KR20130110934A - Organometallic compounds and organic light emitting diodes comprising the compounds - Google Patents

Abstract

PURPOSE: An organometallic compound is provided to obtain an organic electroluminescent device with excellent thermal properties, light emitting efficiency, and color purity, thereby being used in a display or a lamp. CONSTITUTION: An organometallic compound is denoted by chemical formula 1. The half-width of the organometallic compound is 60 nm or less. An organic electroluminescent device comprises an anode, a cathode, and the organometallic compounds between the anode and the cathode. A light emitting layer between the anode and the cathode contains the organometallic compounds. The organic electroluminescent device further comprises one or more layers among a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

Description

Organometallic compounds and organic light emitting diodes comprising the compounds}

The present invention relates to an organometallic compound and an organic electroluminescent device comprising the same, and more particularly to an organic metal compound having a narrow half-width full width of the fluorescence spectrum and an organic electroluminescent device having excellent thermal properties, luminous efficiency and color purity using the same will be.

Recently, as the size of the display device increases, the demand for a flat display device having a small space is increasing. A liquid crystal display, which is a typical flat display device, has a merit of being lighter than a conventional cathode ray tube (CRT). The disadvantage is that the angle is limited and the back light is necessary. In contrast, organic light emitting diodes (OLEDs), which are new flat panel display devices, are displays using self-luminous phenomena, which have a large viewing angle, are thinner and shorter than liquid crystal displays, and have fast response speed In recent years, the application to full-color display or lighting is expected.

An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

The material used as the organic material layer in the organic electroluminescent device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. A host-dopant system can be used as the luminescent material to increase the luminous efficiency through.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

Looking at the light emission principle in the light emitting material, electrons and holes injected from both electrodes form an exciton (exciton) by a combination, where singlet excitons are involved in fluorescence and triplet excitons are involved in phosphorescence. Phosphorescent materials using triplet excitons having a 75% generation probability show superior luminous efficiency than fluorescent materials using singlet excitons with a 25% generation probability.

High efficiency phosphors that can be applied to organic electroluminescent devices are very limited. Molecular structures that can easily emit phosphorescence are metal complexes containing a large atomic number of metals with easy molecular transitions. These include Ir, Pt, Eu, and Tb. The development of phosphors using transition metals such as, Re, Rh, Os, etc. is progressing, and luminescence properties are determined according to the type of ligand. However, since the luminance is low and the stability of the material is low, there is a limit to apply it to an actual device. Therefore, research on new light emitting materials is being actively conducted, and the development of a material having excellent phosphorescence efficiency is required.

Japanese Patent Publication No. 2001-313178 Japanese Patent Publication No. 2002-305083 Japanese Patent Publication No. 2002-352957

An object of the present invention is to provide a novel organic metal compound and an organic light emitting device having excellent thermal properties, luminous efficiency and color purity using the same.

In order to solve the above technical problem, the present invention provides an organometallic compound represented by the following [Formula 1].

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxy group, an alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, a fluorinated alkyl group of 3 to 18 carbon atoms , Alkylamino group having 1 to 40 carbon atoms, arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms Is selected from the group consisting of

R ₄ and R ₅ are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, or a carbon atom Arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, and aryloxy group having 3 to 40 carbon atoms , A heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron;

X and Y represent carbon or nitrogen atoms,

A ₁ and A ₂ are an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, at least one containing a nitrogen atom coordinated to an iridium metal,

G is a single bond or alkylene having 1 to 4 carbon atoms,

L is one or two ligands, m, n and p are integers from 1 to 4,

R ₁ to R ₅ , X, Y, A ₁ , A ₂ , and G are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, and 1 to 40 carbon atoms. Alkoxy group, alkylamino group of 1 to 40 carbon atoms, arylamino group of 6 to 40 carbon atoms, heteroarylamino group of 3 to 40 carbon atoms, alkylsilyl group of 1 to 40 carbon atoms, arylsilyl group of 6 to 40 carbon atoms, It may be substituted by one or more substituents selected from the group consisting of an aryl group having 40, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron.

The organometallic compound according to the present invention may be a compound represented by the following [Formula 2-1] to [Formula 2-3].

[Formula 2-1] [Formula 2-2] [Formula 2-3]

In the above formula, B is a substituted or unsubstituted aromatic ring connected divalent, the aromatic ring may be condensed and connected to 1 to 8 rings, may include a hetero atom, when B is a substituted aromatic ring And the substituents are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, and a 6 to 40 carbon atoms Arylamino group, C3-40 heteroarylamino group, C1-40 alkylsilyl group, C6-40 arylsilyl group, C6-40 aryl group, C3-40 aryloxy group, C3 To 40 heteroaryl group, germanium group, phosphorus and boron may be selected from the group consisting of.

On the other hand, the half width of the fluorescence spectrum of the organometallic compound according to the present invention is preferably 60 nm or less.

In addition, the present invention is an anode; Cathode; And it provides an organic electroluminescent device comprising an organometallic compound according to the [Formula 1] between the anode and the cathode. In this case, the organometallic compound is preferably included in the light emitting layer between the anode and the cathode, the organic electroluminescent device according to the present invention is a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer between the anode and the cathode It may further include one or more layers selected from the group consisting of an electron transport layer and an electron injection layer.

The organometallic compound according to the present invention can provide an organic light emitting device excellent in thermal properties, luminous efficiency and color purity, and thus can be usefully used for a display device, a display or an illumination.

1 is a schematic diagram of an organic light emitting display device according to an embodiment of the present invention.
2 is a view showing TGA and DSC of the formula 84 according to an embodiment of the present invention.
3 is a view showing TGA and DSC of formula 109 according to an embodiment of the present invention.
4 is a view showing TGA and DSC of Formula 178 according to an embodiment of the present invention.
FIG. 5 is a view showing the full width at half maximum of the PL spectrum of Chemical Formula 185 and Comparative Example 1 [Ir (ppy) ₃ ] according to an embodiment of the present invention.
FIG. 6 is a view showing EL spectra of Chemical Formula 109 and Comparative Example 1 [Ir (ppy) ₃ ] according to an embodiment of the present invention.

