KR20050015811A - Iridium compound and organic electroluminescence device employing the same - Google Patents

Abstract

PURPOSE: Provided are an iridium compound useful as a deep blue phosphorescence compound with improved color purity and with lower electric power consumption, and an organic electroluminescence device employing the same. CONSTITUTION: The iridium compound is represented by the formula 1, wherein R1-R7 are independently hydrogen, cyano, hydroxy, halogen, or substituted or non-substituted alkyl, alkoxy, alkenyl, aryl, arylalkyl, aryloxy, heteroaryl, heteroarylalkyl, heteroaryloxy, cycloalkyl, heterocycloalkyl or alkylthio, -Si(R')(R'')(R''') or -N(R')(R'') (in which, R', R'' and R''' are independently hydrogen or C1-C20 alkyl), at least two selected from R1-R7 may be linked each other, S is a nonanionic bidentate ligand, a is an integer of 1-3, b is an integer of 0-2, a+b is 3, provided that compounds in which all of R1-R7 are hydrogen, a is 3 and b is 0, and compounds in which all of R1, R2, R3, R4 and R7 are hydrogen, both of R5 and R6 are fluorine, X is picolinate, a is 3 and b is 1 are excluded. The organic electroluminescence device comprises an organic membrane containing the iridium compound between a pair of electrodes.

Description

Iridium compound and organic electroluminescence device employing the same

The present invention relates to an organometallic compound comprising an iridium (Ir) metal and an organic electroluminescent device employing the same, and more particularly, to an iridium compound usable as a blue phosphorescent material and an organic electroluminescent device employing the same. .

An electroluminescent device (EL device) is a self-luminous display device having advantages of wide viewing angle, excellent contrast, and fast response time.

EL elements are classified into inorganic EL elements and organic EL elements according to materials for forming an emitting layer. Herein, the organic EL device has an advantage of excellent luminance, driving voltage, and response speed, and multicoloring, compared to the inorganic EL device.

A typical organic EL device has a structure in which an anode is formed on a substrate, and a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially formed on the anode. Here, the hole transport layer, the light emitting layer, and the electron transport layer are organic films made of an organic compound.

 The driving principle of the organic EL element having the structure as described above is as follows.

When voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole transport layer. On the other hand, electrons are injected into the light emitting layer from the cathode via the electron transport layer, and carriers are recombined in the light emitting layer to generate excitons. The excitons change from the excited state to the ground state, whereby the molecules of the light emitting layer emit light to form an image.

The light emitting material is classified into a fluorescent material using excitons in a singlet state and a phosphorescent material using a triplet state according to its light emitting mechanism. Phosphorescent materials generally have a structure of organometallic compounds containing heavy atoms, and the heavier atoms cause the triplet state of excitons, which were originally forbidden transitions, to emit phosphorescent light through an acceptable transition. Phosphorescent materials can use triplet excitons with 75% probability of production and can have much higher luminous efficiency than fluorescent materials using 25% singlet excitons.

As luminescent materials using triplets, various phosphorescent materials using iridium and platinum metal compounds have been published (Sergey Lamansky etc. Inorg. Chem., 40, 1704-1711, 2001, Sergey Lamansky etc.). J. Am. Chem. Soc. , 123, 4304-4312, 2001, US 20020182441A, & AB Tamayo etc. J. Am. Chem. Soc. (2003) "Synthesis and Chracterization of Facial and Meridional Tris-cyclimetalated Irdium (III) Blue luminescent material, based on (4,6-F2ppy) 2Irpic (Chihaya Adachi etc. Appl. Phys. Lett ., 79, 2082-2084, 2001) or fluorinated ppy ligand structure Ir compound (Vladimir V. Grushin etc. Chem. Commun ., 1494-1495, 2001) has been developed, but the red and green phosphorescence due to the emission color in the sky blue region or the absence of a host material suitable for blue materials Very low efficiency and long life compared to materials, resulting in deep blue light emission The development of phosphorescent materials is very urgent.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a new blue phosphorescent compound having a deep blue light emission with low power consumption while improving color purity characteristics compared to existing blue light emitting materials in order to solve the above problems.

Another object of the present invention is to provide an organic electroluminescent device employing the blue phosphorescent compound.

