 (C ₇₁ H ₄₅ N ₃ =940.16) 8-15 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 8-16 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 8-17 m/z = 1041.41 (C ₇₉ H ₅₁ N ₃ =1042.30) 8-18 m/z=989.38 (C ₇₅ H ₄₇ N ₃ =990.22) 8-19 m/z = 1115.42 (C ₈₅ H ₅₃ N ₃ =1116.38) 8-20 m/z=1196.46 (C ₈₈ H ₅₆ N ₆ =1197.46) 8-21 m/z = 991.37 (C ₇₃ H ₄₅ N ₅ =992.20) 8-22 m/z = 979.39 (C ₇₄ H ₄₉ N ₃ =980.23) 8-23 m/z=1095.36 (C ₈₁ H ₄₉ N ₃ S=1096.36) 8-24 m/z = 1028.39 (C ₇₇ H ₄₈ N ₄ =1029.26) 8-25 m/z = 889.35 (C ₆₇ H ₄₃ N ₃ =890.10) 8-26 m/z=1045.35 (C ₇₇ H ₄₇ N ₃ S=1046.30) 8-27 m/z=939.36 (C ₇₁ H ₄₅ N ₂ =940.16) 8-28 m/z = 1042.40 (C ₇₈ H ₅₀ N ₄ =1043.29)

[ synthesis example 2]

Synthesis examples of Product 9-9 among the final products represented by Chemical Formula 2 according to the present invention are shown in Scheme 4 below, but are not limited thereto.

<Scheme 4>

Sub 9-2 synthesis method

Sub 9-1 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reactant was stirred at 0 °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78 °C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and then extracted with ether. After removing water from the reactant with anhydrous MgSO ₄ , filtering under reduced pressure, and concentrating the organic solvent, the resulting product was separated using column chromatography to obtain desired Sub 9-2.

Sub 9-3 synthesis method

The resulting Sub 9-2, 1-iodo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , and K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated using column chromatography to obtain the desired Sub 9-3.

Sub 9-4 synthesis method

Obtained Sub 9-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain desired Sub 9-4.

Product 9-9 Synthesis

Sub 9-4 (1 equivalent) and Sub 9-6 (1.1 equivalent) were added to toluene and Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent) and NaO t -Bu (3 equivalents) were added, respectively, followed by stirring and refluxing at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain Product 9-9.

compound FD-MS compound FD-MS 9-1 m/z=349.09 (C ₂₄ H ₁₅ NS=349.45) 9-2 m/z=504.14 (C ₃₃ H ₂₀ N ₄ S=504.60) 9-3 m/z=503.15 (C ₃₄ H ₂₁ N ₃ S=503.62) 9-4 m/z=477.13 (C ₃₂ H ₁₉ N ₃ S=477.58) 9-5 m/z=527.15 (C ₃₆ H ₂₁ N ₃ S=527.64) 9-6 m/z=653.19 (C ₄₆ H ₂₇ N ₃ S=653.79) 9-7 m/z = 720.17 (C ₅₀ H ₂₈ N ₂ S ₂ =720.90) 9-8 m/z=579.18 (C ₄₀ H ₂₅ N ₃ S=579.71) 9-9 m/z=503.15 (C ₃₄ H ₂₁ N ₃ S=503.62) 9-10 m/z=504.14 (C ₃₃ H ₂₀ N ₄ S=504.60) 9-11 m/z=477.13 (C ₃₂ H ₁₉ N ₃ S=477.58) 9-12 m/z=541.16 (C ₃₇ H ₂₃ N ₃ S=541.66) 9-13 m/z=527.15 (C ₃₆ H ₂₁ N ₃ S=527.64) 9-14 m/z=527.15 (C ₃₆ H ₂₁ N ₃ S=527.64) 9-15 m/z=527.15 (C ₃₆ H ₂₁ N ₃ S=527.64) 9-16 m/z=553.16 (C ₃₈ H ₂₃ N ₃ S=553.67) 9-17 m/z=774.23 (C ₅₂ H ₃₂ N ₄ S=744.90) 9-18 m/z=554.16 (C ₃₇ H ₂₂ N ₄ S=554.66) 9-19 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.70) 9-20 m/z=641.19 (C ₄₅ H ₂₇ N ₃ S=641.78) 9-21 m/z=563.21 (C ₃₉ H ₂₅ N ₅ =563.65) 9-22 m/z=562.22 (C ₄₀ H ₂₆ N ₄ =562.66) 9-23 m/z=504.14 (C ₃₃ H ₂₀ N ₄ S=504.60) 9-24 m/z=563.21 (C ₃₉ H ₂₅ N ₅ =563.65) 9-25 m/z=514.22 (C ₃₆ H ₂₆ N ₄ =514.62) 9-26 m/z=488.16 (C ₃₃ H ₂₀ N ₄ O=488.54) 9-27 m/z=427.11 (C ₂₈ H ₁₇ N ₃ S=427.52) 9-28 m/z=514.22 (C ₃₆ H ₂₆ N ₄ =514.62) 9-29 m/z = 680.26 (C ₄₈ H ₃₂ N ₄ O = 680.79) 9-30 m/z=590.25 (C ₄₂ H ₃₀ N ₄ =590.71) 9-31 m/z=694.22 (C ₄₈ H ₃₀ N ₄ S=694.84) 9-32 m/z=513.22 (C ₃₇ H ₂₇ N ₃ =513.63) 9-33 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) 9-34 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) 9-35 m/z=567.14 (C ₃₈ H ₂₁ N ₃ OS=567.67) 9-36 m/z = 583.12 (C ₃₈ H ₂₁ N ₃ S ₂ =583.73)