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

The organometallic compound according to the present invention may be represented by the following [Formula 1].

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxy group, an alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, a fluorinated alkyl group of 3 to 18 carbon atoms , Alkylamino group having 1 to 40 carbon atoms, arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms Is selected from the group consisting of

R ₄ and R ₅ are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, or a carbon atom Arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, and aryloxy group having 3 to 40 carbon atoms , A heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron;

X and Y represent carbon or nitrogen atoms,

A ₁ and A ₂ are an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, at least one containing a nitrogen atom coordinated to an iridium metal,

G is a single bond or alkylene having 1 to 4 carbon atoms,

L is one or two ligands, m, n and p are integers from 1 to 4,

R ₁ to R ₅ , X, Y, A ₁ , A ₂ , and G are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, and 1 to 40 carbon atoms. Alkoxy group, alkylamino group of 1 to 40 carbon atoms, arylamino group of 6 to 40 carbon atoms, heteroarylamino group of 3 to 40 carbon atoms, alkylsilyl group of 1 to 40 carbon atoms, arylsilyl group of 6 to 40 carbon atoms, It may be substituted by one or more substituents selected from the group consisting of an aryl group having 40, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron.

In addition, the organometallic compound according to the present invention may be a compound represented by the following [Formula 2].

[Formula 2-1] [Formula 2-2] [Formula 2]

In the above formula, B is a substituted or unsubstituted aromatic ring which is divalently linked, and the aromatic ring may be condensed and connected to 1 to 8 rings, and may include a hetero atom. In addition, when B is a substituted aromatic ring, the substituents are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 An alkylamino group of 40 to 40 carbon atoms, an arylamino group of 6 to 40 carbon atoms, a heteroarylamino group of 3 to 40 carbon atoms, an alkylsilyl group of 1 to 40 carbon atoms, an arylsilyl group of 6 to 40 carbon atoms, an aryl group of 6 to 40 carbon atoms It may be selected from the group consisting of an aryloxy group having 3 to 40, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron.

In addition, according to an embodiment of the present invention, the ligand L may be selected from, for example, a divalent ligand represented by the following [Formula 3].

(3)

In the ligand,

Each R ₆ independently represents a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, and a 6 to 40 carbon atoms Arylamino group, C3-40 heteroarylamino group, C1-40 alkylsilyl group, C6-40 arylsilyl group, C6-40 aryl group, C3-40 aryloxy group, C3 To 40 heteroaryl groups, substituted or unsubstituted germanium groups, substituted or unsubstituted phosphorus, and substituted or unsubstituted boron, and adjacent groups are bonded to each other to form an aliphatic, aromatic, heteroaliphatic or hetero Can form an aromatic condensed ring,

R ₆ is a deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, C1-40 alkyl group, C1-40 alkoxy group, C1-40 alkylamino group, C6-40 arylamino group, carbon number 3-40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 aryloxy group, C3-C40 heteroaryl It may be substituted by one or more substituents selected from the group consisting of a group, a germanium group, phosphorus, boron.

Also specifically, the organometallic compound according to the present invention may be, for example, one of the compounds of the following [Formula 4] to [Formula 184].

[Formula 4] [Formula 5] [Formula 6] [Formula 7]

[Formula 8] [Formula 9] [Formula 10] [Formula 11]

[Formula 12] [Formula 13] [Formula 14] [Formula 15]

[Formula 16] [Formula 17] [Formula 18] [Formula 19]

[Formula 20] [Formula 21] [Formula 22] [Formula 23]

[Formula 24] [Formula 25] [Formula 26] [Formula 27]

[Formula 28] [Formula 29] [Formula 30] [Formula 31]

[Formula 32] [Formula 33] [Formula 34] [Formula 35]

[Formula 36] [Formula 37] [Formula 38] [Formula 39]

[Formula 40] [Formula 41] [Formula 42] [Formula 43]

[Formula 44] [Formula 45] [Formula 46] [Formula 47]

[Formula 48] [Formula 49] [Formula 50] [Formula 51]

[Formula 52] [Formula 53] [Formula 54] [Formula 55]

[Formula 56] [Formula 57] [Formula 58] [Formula 59]

[Formula 60] [Formula 61] [Formula 62] [Formula 63]

[Formula 64] [Formula 65] [Formula 66] [Formula 67]

[Formula 68] [Formula 69] [Formula 70] [Formula 71]

[Formula 72] [Formula 73] [Formula 74] [Formula 75]

[Formula 76] [Formula 77] [Formula 78] [Formula 79]

[Formula 80] [Formula 81] [Formula 82] [Formula 83]

[Formula 84] [Formula 85] [Formula 86] [Formula 87]

[Formula 88] [Formula 89] [Formula 90] [Formula 91]

[Formula 92] [Formula 93] [Formula 94] [Formula 95]

[Formula 96] [Formula 97] [Formula 98] [Formula 99]

[Formula 100] [Formula 101] [Formula 102] [Formula 103]

[Formula 104] [Formula 105] [Formula 106] [Formula 107]

[Formula 108] [Formula 109] [Formula 110] [Formula 111]

[Formula 112] [Formula 113] [Formula 114] [Formula 115]

[Formula 116] [Formula 117] [Formula 118] [Formula 119]

[Formula 120] [Formula 121] [Formula 122] [Formula 123]

[Formula 124] [Formula 125] [Formula 126] [Formula 127]

[Formula 128] [Formula 129] [Formula 130] [Formula 131]

[Formula 132] [Formula 133] [Formula 134] [Formula 135]

[Formula 136] [Formula 137] [Formula 138] [Formula 139]

[Formula 140] [Formula 141] [Formula 142] [Formula 143]

[Formula 144] [Formula 145] [Formula 146] [Formula 147]

[Formula 148] [Formula 149] [Formula 150] [Formula 151]

[Formula 152] [Formula 153] [Formula 154] [Formula 155]

[Formula 156] [Formula 157] [Formula 158] [Formula 159]

[Formula 160] [Formula 161] [Formula 162] [Formula 163]

[Formula 164] [Formula 165] [Formula 166] [Formula 167]

[Formula 168] [Formula 169] [Formula 170] [Formula 171]

[Formula 172] [Formula 173] [Formula 174] [Formula 175]

[Formula 176] [Formula 177] [Formula 178] [Formula 179]

[Formula 177] [Formula 178] [Formula 179] [Formula 180]

[Formula 181] [Formula 182] [Formula 183] [Formula 184]

The organometallic compound according to the present invention includes organosilicon, and the half width of the fluorescence spectrum is 60 nm or less. According to the present invention, color purity, efficiency, and the like are improved as compared with using a light emitting layer material having a half width of 60 nm or more for an organic field device. In particular, the use of a resonant substrate has the advantage that this effect is even greater.