In order to achieve the first technical problem, the present invention provides an iridium compound represented by the following Chemical Formula 1.

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are each independently a hydrogen atom, a cyano group, a hydroxyl group, a thiol group, a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C6-C30 Arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C2-C30 heteroarylalkyl group, substituted or unsubstituted C2- C30 heteroaryloxy group, substituted or unsubstituted C5-C20 cycloalkyl group, substituted or unsubstituted C2-C20 heterocycloalkyl group, C1-C20 alkylthio group or -Si (R ') (R ") (R ''') (wherein R' and R '' is hydrogen or an alkyl group of C1-C20 irrespective of each other) , -N (R ') (R'') (wherein R' and R '' Is independently of each other hydrogen or C1-C20 Alkyl group),

At least two selected from R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, and R ₇ may be connected to each other,

X is a monoanionic, bidentate ligand,

a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 3.

Provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are all hydrogen, a is 3 and b is 0, and R ₁ , R ₂ , R ₃ , R ₄ and R All ₇ are hydrogen, R ₅ and R ₆ are all fluorine, X is picolinate (pic), a is 2 and b is 1 except where.

Another technical problem of the present invention is to provide an organic electroluminescent device having an organic film between a pair of electrodes,

The organic film is made of an organic electroluminescent device, characterized in that it comprises the iridium compound.

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

The present invention provides an iridium compound represented by the following Chemical Formula 1, which is a blue light emitting material, and has a dark blue light emission characteristic than the conventionally proposed molecules, and therefore, a blue color for a full color organic electroluminescent device. It can be used as a phosphorescent dopant.

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are each independently a hydrogen atom, a cyano group, a hydroxyl group, a thiol group, a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C6-C30 Arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C2-C30 heteroarylalkyl group, substituted or unsubstituted C2- C30 heteroaryloxy group, substituted or unsubstituted C5-C20 cycloalkyl group, substituted or unsubstituted C2-C20 heterocycloalkyl group, C1-C20 alkylthio group or -Si (R ') (R ") (R ''') (wherein R' and R '' is hydrogen or an alkyl group of C1-C20 irrespective of each other) , -N (R ') (R'') (wherein R' and R '' Is independently of each other hydrogen or C1-C20 Alkyl group),

At least two selected from R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, and R ₇ may be connected to each other,

X is a monoanionic, bidentate ligand,

a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 3.

Provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are all hydrogen, a is 3 and b is 0, and R ₁ , R ₂ , R ₃ , R ₄ and R All ₇ are hydrogen, R ₅ and R ₆ are all fluorine, X is picolinate (pic), a is 2 and b is 1 except where.

In particular, in Formula 1, two or more selected from R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, and R ₇ may be connected to each other to form a ring system. For example, R ₁ and R ₂ , R ₂ and R ₃ , R ₁ , R ₂ and R ₃ , R ₄ and R ₅ , R ₅ and R ₆ , R ₄ , R ₅ and R ₆ , R ₆ and One or more selected from R ₇ , R ₅ , R ₆ and R ₇ may be linked to each other to form a ring system.

In particular, the iridium compound of Formula 1 is represented by the following formula (2a) or (2b) according to a combination of a and b. The compound of Formula 2b is when a is 3, b is 0, and the compound of Formula 2a is a is 2, b is 1.

Wherein X is as defined in formula (1).

The X is acetylacetonate (acac), hexafluoroacetylacetonate (hexafluoroacetylacetonate), salicylidene (sal), picolinate (picolinate: pic), 8-hydride represented by the following structural formula Oxyquinolinate (8-hydroxyquinolinate), α-amino acid L-proline (L-pro), benzoylacetonate (benzoylacetonate (bza), dibenzoylmethane (dbm), tetramethylheptanedione (tetrametylheptandione: tmd), (1- (2-hydroxyphenyl) pyrazolate) (1- (2-hydoxyphenyl) pyrazolate: oppz).

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are methyl, ethyl, propyl, n-butyl, isopropyl, tert-butyl, sec- regardless of each other. Butyl, tert-amyl, trifluoromethyl, pentafluoroethyl, perfluoroalkyl, benzyl, 4- (tertbutyl) benzyl, 3,5-di- (tertbutyl) benzyl, 3,5-di- ( Isopropyl) benzyl, naphthyl, phenyl, furyl, thienyl, pyridyl, cyano, It is preferably selected from the group consisting of methoxy, ethoxy and halogen atoms.