[ synthesis example 3]

Synthesis of Product 10-1 among the final products represented by Chemical Formula 3 according to the present invention is prepared by reacting with Reaction Scheme 5 below, but is not limited thereto.

<Scheme 5>

After dissolving 3-bromo-9-phenyl-9H-carbazole (6.4g, 20mmol) in THF, (9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazol- After adding 3-yl)boronic acid (8.8g, 20mmol), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent), and water, the mixture was stirred and refluxed. After the reaction was completed, extraction was performed with ether and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 9.2 g (yield: 72%) of the product.

compound FD-MS compound FD-MS 10-1 m/z = 639.24 (C ₄₅ H ₂₉ N ₅ =639.75) 10-2 m/z = 715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 10-3 m/z = 780.33 (C ₅₇ H ₄₀ N ₄ =780.95) 10-4 m/z = 639.24 (C ₄₅ H ₂₉ N ₅ =639.75) 10-5 m/z = 715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 10-6 m/z = 780.33 (C ₅₇ H ₄₀ N ₄ =780.95) 10-7 m/z=612.23 (C ₄₄ H ₂₈ N ₄ =612.72) 10-8 m/z=612.23 (C ₄₄ H ₂₈ N ₄ =612.72) 10-9 m/z = 662.25 (C ₄₈ H ₃₀ N ₄ =662.78) 10-10 m/z=484.19 (C ₃₆ H ₂₄ N ₂ =484.59) 10-11 m/z = 639.24 (C ₄₅ H ₂₉ N ₅ =639.75) 10-12 m/z = 715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 10-13 m/z = 715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 10-14 m/z=638.25 (C ₄₆ H ₃₀ N ₄ =638.76) 10-15 m/z=579.18 (C ₄₀ H ₂₅ N ₃ S=579.71) 10-16 m/z=410.14 (C ₂₉ H ₁₈ N ₂ S=410.47) 10-17 m/z=486.17 (C ₃₅ H ₂₂ N ₂ O=486.56) 10-18 m/z=486.17 (C ₃₅ H ₂₂ N ₂ O=486.56) 10-19 m/z=486.17 (C ₃₅ H ₂₂ N ₂ O=486.56) 10-20 m/z=563.20 (C ₄₀ H ₂₅ N ₃ O=563.65) 10-21 m/z=460.16 (C ₃₃ H ₂₀ N ₂ O=460.52) 10-22 m/z=536.19 (C ₃₉ H ₂₄ N ₂ O=536.62) 10-23 m/z = 689.26 (C ₄₉ H ₃₁ N ₅ =689.80) 10-24 m/z=585.22 (C ₄₃ H ₂₇ N ₃ =585.69) 10-25 m/z=484.19 (C ₃₆ H ₂₄ N ₂ =484.60) 10-26 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.66) 10-27 m/z=560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 10-28 m/z=560.23 (C ₄₂ H ₂₈ N ₂ =560.70)

[ synthesis example 4]

Synthesis of Product 11-6 among the final products represented by Chemical Formula 4 according to the present invention is prepared by reacting with Reaction Scheme 6 below, but is not limited thereto.