The present invention also provides an organic electroluminescent device comprising an anode, a cathode and an organometallic compound represented by the above [Formula 1] between the anode and the cathode. At this time, the layer containing the organometallic compound is preferably a light emitting layer between the anode and the cathode, and between the anode and the cathode as a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer It may further comprise one or more layers selected from the group consisting of.

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the material of the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A hole injection layer (HIL) may be further stacked on the lower portion of the hole transport layer. The hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. For example, CuPc (copperphthalocyanine) or starburst amines TCTA (4,4 ', 4 "-tri (N-carbazolyl) triphenyl-amine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenyl amino) triphenylamine) and the like can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, .

The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and for example, oxadiazole derivatives such as PBD, BMD, BND or Alq ₃ may be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic light emitting display device according to the present invention can be used for a display device, a display device and a monochrome or white lighting device.

1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are presented by way of example to help understanding of the present invention, and the scope of the present invention is not limited thereto.

< Synthetic example  1> Preparation of the compound represented by Formula 8

1) Synthesis of Compound Represented by Chemical Formula 1-a

A compound represented by Chemical Formula 1-a was synthesized according to Scheme 1 below.

[Reaction Scheme 1]

                         [Chemical Formula 1-a]

20.0 g (164 mmol) phenylboronic acid, 42.7 g (180 mmol) 2,5-dibromopyridine, 10.4 g (9.0 mmol) tetrakistriphenylphosphine palladium, 49.7 g (360 mmol) sodium carbonate, in a 1 L round bottom flask 420mL, tetrahydrofuran 840mL was added and refluxed for 12 hours. The temperature was lowered to room temperature to terminate the reaction, followed by filtration. The organic layer was extracted using diethyl ether and water, concentrated under reduced pressure, and purified by column using ethyl acetate and normal hexane as a developing solvent to obtain 30.3 g (yield 79.0%) of the compound represented by Chemical Formula 1-a.

2) Synthesis of Compound Represented by Chemical Formula 1-b

The compound represented by Chemical Formula 1-b was synthesized by Reaction Scheme 2 below.

[Reaction Scheme 2]

                            [Chemical Formula 1-b]

Into a 500 mL round bottom flask, 20.0 g (85.4 mmol) of a compound represented by Chemical Formula 1-a obtained from Scheme 1 and 200 m of THF were added and then cooled to -78 ° C. 42.9 g (102.5 mmol) of normal butyllithium was slowly added dropwise to this solution, and after stirring for 1 hour at the same temperature, 11.1 g (102.5 mmol) of chlorotrimethylsilane was added slowly. The reaction product was heated to room temperature, and then stirred for 12 hours. The reaction was terminated with saturated brine, extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure and distilled under reduced pressure to obtain 15.0 g (yield 77.2%) of the compound represented by compound 1-b.

3) Synthesis of Compound Represented by Chemical Formula 1-c

The compound represented by Chemical Formula 1-c was synthesized by Reaction Scheme 3 below.

Scheme 3

                                           [Chemical Formula 1-c]

Synthesis was carried out in the same manner as in Scheme 2 of Synthesis Example 1 to obtain 16.0 g (yield 82.2%) of the compound represented by Chemical Formula 1-c.

4) Synthesis of Compound Represented by Chemical Formula 1-d

The compound represented by Chemical Formula 1-d was synthesized by Reaction Scheme 4 below.

[Reaction Scheme 4]

                                           [Formula 1-d]

Into a 500 mL round bottom flask, 15.0 g (65.2 mmol) of the compound represented by Chemical Formula 1-c obtained from Scheme 3 and 150 mL of tetrahydrofuran were added, and the temperature was cooled to -78 degrees. 32.8 g (78.3 mmol) of normal butyllithium was slowly added dropwise, followed by stirring for 1 hour at the same temperature, and then 8.1 g (78.3 mmol) of trimethylborate was slowly added dropwise. The temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction was terminated and extracted with a 2 molar hydrochloric acid aqueous solution, the organic layer was concentrated under reduced pressure, recrystallized with hexane and dried to give 8.6g (yield 65.6%) of the compound represented by the formula (1-d).

5) Synthesis of Compound Represented by Chemical Formula 1-e

A compound represented by Chemical Formula 1-e was synthesized by Reaction Scheme 5 below.

[Reaction Scheme 5]

                                          [Formula 1-e]

Synthesis was performed in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 7.2 g (yield 77.2%) of the compound represented by Chemical Formula 1-e.

6) Synthesis of Compound Represented by Chemical Formula 1-f

The compound represented by Chemical Formula 1-f was synthesized by Reaction Scheme 6 below.

[Reaction Scheme 6]

                                  [Formula 1-f]

Into a 250 mL round bottom flask was added compound 7.0g (30.8mmol), iridium chloride 4.6g (15.4mmol), ethoxyethanol 60mL, 20mL of water represented by the formula 1-b obtained in Scheme 2 of Synthesis Example 1 and then 120 degrees Reflux for 18 hours. The temperature was lowered to room temperature, poured into water (200 mL), and the resulting solid was filtered and washed with water, methanol, ether and hexane to obtain 8.6 g (yield 82.0%) of the compound represented by Chemical Formula 1-f.

7) Synthesis of Compound Represented by Formula 8

The compound represented by Chemical Formula 8 was synthesized according to Scheme 7 below.