<Scheme 6>

After dissolving triphenylen-2-ylboronic acid (5.4g, 20mmol) in THF, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.8g, 20mmol), Pd (PPh ₃ ) ₄ (0.03 equiv.), K ₂ CO ₃ (3 equiv.), and water were added, followed by stirring to reflux. After the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 7.5 g (yield: 70%) of the product.

compound FD-MS compound FD-MS 11-1 m/z=401.11 (C ₃₀ H ₁₈ S=410.53) 11-2 m/z=401.11 (C ₃₀ H ₁₈ S=410.53) 11-3 m/z=486.14 (C ₃₆ H ₂₂ S=486.62) 11-4 m/z=486.14 (C ₃₆ H ₂₂ S=486.62) 11-5 m/z=534.21 (C ₄₀ H ₂₆ N ₂ =534.65) 11-6 m/z=535.20 (C ₃₉ H ₂₅ N ₃ =535.64) 11-7 m/z=536.16 (C ₄₀ H ₂₄ S=536.68) 11-8 m/z=536.16 (C ₄₀ H ₂₄ S=536.68) 11-9 m/z=575.17 (C ₄₂ H ₂₅ NS=575.72) 11-10 m/z=559.19 (C ₄₂ H ₂₅ NO=559.65) 11-11 m/z=585.25 (C ₄₅ H ₃₁ N=585.73) 11-12 m/z=575.17 (C ₄₂ H ₂₅ NS=575.72)

[ synthesis example 5]

The compound represented by Formula 18 according to the present invention (final products) is prepared by reacting with the following Reaction Scheme 7 or Reaction Scheme 8, but is not limited thereto.

<Scheme 7> When L is 3

<Scheme 8> When L is 1 to 2

Synthesis example of Sub 18

Sub 18 of Reaction Scheme 7 is prepared by reacting with Reaction Scheme 9 below, but is not limited thereto.

<Scheme 9>

After dissolving 2-chloropyridine (1 equivalent) in THF, phenylboronic acid (1 equivalent), Pd(PPh ₃ ) ₄ (0.05 equivalent), K ₂ CO ₃ (3 eq.), water was added and stirred at 80°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product.

An example of Sub 18 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub 18-1 m/z=205.09 (C ₁₅ H ₁₁ N=205.25) Sub 18-2 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 18-3 m/z=255.10 (C ₁₉ H ₁₃ N=255.31) Sub 18-4 m/z=233.12 (C ₁₇ H ₁₅ N=233.31) Sub 18-5 m/z=261.15 (C ₁₉ H ₁₉ N=261.36) Sub 18-6 m/z=255.10 (C ₁₉ H ₁₃ N=255.31) Sub 18-7 m/z=205.09 (C ₁₅ H ₁₁ N=205.25) Sub 18-8 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 18-9 m/z=247.14 (C ₁₈ H ₁₇ N=247.33) Sub 18-10 m/z=281.12 (C ₂₁ H ₁₅ N=281.35) Sub 18-11 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 18-12 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 18-13 m/z=223.08 (C ₁₅ H ₁₀ FN=223.25) Sub 18-14 m/z=223.08 (C ₁₅ H ₁₀ FN=223.25) Sub 18-15 m/z=229.09 (C ₁₇ H ₁₁ N=229.28) Sub 18-16 m/z=183.10 (C ₁₃ H ₁₃ N=183.25) Sub 18-17 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 18-18 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 18-19 m/z=259.14 (C ₁₉ H ₁₇ N=259.34) Sub 18-20 m/z=259.14 (C ₁₉ H ₁₇ N=259.34) Sub 18-21 m/z=259.14 (C ₁₉ H ₁₇ N=259.34) Sub 18-22 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 18-23 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 18-24 m/z=183.10 (C ₁₃ H ₁₃ N=183.25) Sub 18-25 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 18-26 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 18-27 m/z=187.08 (C ₁₂ H ₁₀ FN=187.21) Sub 18-28 m/z=191.05 (C ₁₁ H ₇ F ₂ N=191.18) Sub 18-29 m/z=215.09 (C ₁₃ H ₁₃ NO ₂ =215.25) Sub 18-30 m/z=281.12 (C ₂₁ H ₁₅ N=281.35) Sub 18-31 m/z=261.06 (C ₁₇ H ₁₁ NS=261.34) Sub 18-32 m/z=211.05 (C ₁₃ H ₉ NS=211.28) Sub 18-33 m/z=225.06 (C ₁₄ H ₁₁ NS=225.31) Sub 18-34 m/z=267.11 (C ₁₇ H ₁₇ NS=267.39) Sub 18-35 m/z=261.06 (C ₁₇ H ₁₁ NS=261.34) Sub 18-36 m/z=377.12 (C ₂₆ H ₁₉ NS=377.50) Sub 18-37 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 18-38 m/z=219.10 (C ₁₆ H ₁₃ N=219.28)

Synthesis Example of Product 18

Ir(acac) ₃ (1 equivalent) was added to Sub 18 (4 equivalents) and refluxed with glycerol for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain the final compound.

18-4 Synthesis

Ir(acac) ₃ (489.54 g, 20 mmol) was added to 2-(m-tolyl)pyridine (13.5 g, 80 mmol) and refluxed with glycerol for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain 42.5 g of the final compound (yield: 76%).

18-6 Synthesis

Ir(acac) ₃ (489.54 g, 20 mmol) was added to 2,4-diphenylpyridine (18.5 g, 80 mmol) and refluxed with glycerol for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain 52.5 g of the final compound (yield: 74%).

Example synthesis of Product 19-1

Product 19-1 of Reaction Scheme 8 is prepared by reacting with Reaction Scheme 10 below, but is not limited thereto.

<Scheme 10>

Sub 18(3) Synthesis example

IrCl ₃ (1 equivalent) was added to 2-phenylpyridine (2.5 equivalents), and 2-ethoxy ethanol: H ₂ O ratio was added to a solution of 3: 1, followed by reaction at 140° C. for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain the final compound.

Product 19- 1 synthesis example

Sub 18(3) (1 equivalent) was added with pentane-2,4-dione (10 equivalents), Na ₂ CO ₃ (10 equivalents), and 2-ethoxy ethanol, and reacted at 130°C for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain the final compound.

19-2 Synthesis

2,2,6,6-tetramethylheptane-3,5-dione (10 equivalents), Na ₂ CO ₃ (10 equivalents), and 2-ethoxy ethanol were added to the Ir compound (1 equivalent) and reacted at 130℃ for 24 hours under nitrogen. made it After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain the final compound 19-2.

19-6 Synthesis

Ir compound (1 equivalent) was added with pentane-2,4-dione (10 equivalents), Na ₂ CO ₃ (10 equivalents), and 2-ethoxy ethanol, and reacted under nitrogen at 130°C for 24 hours. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain the final compound 19-6.

Example synthesis of Product 19-2

Product 19-1 (1 equivalent) and Sub 19 (2 equivalents) were added and microwaved for 20 minutes with Glycerol. After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain the final compound.

Sub 19 is the same as the example of Sub 18.

19-7 Synthesis

Ancillary ligand, 2-([1,1'-biphenyl]-3-yl)pyridine (9.3g, 40mmol) was added to Ir compound (12.2g, 20mmol) as a ligand and microwaved at 240℃ for 20 minutes with glycerol. . After the reaction was completed, the solid obtained was filtered, purified through column chromatography, and dried under a vacuum pump for 3 hours to obtain 8.8 g of the final compound (yield: 60%).

Synthesis of Product 19-39

Ancillary ligand, 2-([1,1'-biphenyl]-3-yl)pyridine (6.2g, 40mmol) was added to Ir compound (18.1g, 20mmol) as a ligand and microwaved at 240℃ for 20 minutes with glycerol. . After the reaction was completed, the obtained solid material was filtered, purified through column chromatography, and dried for 3 hours under a vacuum pump to obtain 11.3 g of the final compound (yield: 58%).