[Reaction Scheme 7]

                                            [Formula 8]

In a 100 mL round bottom flask, 8.0 g (5.9 mmol) of the compound represented by Formula 1-f from Scheme 6, 3.1 g (15.5 mmol) of the compound represented by Formula 1-e obtained in Scheme 5, and 6.4 g (58.8 mmol) of sodium carbonate ), 60 mL of ethoxyethanol was added and refluxed at 120 ° C. for 18 hours. After the temperature was lowered, the reaction product was poured into 500 mL of water, the resulting solid was filtered, dissolved in dichloromethane, and separated by column chromatography using hexane and ethyl acetate as a developing solvent. The compound represented by the formula (8) was 2.8 g (yield 55.2%). Got it.

MS: m / z calcd 871.28; found 871.Anal. Calcd. for C ₄₂ H ₄₈ N ₃ IrSi ₃ : C, 57.89; H, 5.55; N, 4.82. Found: C, 57.93; H, 5.83; N, 4.73.

< Synthetic example  2> Preparation of the compound represented by Formula 14

1) Synthesis of Compound Represented by Chemical Formula 2-a

The compound represented by Chemical Formula 2-a was synthesized according to Scheme 8 below.

[Reaction Scheme 8]

                                        [Chemical Formula 2-a]

Synthesis was carried out in the same manner as in Scheme 2 of Synthesis Example 1 to obtain 17.2 g (yield 88.4%) of the compound represented by Formula 2-a.

2) Synthesis of Compound Represented by Formula 2-b

The compound represented by Chemical Formula 2-b was synthesized by Reaction Scheme 9 below.

Scheme 9

                                     [Formula 2-b]

Synthesis was carried out in the same manner as in Scheme 4 of Synthesis Example 1 to obtain 10.3 g (yield 71.4%) of the compound represented by Formula 2-b.

 3) Synthesis of Compound Represented by Chemical Formula 2-c

A compound represented by Chemical Formula 2-c was synthesized by Reaction Scheme 10 below.

[Reaction Scheme 10]

                                   [Chemical Formula 2-c]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 12.9 g (yield 81.8%) of the compound represented by Formula 2-c.

4) Synthesis of Compound Represented by Chemical Formula 2-d

The compound represented by Chemical Formula 2-d was synthesized by Reaction Scheme 11 below.

[Reaction Scheme 11]

                                           [Formula 2-d]

12.0 g (39.2 mmol) of compound represented by the formula 2-c obtained in Scheme 10 in 2.1 g (47.0 mmol) of dimethylamine in a 250 mL round bottom flask, 38.0 g (392 mmol) of sodium butyl butoxide, 0.4 g of tributyl butyl phosphine (2.0 mmol) and 120 mL of toluene were added and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted, and the organic layer was concentrated under reduced pressure, separated by column chromatography using ethyl acetate and hexane, and dried to obtain 6.5 g (yield 61.9%) of the compound represented by formula 2-d.

5) Synthesis of Compound Represented by Formula 2-e

The compound represented by Chemical Formula 2-e was synthesized by Reaction Scheme 12 below.

[Reaction Scheme 12]

                               [Formula 2-e]

13.1g (yield 77.2%) of compounds represented by the formula 2-e were obtained by synthesis in the same manner as in Scheme 6 of Synthesis Example 1.

6) Synthesis of Compound Represented by Formula 14

A compound represented by Chemical Formula 14 was synthesized according to Scheme 13 below.

[Reaction Scheme 13]

                                               [Formula 14]

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 3.0 g (yield 49.2%) of the compound represented by Formula 14.

MS: m / z calcd 957.36; found 957.Anal. Calcd. for C ₄₆ H ₅₈ N ₅ Irt Si ₃ : C, 57.7; H, 6.11; N, 7.31. Found: C, 58.3; H, 6.43 N, 7.18.

< Synthetic example  3> Preparation of the compound represented by Formula 17

1) Synthesis of Compound Represented by Formula 3-a

The compound represented by Chemical Formula 3-a was synthesized according to Scheme 14 below.

[Reaction Scheme 14]

                              [Formula 3-a]

25.0 g (220.0 mmol) of 2,6-difluoropyridine and 170 mL of glacial acetic acid were added to a 1 L round bottom flask, followed by adding 29.6 g (870.2 mmol) of 30% hydrogen peroxide solution and stirring at 70 ° C. for 5 hours. At the same temperature, 7.4 g of 30% hydrogen peroxide solution is added and heated at 75 ° C. for 8 hours. After the temperature was lowered to room temperature, 700 mL of acetone was added thereto to obtain 24.2 g (yield 85.1%) of the compound represented by Chemical Formula 2-a.

2) Synthesis of Compound Represented by Formula 3-b

The compound represented by Chemical Formula 3-b was synthesized by Reaction Scheme 15 below.

[Reaction Scheme 15]

                                  [Formula 3-b]

Into a 500 mL round bottom flask, 24.0 g (180.2 mmol) of the compound represented by the formula (3-a) obtained from Scheme 14 and 240 mL of tetrahydrofuran were added, followed by cooling to -78 ° C. 88.2 g (220.4 mmol) of LDA was slowly added dropwise to this solution, followed by stirring at the same temperature for 2 hours, and then 32.1 g (220.4 mmol) of triethyl borate was slowly added thereto. The reaction product was warmed to room temperature, stirred for 12 hours, and 400 mL of 1M NaOH was added. The aqueous layer was separated and the aqueous layer was adjusted to pH 8 with 2N HCl, extracted with 100 mL of ethyl acetate, the aqueous layer was adjusted to pH 6.5, extracted twice with ethyl acetate, and the aqueous layer was adjusted to pH 4 again with ethyl acetate. Extracted twice. The extract was dried and the solvent was removed and then recrystallized with ethyl acetate and ether to give 22.6 g (yield 95.2%) of the compound represented by formula 3-b.

3) Synthesis of Compound Represented by Chemical Formula 3-c

A compound represented by Chemical Formula 3-c was synthesized by Reaction Scheme 16 below.

[Reaction Scheme 16]

                                [Chemical Formula 3-c]

 Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 23.1 g (yield 88.1%) of the compound represented by Chemical Formula 3-c.

4) Synthesis of Compound Represented by Formula 14

The compound represented by Chemical Formula 14 was synthesized by Reaction Scheme 17 below.

[Reaction Scheme 17]

                                     [Formula 14]

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 1.7 g (yield 55.1%) of the compound of formula (14).

MS: m / z calcd 852.21; found 852. Anal. Calcd. for C ₃₈ H ₃₃ N ₄ IrOSi ₂ : C, 53.56; H, 4.38; N, 6.58. Found: C, 53.77; H, 4.51; N, 6.38.

< Synthetic example  4> chemical formula By 56  Preparation of the Compounds Displayed

1) Synthesis of Compound Represented by Chemical Formula 4-a

The compound represented by Chemical Formula 4-a was synthesized according to Scheme 18 below.

[Reaction Scheme 18]

                               [Chemical Formula 4-a]

 Synthesis was carried out in the same manner as in Scheme 2 of Synthesis Example 1 to obtain 11.8 g (yield 61.5%) of the compound represented by the formula (4-a).

2) Synthesis of Compound Represented by Formula 4-b

The compound represented by Chemical Formula 4-b was synthesized according to Reaction Scheme 19 below.

Scheme 19

                                 [Formula 4-b]

 Into a 250 mL round bottom flask, 1.1 g (43.8 mmol) of magnesium and 50 mL of tetrahydrofuran were added, and 11.0 g (36.5 mmol) of the compound represented by Formula 4-a obtained in Scheme 18 was dissolved in 60 mL of tetrahydrofuran, and then slowly added dropwise thereto. It was refluxed for 1 hour. After the temperature was lowered to room temperature, 4.4 g (36.5 mmol) of 4-methylpicolin aldehyde was dissolved in tetrahydrofuran (40 mL), and the mixture was stirred for 10 hours. The reactant was poured into a saturated aqueous ammonium chloride solution, the organic layer was dried and concentrated under reduced pressure, and then the solid obtained by column chromatography with ethyl acetate developing solvent was dried to obtain a compound represented by Chemical Formula 4-b. 6.8 g (55.2% yield)

3) Synthesis of Compound Represented by Chemical Formula 4-c

The compound represented by Chemical Formula 4-c was synthesized by Reaction Scheme 20 below.

[Reaction Scheme 20]

                           [Chemical formula 4-c]

In a 100 mL round bottom flask, 6.5 g (18.9 mmol) of the compound represented by Chemical Formula 4-b obtained in Scheme 19 was dissolved in 50 mL of methanol and 10 mL of sulfuric acid, and 10 g of Pd / C was added thereto. Hydrogen was added at room temperature, stirred until the hydrogen was consumed, the catalyst was filtered off, neutralized with 10% aqueous sodium hydroxide solution, extracted with dichloromethane, and concentrated under reduced pressure. The solid obtained by column chromatography with ethyl acetate developing solvent was dried to obtain a compound represented by the formula (4-c). 3.0 g (49.1% yield)

4) Synthesis of Compound Represented by Chemical Formula 4-d

The compound represented by Chemical Formula 4-c was synthesized according to Scheme 21 below.

[Reaction Scheme 21]

                                    [Chemical formula 4-c]

Synthesis was performed in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 20.9 g (yield 89.3%) of the compound represented by the formula (4-c).

5) Synthesis of Compound Represented by Formula 4-e

The compound represented by Chemical Formula 4-e was synthesized according to Scheme 22 below.

[Reaction Scheme 22]

                                 [Formula 4-e]

Synthesis was carried out in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 4.4 g (yield 55.2%) of the compound represented by formula 4-e.

6) Chemical formula By 56  Synthesis of displayed compounds

The compound represented by Chemical Formula 56 was synthesized according to Scheme 23 below.

[Reaction Scheme 23]

                                         (56)

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 3.0 g (yield 49.2%) of the compound represented by the formula (56).

MS: m / z calcd 1071.79; found 1071.Anal. Calcd. for C ₅₂ H ₇₂ N ₃ IrSi ₅ : C, 58.27; H, 6.77; N, 3.92. Found: C, 58.36; H, 6.91 N, 3.79.

< Synthetic example  5> Preparation of a compound represented by Chemical Formula 109

1) Synthesis of Compound Represented by Chemical Formula 5-a

The compound represented by Chemical Formula 5-a was synthesized according to Scheme 24 below.

Scheme 24

                                  [Formula 5-a]

Synthesis was carried out in the same manner as in Scheme 2 of Synthesis Example 1 to obtain 7.6 g (yield 77.6%) of the compound represented by Formula 5-a.

2) Synthesis of Compound Represented by Chemical Formula 5-b

The compound represented by Chemical Formula 5-b was synthesized by Reaction Scheme 25 below.

[Reaction Scheme 25]

                             [Chemical Formula 5-b]

Synthesis was performed in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 7.9 g (yield 81.3%) of the compound represented by Formula 5-b.

3) Synthesis of Compound Represented by Chemical Formula 5-c

The compound represented by Chemical Formula 5-c was synthesized according to Scheme 26 below.

[Reaction Scheme 26]

                               [Chemical Formula 5-c]

Synthesis was carried out in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 14.2 g (yield 60.6%) of the compound represented by the formula (5-c).

4) Synthesis of Compound Represented by Chemical Formula 109

The compound represented by Chemical Formula 109 was synthesized according to Scheme 27 below.

[Reaction Scheme 27]

                                        (109)

Synthesis was performed in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 2.8 g (yield 45.1%) of the compound represented by the formula (109).

MS: m / z calcd 1033.37; found 1033.Anal. Calcd. for C ₅₂ H ₆₂ N ₃ IrSi ₄ : C, 60.42; H, 6.05; N, 4.07. Found: C, 60.99; H, 6.21 N, 3.99.

< Synthetic example  6> chemical formula With 136  Preparation of the Compounds Displayed

1) Synthesis of Compound Represented by Chemical Formula 6-a

The compound represented by Chemical Formula 6-a was synthesized according to Scheme 28 below.