Manufacturing evaluation of organic electric devices

Comparative Example 1) Fabrication and Testing of Green Organic Light-Emitting Device

First, on the ITO layer (anode) formed on the glass substrate, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film is vacuum deposited to form a 60 nm thick 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. Subsequently, the inventive compound represented by Formula 1 as a light emitting auxiliary layer material was vacuum deposited to a thickness of 20 nm to form a light emitting auxiliary layer. After forming the light emitting auxiliary layer, the inventive compound represented by formulas (2) to (4) is used as a host and 18-1 of the inventive compound represented by formula (18) is used as a dopant on the top of the light emitting auxiliary layer. A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping with a weight of:5. As a hole-blocking layer, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm, and an electron transport layer was formed. A film of tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed to a thickness of 40 nm. Thereafter, LiF, 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 and used as a cathode, thereby manufacturing an organic light emitting device.

A forward bias DC voltage was applied to the organic electroluminescent devices of Examples and Comparative Examples prepared as described above to measure electroluminescence (EL) characteristics with PR-650 of Photoresearch, and as a result of the measurement, at a standard luminance of 5000 cd/m2 T95 life was measured through life measurement equipment manufactured by McScience. The table below shows the results of device fabrication and evaluation.

Comparative Examples 1 to 3)

An organic light emitting device was manufactured in the same manner as in Example 1 except that the light emitting auxiliary layer was not used.

Comparative Examples 4 to 6)

An organic light emitting device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used as the light emitting auxiliary layer.

Comparative Examples 7 to 12)

An organic light emitting device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 was used as a host.

Comparative Compound 1 Comparative Compound 2

light emitting auxiliary layer compound host compound Voltage Current Density Brightness
(cd/m2) Efficiency Lifetime
T(95) Comparative Example (1) doesn't exist compound (9-9) 5.3 17.4 5000.0 28.7 71.8 Comparative example (2) compound (10-28) 5.5 18.7 5000.0 26.8 86.2 Comparative Example (3) compound (11-4) 5.8 19.9 5000.0 25.1 91.2 Comparative example (4) comparative compound 1 compound (9-9) 5.5 12.6 5000.0 39.6 101.2 Comparative example (5) compound (10-28) 5.8 13.1 5000.0 38.1 107.5 Comparative Example (6) compound (11-4) 6.2 14.0 5000.0 35.8 112.7 Comparative Example (7) Compound (1-1) comparative compound 2 5.8 13.5 5000.0 37.1 110.0 Comparative Example (8) compound (2-8) 5.7 12.8 5000.0 39.1 109.5 Comparative Example (9) compound (3-4) 5.7 13.2 5000.0 38.0 102.2 Comparative Example (10) Compound (4-1) 5.2 12.5 5000.0 39.9 115.5 Comparative Example (11) Compound (6-1) 5.4 13.7 5000.0 36.5 101.5 Comparative Example (12) Compound (7-1) 5.3 13.6 5000.0 36.7 109.0 Example (1) Compound (1-1) compound (9-9) 4.3 10.2 5000.0 49.0 123.5 Example (2) compound (2-8) 4.5 10.2 5000.0 49.0 128.3 Example (3) compound (3-4) 4.4 10.4 5000.0 48.0 121.9 Example (4) Compound (4-1) 4.3 10.0 5000.0 50.2 121.3 Example (5) Compound (6-1) 4.5 10.1 5000.0 49.4 120.9 Example (6) Compound (7-1) 4.3 10.1 5000.0 49.7 122.8 Example (7) Compound (1-1) compound (10-28) 4.7 10.7 5000.0 46.8 124.1 Example (8) compound (2-8) 4.8 10.8 5000.0 46.4 124.8 Example (9) compound (3-4) 4.5 10.6 5000.0 47.4 125.6 Example (10) Compound (4-1) 4.5 10.4 5000.0 48.3 124.0 Example (11) Compound (6-1) 4.6 10.9 5000.0 46.0 126.8 Example (12) Compound (7-1) 4.7 10.4 5000.0 48.0 122.5 Example (13) Compound (1-1) compound (11-4) 4.8 11.4 5000.0 43.7 130.5 Example (14) compound (2-8) 4.8 11.4 5000.0 43.9 131.2 Example (15) compound (3-4) 4.9 11.4 5000.0 43.8 132.4 Example (16) Compound (4-1) 4.8 10.9 5000.0 45.8 132.3 Example (17) Compound (6-1) 4.9 11.6 5000.0 43.2 133.3 Example (18) Compound (7-1) 4.8 11.5 5000.0 43.5 132.4