[Reaction Scheme 28]

                           [Chemical Formula 6-a]

Synthesis was performed in the same manner as in Scheme 4 of Synthesis Example 1 to obtain 7.9 g (yield 60.0%) of the compound represented by Chemical Formula 6-a.

2) Synthesis of Compound Represented by Chemical Formula 6-b

The compound represented by Chemical Formula 6-b was synthesized by Reaction Scheme 29 below.

[Reaction Scheme 29]

                            [Chemical Formula 6-b]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 8.2 g (yield 77.6%) of the compound represented by Chemical Formula 6-b.

3) Synthesis of Compound Represented by Chemical Formula 6-c

The compound represented by Chemical Formula 6-c was synthesized by Reaction Scheme 30 below.

[Reaction Scheme 30]

                              [Formula 6-c]

Synthesis was performed in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 9.9 g (yield 45.7%) of the compound represented by Chemical Formula 6-c.

4) Chemical formula With 136  Synthesis of displayed compounds

The compound represented by Chemical Formula 136 was synthesized by Reaction Scheme 31 below.

[Reaction Scheme 31]

                                        &Lt; EMI ID =

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 2.3 g (yield 44.2%) of the compound represented by the formula (136).

MS: m / z calcd 971.35; found 971.Anal. Calcd. for C ₄₇ H ₆₀ N ₃ IrSi ₄ : C, 58.10; H, 6.22; N, 4.33. Found: C, 57.89; H, 6.01; N, 4.55.

< Synthetic example  7> Preparation of the compound represented by Chemical Formula 138

1) Synthesis of Compound Represented by Chemical Formula 7-a

The compound represented by Chemical Formula 7-a was synthesized according to Scheme 32 below.

[Reaction Scheme 32]

                             [Formula 7-a]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 10.9 g (yield 77.8%) of the compound represented by Chemical Formula 7-a.

2) Synthesis of Compound Represented by Chemical Formula 7-b

The compound represented by Chemical Formula 7-b was synthesized by Reaction Scheme 33 below.

[Reaction Scheme 33]

                             [Formula 7-b]

Synthesis was carried out in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 16.1 g (yield 61.8%) of the compound represented by Chemical Formula 7-b.

3) Synthesis of Compound Represented by Formula (138)

The compound represented by Chemical Formula 138 was synthesized according to Scheme 34 below.

[Reaction Scheme 34]

                                            &Lt; EMI ID =

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 2.4 g (yield 40.0%) of the compound represented by the formula (138).

MS: m / z calcd 1177.44; found 1177.Anal. Calcd. for C ₅₈ H ₇₈ N ₃ IrSi ₆ : C, 59.14; H, 6.67; N, 3.57. Found: C, 59.33; H, 6.78 N, 3.41.

< Synthetic example  8> chemical formula To 169  Preparation of the Compounds Displayed

1) Synthesis of Compound Represented by Chemical Formula 8-a

The compound represented by Chemical Formula 8-a was synthesized according to Reaction Scheme 35 below.

[Reaction Scheme 35]

                               [Formula 8-a]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 13.6 g (yield 70.1%) of the compound represented by Formula 8-a.

2) Synthesis of Compound Represented by Chemical Formula 8-b

The compound represented by Chemical Formula 8-b was synthesized by Reaction Scheme 36 below.

[Reaction Scheme 36]

                                  [Formula 8-b]

Synthesis was performed in the same manner as in Scheme 4 of Synthesis Example 1 to obtain 7.3 g (yield 69.1%) of the compound represented by Formula 8-b.

3) Synthesis of Compound Represented by Chemical Formula 8-c

The compound represented by Chemical Formula 8-c was synthesized by Reaction Scheme 37 below.

[Reaction Scheme 37]

                                        [Formula 8-c]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 7.8 g (yield 77.0%) of the compound represented by Formula 8-c.

4) Synthesis of Compound Represented by Chemical Formula 8-d

The compound represented by Chemical Formula 8-d was synthesized according to Scheme 38 below.

[Reaction Scheme 38]

                                       [Formula 8-d]

Synthesis was carried out in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 10.8 g (yield 59.3%) of the compound represented by Chemical Formula 8-d.

5) Chemical formula To 169  Synthesis of displayed compounds

The compound represented by Chemical Formula 169 was synthesized according to Scheme 39 below.

[Reaction Scheme 39]

                                      [169]

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 2.3 g (yield 41.1%) of the compound represented by Chemical Formula 169.

MS: m / z calcd 1109.40; found 1109.Anal. Calcd. for C ₅₈ H ₆₆ N ₃ IrSi ₄ : C, 62.77; H, 5.99; N, 3.79. Found: C, 63.01; H, 6.07; N, 3.61.

< Synthetic example  9> chemical formula 176 with  Preparation of the Compounds Displayed

1) Synthesis of Compound Represented by Chemical Formula 6-a

The compound represented by Chemical Formula 9-a was synthesized by Reaction Scheme 40 below.

[Reaction Scheme 40]

                            [Chemical Formula 9-a]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 11.8 g (yield 77.6%) of the compound represented by Formula 9-a.

2) Synthesis of Compound Represented by Formula 9-b

The compound represented by Chemical Formula 9-b was synthesized by Reaction Scheme 41 below.

[Reaction Scheme 41]

                               [Formula 9-b]

Synthesis was carried out in the same manner as in Scheme 4 of Synthesis Example 1 to obtain 6.4 g (yield 65.6%) of the compound represented by Formula 9-b.

3) Formula 9- c  Synthesis of displayed compounds

The compound represented by Chemical Formula 9-c was synthesized according to Scheme 42 below.

[Reaction Scheme 42]

                                     [Formula 9-c]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 5.3 g (yield 61.3%) of the compound represented by Formula 9-c.

4) Synthesis of Compound Represented by Chemical Formula 9-d

The compound represented by Chemical Formula 9-d was synthesized according to Scheme 43 below.

[Reaction Scheme 43]

                                [Formula 9-d]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 10.0 g (yield 77.2%) of the compound represented by Chemical Formula 9-d.