As can be seen from the results of Table 8, the compounds represented by Formula (1) were used as the light emitting auxiliary layer, and the compounds represented by Formulas (2) to (4) were used as hosts of the light emitting layer, and the compounds represented by Formula (18) were used. The examples using the compound as the dopant of the light emitting layer do not use the light emitting auxiliary layer (Comparative Examples 1 to 3), Comparative Compound 1 is used as the light emitting auxiliary layer (Comparative Examples 4 to 6), or Comparative Compound 2 is used as the light emitting layer. It can be seen that the driving voltage, efficiency and lifespan of the organic light emitting device are significantly improved compared to Comparative Examples 7 to 12 used as a throttle.

In other words, Comparative Examples 4 to 12 and Examples 1 to 18 using Comparative Compound 1 or the inventive compound as a light emitting auxiliary layer improve driving voltage, lifespan, and especially efficiency, compared to Comparative Examples 1 to 3 without using an auxiliary light emitting layer. Able to know. That is, this shows that the use of the light emitting auxiliary layer can increase the efficiency compared to the device without using it.

In addition, compared to Comparative Examples 4 to 12 in which Comparative Compound 1 and Comparative Compound 2 were used as light emitting auxiliary layers or host compounds, the inventive compound represented by Chemical Formula 1 was used as the light emitting auxiliary layer, and the compounds represented by Chemical Formulas 2 to 4 were used as host compounds. 1 to 18 showed significantly superior results in driving voltage, efficiency and lifespan, which is because the compound represented by Formula 1 has characteristics such as deep HOMO, high T1, and high thermal stability compared to Comparative Compound 1, and here the formula ( By using the compounds represented by 2) to (4) as a phosphorescent host, it is believed that the combination of these devices has a synergistic effect electrochemically to improve the performance of the device as a whole.

That is, since the combination of the compound represented by Chemical Formula 1 and the compounds represented by Chemical Formulas 2 to 4 exhibited significantly better performance than other combinations, it can be seen that it is the most ideal combination.

The above description is merely illustrative of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in this specification are not intended to limit the present invention, but to explain, 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 according to the following claims, and all technologies within the equivalent range should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode (anode) 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 (cathode)

Claims (16)

In the organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer includes a light emitting auxiliary layer formed between the first electrode and the light emitting layer, a hole transport layer formed between the first electrode and the light emitting auxiliary layer, and a light emitting layer, wherein the light emitting layer includes a host and a dopant material, respectively,
The hole transport layer or the light emitting auxiliary layer includes a compound represented by the following formula (1), and the light emitting layer includes at least one of the compounds represented by the formula (2), (3) or (4). organic electric element that does.
chemical formula (1)

Formula (2) Formula (3) Formula (4)

{In the above formulas (1) to (4),
1) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a C ₆ to C ₆₀ aryl group; fluorenyl group; and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; is selected from the group consisting of
2) a, b, d, e, h, i, k are integers from 0 to 4, c, f, g are integers from 0 to 3, j is an integer from 0 to 2, and R ¹ to R ²³ are each other hydrogen independently; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; is selected from the group consisting of, or adjacent R ¹ , adjacent R ² , adjacent R ³ , adjacent R ⁴ , adjacent R ⁵ , adjacent R ⁶ , adjacent R ⁷ , Neighboring R ⁸ , Neighboring R ⁹ , Neighboring R ¹⁰ , Neighboring R ¹¹ , Neighboring R ¹² , Neighboring R ¹³ , Neighboring R ¹⁴ , Neighboring R ¹⁵ , Neighboring R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R 22 22 22 ²² 22 R ²² can form,
3) L ¹ to L ⁵ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; And C ₂ ~ C ₆₀ It is selected from the group consisting of a divalent heterocyclic group;
4) X and Y are directly bonded independently of each other; S, O, NR', or CR'R", and W is S, O, NR' or CR'R";
R' and R” are hydrogen; C ₆ ~ C ₆₀ aryl group; C ₃ ~ C ₆₀ heterocyclic group; It is selected from the group consisting of; C ₁ ~ C ₅₀ Alkyl group, and can be combined with each other to form a spyro compound;
5) l and m are integers from 0 to 1, l + m is 1 or more, and when l and m are 0, it means a direct bond,
6) Z ¹ to Z ¹⁶ are each independently CR or N, R is hydrogen, C ₆ ~ C ₆₀ aryl group; O, N, S, Si, P containing at least one heteroatom C ₃ ~ C ₆₀ heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; It is selected from the group consisting of; and a fluorene group, and is capable of forming a ring by bonding with a neighboring group.}
According to claim 1,
An organic electric device, characterized in that the compound represented by the formula (1) is a compound represented by the following formula (5) or (6).
Formula (5) Formula (6)