5) Formula 9- with e  Synthesis of displayed compounds

The compound represented by Chemical Formula 9-e was synthesized according to Scheme 44 below.

[Reaction Scheme 44]

                                          [Formula 9-e]

Synthesis was performed in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 7.6 g (yield 59.3%) of the compound represented by Formula 9-e.

6) Chemical formula To 176  Synthesis of displayed compounds

The compound represented by Chemical Formula 176 was synthesized according to Scheme 45 below.

[Reaction Scheme 45]

                                                   [176]

Synthesis was performed in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 2.0 g (yield 44.9%) of the compound represented by the formula (176).

MS: m / z calcd 1275.29; found 1275.Anal. Calcd. for C ₅₇ H ₅₄ F ₁₀ N ₅ IrSi ₄ : C, 53.67; H, 4. 27; N, 3.29. Found: C, 54.00; H, 4.39; N, 3.14.

< Synthetic example  10> Preparation of the compound represented by Chemical Formula 178

1) Synthesis of Compound Represented by Chemical Formula 10-a

The compound represented by Chemical Formula 10-a was synthesized according to Scheme 46 below.

[Reaction Scheme 46]

                          [Formula 10-a]

Synthesis was carried out in the same manner as in Scheme 2 of Synthesis Example 1 to obtain 19.1 g (yield 77.2%) of the compound represented by Formula 10-a.

2) Synthesis of Compound Represented by Chemical Formula 10-b

The compound represented by Chemical Formula 10-b was synthesized by Reaction Scheme 47 below.

[Reaction Scheme 47]

                         [Formula 10-b]

Synthesis was carried out in the same manner as in Scheme 4 of Synthesis Example 1 to obtain 10.4 g (yield 62.4%) of the compound represented by Formula 10-b.

3) Synthesis of Compound Represented by Chemical Formula 10-c

The compound represented by Chemical Formula 10-c was synthesized according to Scheme 48 below.

[Reaction Scheme 48]

                                 [Formula 10-c]

Synthesis was carried out in the same manner as in Scheme 1 of Synthesis Example 1 to obtain 11.6 g (yield 82.3%) of a compound represented by Chemical Formula 10-c.

4) Synthesis of Compound Represented by Chemical Formula 10-d

The compound represented by Chemical Formula 10-d was synthesized by Reaction Scheme 49 below.

[Reaction Scheme 49]

                             [Formula 10-d]

Synthesis was carried out in the same manner as in Scheme 6 of Synthesis Example 1 to obtain 14.7 g (yield 55.9%) of the compound represented by Formula 10-d.

7) Synthesis of Compound Represented by Chemical Formula 178

The compound represented by Chemical Formula 178 was synthesized by Reaction Scheme 50 below.

[Reaction Scheme 50]

                                               [178]

Synthesis was carried out in the same manner as in Scheme 7 of Synthesis Example 1 to obtain 2.4 g (yield 39.4%) of the compound represented by Chemical Formula 178.

MS: m / z calcd 1139.39; found 1139.Anal. Calcd. for C ₅₈ H ₆₈ N ₃ IrSi ₅ : C, 61.12; H, 6.01; N, 3.69. Found: C, 60.89; H, 5.91; N, 3.75.

< Example  1 to 10 The organic electroluminescent device  Produce

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in a vacuum chamber, the base pressure is 1 × 10 ^-6 torr, and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), CBP + the compound (7%) prepared by the present invention ( 300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in this order and measured at 0.4 mA.

[DNTPD]

[NPD]

[CBP]

[Alq ₃ ]

< Comparative Example  1>

An organic light emitting display device for a comparative example was manufactured in the same manner except for using Ir (ppy) ₃ of the following structural formula instead of the compound prepared by the invention in the device structure of Examples 1 to 10.

[Ir (ppy) ₃ ]

division Host Dopant Doping concentration (%) ETL V Cd / A CIEx CIEy T ₈₀ (hr) Comparative Example 1 CBP Ir (ppy) ₃ 15 Alq ₃ 7.5 38.9 0.33 0.64 68 Example 1 CBP 8 15 Alq ₃ 3.7 48.0 0.31 0.63 201 Example 2 CBP Formula 14 15 Alq ₃ 3.6 43.9 0.32 0.63 155 Example 3 CBP Formula 17 15 Alq ₃ 4.1 40.5 0.32 0.63 116 Example 4 CBP Formula 56 15 Alq ₃ 3.8 40.6 0.32 0.63 85 Example 5 CBP Formula 109 15 Alq ₃ 4.2 53.5 0.32 0.64 141 Example 6 CBP Formula 136 15 Alq ₃ 3.9 50.5 0.31 0.63 174 Example 7 CBP Formula 138 15 Alq ₃ 4.1 52.6 0.32 0.62 165 Example 8 CBP Formula 169 15 Alq ₃ 4.1 49.7 0.32 0.63 171 Example 9 CBP Formula 176 15 Alq ₃ 4.1 43.7 0.31 0.63 125 Example 10 CBP Formula 178 15 Alq ₃ 4.1 55.1 0.32 0.63 212

 In order to measure the bandgap of Formulas 8 and 14, 17, 56, 109, 136, 138, 169, 176, and 178 of the present invention, UV / Vis absorption spectrometer and Cyclic voltammetry were used. Measured.

division UVl _max PLl _max HOMO (eV) LUMO (eV) Band gap (eV) 8 291, 394, 419, 460 514 5.3 2.6 2.7 Formula 14 289, 387, 420, 460 519 5.4 2.8 2.6 Formula 17 288, 397, 422, 456 518 5.6 2.8 2.8 Formula 56 287, 382, 420, 457 517 5.6 3.0 2.6 (109) 288, 389, 420, 458 519 5.1 2.7 2.4 Formula 136 291, 389, 420, 461 519 5.3 2.6 2.7 138 290, 389, 420, 459 519 5.1 2.4 2.7 Formula 169 290, 394, 420, 462 520 5.2 2.6 2.6 Formula 176 289, 391, 419, 460 518 5.4 2.7 2.7 Formula 178 288, 392, 420, 458 519 5.3 2.6 2.7

From the results of Table 1 and Figures 2 to 6, the compound represented by [Formula 1] according to the present invention is superior in thermal properties, luminous efficiency, color purity and the like compared to Ir (ppy) ₃ is widely used as a phosphorescent material As shown, it can be seen that it can be usefully used for display devices, display devices and lighting.