(In Formulas (5) and (6), ^{R 1-8} , a, b, c, d, e, f, g, h, Ar ^1-2 , L ^1-3 are as defined in claim 1 above. same.)
The organic electric device according to claim 1, wherein the compound represented by Chemical Formula (2) is a compound represented by any one of Chemical Formulas (7) to (12) below.
Formula (7) Formula (8) Formula (9)

Formula (10) Formula (11) Formula (12)

(In Formulas (7) to (12), R ^{9 to 11} , i, j, k, Ar ³ , L ⁴ , X, Y are as defined in claim 1 above.)
The organic electric device according to claim 1, wherein the compound represented by Chemical Formula (3) is a compound represented by any one of Chemical Formulas (13) to (16) below.
Formula (13) Formula (14)

Formula (15) Formula (16)

(In the formulas (13) to (16), Z ^{1 to 16} , Ar ⁴ , L ⁵ , R'. R” is as defined in claim 1 above.)
The organic electric device according to claim 1, wherein the compound represented by the formula (4) is represented by the following formula (17).
Formula (17)

{In the formula (17),
1) R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²² and R ²³ are as defined in claim 1 above,
2) R ²⁴ is hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; selected from the group consisting of, n is an integer from 0 to 4, and adjacent R ²⁴ They can combine with each other to form a ring,
3) L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; and C ₂ ~C ₆₀ divalent heterocyclic group; is selected from the group consisting of
4) T is S, O, NR', or CR'R”, and R', R” are as defined in claim 1 above.}
The organic electric device according to claim 2, wherein the compound represented by Formula (1), Formula (5) or (6) is selected from among the compounds represented by the following

4. The organic electric device according to claim 3, wherein the compounds represented by Chemical Formula (2) or Chemical Formulas (7) to (12) are represented by any one of the following compounds.

The organic electric device according to claim 4, wherein the compound represented by Chemical Formula (3) or Chemical Formulas (13) to (16) is any one of the compounds represented by the following

The organic electric device according to claim 5, wherein the compound represented by Formula (4) or Formula (17) is a compound represented by any one of the following.

The organic electric device according to claim 1, wherein a dopant in the light emitting layer includes a compound represented by the following Chemical Formula (18).

Formula (18)

{In the formula (18),
1) R ²⁵ to R ³² are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; It is selected from the group consisting of; C ₁ ~ C ₅₀ alkyl group;
2) L is an integer from 1 to 3
3) A is an independent ligand represented by the following formula (18-1) or formula (18-2), having a covalent bond with C, a coordination bond with N, a covalent bond with O, or a coordination bond with another O As a result, it forms a complex with Ir,
Formula (18-1) Formula (18-2)

4) R ³³ and R ³⁴ are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; It is selected from the group consisting of; C ₁ ~ C ₅₀ alkyl group;
5) CyN is a cyclic group containing N, and CyC is a cyclic group containing C.}
11. The organic electric device according to claim 10, wherein the compound represented by the formula (18) is any one of the compounds represented below.

According to claim 1,
An organic electric device further comprising a light efficiency improvement layer formed on at least one of 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.
According to claim 1,
The organic layer may be formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
According to claim 1,
in the organic layer
The hole transport layer or the light emitting auxiliary layer is a compound represented by the following formula (1),
The light-emitting layer is a compound represented by the following formula (2), (3) or (4),
An organic electric device characterized in that it is used in a mixture of the same or heterogeneous compounds.
A display device comprising the organic electric element of claim 1; and a controller for driving the display device.
According to claim 15,
The organic electric device is an electronic device, characterized in that any one of an organic light emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting device

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