Claims (8)

An organometallic compound represented by the following [Formula 1]:
[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a fluorinated alkyl group having 3 to 18 carbon atoms , Alkylamino group having 1 to 40 carbon atoms, arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms Is selected from the group consisting of
R ₄ and R ₅ are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, or a carbon atom Arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, and aryloxy group having 3 to 40 carbon atoms , A heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron;
X and Y represent carbon or nitrogen atoms,
A ₁ and A ₂ are an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, at least one containing a nitrogen atom coordinated to an iridium metal,
G is a single bond or alkylene having 1 to 4 carbon atoms,
L is one or two ligands, m, n and p are integers from 1 to 4,
R ₁ to R ₅ , X, Y, A ₁ , A ₂ , and G are each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, and 1 to 40 carbon atoms. Alkoxy group, alkylamino group of 1 to 40 carbon atoms, arylamino group of 6 to 40 carbon atoms, heteroarylamino group of 3 to 40 carbon atoms, alkylsilyl group of 1 to 40 carbon atoms, arylsilyl group of 6 to 40 carbon atoms, It may be substituted by one or more substituents selected from the group consisting of an aryl group having 40, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron. The organometallic compound of claim 1, represented by the following [Formula 2-1] to [Formula 2-3]:
[Formula 2-1] [Formula 2-2] [Formula 2-3]

In the above formula, B is a substituted or unsubstituted aromatic ring connected divalent, the aromatic ring may be condensed and connected to 1 to 8 rings, may include a hetero atom, when B is a substituted aromatic ring Each substituent is independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, an alkylamino group of 1 to 40 carbon atoms, or 6 to 40 carbon atoms Arylamino group, C3-40 heteroarylamino group, C1-40 alkylsilyl group, C6-40 arylsilyl group, C6-40 aryl group, C3-40 aryloxy group, C3 To 40 heteroaryl group, germanium group, phosphorus and boron. The organometallic compound according to claim 2, wherein L is selected from divalent ligands represented by the following formulas:

In the ligand, R ₆ is each independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, Arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, aryl jade having 3 to 40 carbon atoms And a heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, and a substituted or unsubstituted boron, and adjacent groups are bonded to each other to form an aliphatic, aromatic, Can form a condensed ring of heteroaliphatic or heteroaromatic,
R ₆ is a deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, C1-40 alkyl group, C1-40 alkoxy group, C1-40 alkylamino group, C6-40 arylamino group, carbon number 3-40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 aryloxy group, C3-C40 heteroaryl It may be substituted by one or more substituents selected from the group consisting of a group, a germanium group, phosphorus, boron. The organometallic compound according to claim 1, which is any one compound selected from the group represented by the following [Formula 4] to [Formula 184]:

[Formula 4] [Formula 5] [Formula 6] [Formula 7]

[Formula 11] &lt; EMI ID =

[Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15]

[Formula 16] [Formula 17] [Formula 18] [Formula 19]

[Formula 20] [Formula 21] [Formula 22] [Formula 23]

[Formula 24] [Formula 25] [Formula 26] [Formula 27]

[Formula 28] [Formula 29] [Formula 30] [Formula 31]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 40] [Chemical Formula 41]

[Chemical Formula 45] [Chemical Formula 46] [Chemical Formula 47]

[Chemical Formula 49] [Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58] [Chemical Formula 59]

[Chemical Formula 60] [Chemical Formula 62] [Chemical Formula 63]

[Chemical Formula 65] [Chemical Formula 66] [Chemical Formula 67]

[Chemical Formula 70] [Chemical Formula 70] [Chemical Formula 70]

[Formula 75] [Formula 75] [Formula 75]

[Chemical Formula 77] [Chemical Formula 78] [Chemical Formula 79]

[Chemical Formula 81] [Chemical Formula 82] [Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 90] [Chemical Formula 90] [Chemical Formula 90]

[Chemical Formula 93] [Chemical Formula 95] [Chemical Formula 95]

[Chemical Formula 98] [Chemical Formula 98]

[Chemical Formula 100] [Chemical Formula 101] [Chemical Formula 102] [Chemical Formula 103]

[Chemical Formula 106] [Chemical Formula 106]

[Formula 110] [Formula 110] [Formula 111]

[Formula 113] &lt; EMI ID = 113.1 &gt;

(119) &lt; EMI ID = 116.1 &gt;

[Formula 120] &lt; EMI ID =

[Formula 124] [Formula 125] [Formula 126] [Formula 127]

[Formula 131] [Formula 130] [Formula 131]

[Formula 135] [Formula 135]

[Chemical Formula 138] [Chemical Formula 138] [Chemical Formula 138]

[Formula 140] &lt; EMI ID = 141.0 &gt;

[Chemical Formula 144] [Chemical Formula 145] [Chemical Formula 146]

[Formula 148] [Formula 150] [Formula 151]

[Formula 154] [Formula 154] [Formula 155]

[Formula 15] [Formula 15]

[Formula 161] [Formula 161] [Formula 163]

[166] [166] [166]

[Formula 17] [Formula 17]

[Formula 17] [Formula 17] [Formula 17] [Formula 17]

[Formula 177] [Formula 177] [Formula 179] [Formula 179]

[Formula 177] [Formula 178] [Formula 179] [Formula 180]

[Formula 181] [Formula 182] [Formula 183] [Formula 184] The organometallic compound according to claim 1, wherein the half width of the fluorescence spectrum is 60 nm or less. Anode;
Cathode; And
An organic electroluminescent device interposed between the anode and the cathode and comprising the organometallic compound of any one of claims 1 to 5. The method according to claim 6,
The organometallic compound is an organic light emitting device, characterized in that contained in the light emitting layer between the anode and the cathode. The method of claim 7, wherein
Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode.

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