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are selected from the group consisting of halogen atoms, methyl, ethyl, propyl, phenyl, cyano groups regardless of each other. It is preferable.

In addition, in the iridium compound of formula 1 according to the present invention, R ₁ , R ₂ , R ₃ are methyl or ethyl irrespective of each other, and R ₄ , R ₅ , R ₆ , R ₇ are halogen atoms, irrespective of each other, It is preferably selected from the group consisting of methyl, ethyl, phenyl and cyano groups. Specific examples of such cases are as follows.

Wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are all methyl groups, R ₁₄ is a methyl group, a phenyl group, a cyano group, or a halogen atom, and R ₁₅ and R ₁₆ are Regardless, it is a methyl group, a phenyl group, a cyano group or a halogen atom.

The compound represented by the formula (1) according to the present invention is a blue light emitting material, especially a dark blue light emitting material. The main reason for the dark blue light emission of the iridium compound of Chemical Formula 1 is that the p conjugation of the pyridine ring pentagon structure of the pyrisol ring pentagon structure, unlike the conventional material, is converted into a pyrazole ring pentagon structure. Reducing the length increases the band gap (Eg) and enables blue-shift. In particular, by introducing a -CN substituent, a strong electron withdrawing group in the phenyl ring to increase the repulsive force between molecules and molecules, the volatilization property is increased to facilitate deposition. In addition, it reduces the intermolecular interactions to prevent the concentration decay effect, thereby suppressing the crystallization, increase the thin film stability and increase the luminous efficiency. In the case of phenyl group substitution, an aromatic ring substituent is introduced to increase thermal stability and thus to increase thin film stability to increase luminous efficiency. Introduction of an alkyl group such as a methyl group induces a steric hindrance effect by substitution of a methyl group, thereby reducing intermolecular interactions and preventing a concentration decay effect resulting from intermolecular interactions, as shown in FIG. 8. The efficiency was greatly increased. Such properties increase the luminous efficiency by suppressing crystallization in the thin film to improve the thin film properties.

The iridium compound represented by Chemical Formula 1 is particularly preferably a compound represented by Chemical Formulas 4, 5, 7 to 24.

Looking at the synthesis method of the compound represented by Formula 1 as follows. Compound of formula (1) can be synthesized by various reaction routes known in the art, wherein the synthesis method according to an embodiment is as follows.

First, a phenyl pyrazole compound is synthesized as shown in Scheme 1 below.

Phenyl pyrazole compound

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are as described above,

X is a halogen atom.

Thereafter, the phenyl pyrazole compound and the iridium compound are reacted to obtain an iridium compound represented by the formula (2b) (when there is no X ligand) among the compounds of the formula (1). Here, as the iridium compound, Ir (acac) ₃ or the like is used.

In the compound of Formula 1, the iridium compound of Formula 2a (when X ligand is present) is prepared by reacting the phenyl pyrazole compound, the iridium compound, and the X ligand-containing compound (XH). Here, as an example of the iridium compound, IrCl ₃ or the like is used.

Specific examples of the unsubstituted C1-C20 alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like. The hydrogen atom is a halogen atom, C1-C30 alkyl group, C1-C30 alkoxy group, lower alkylamino group, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group, sulfonic acid group, phosphoric acid group It may be substituted with a substituent.

Specific examples of the unsubstituted C2-C20 alkenyl group which is a substituent used in the present invention include an ethylene group, a propylene group, an isobutylene group, a vinyl group, an allyl group, and the like, and at least one hydrogen in the alkenyl group. Atoms include substituents such as halogen atoms, C1-C30 alkyl groups, C1-C30 alkoxy groups, lower alkylamino groups, hydroxy groups, nitro groups, cyano groups, amino groups, amidino groups, hydrazines, hydrazones, carboxyl groups, sulfonic acid groups, and phosphoric acid groups. It may be substituted by.

Specific examples of the unsubstituted C1-C20 alkoxy group which is a substituent used in the compound of the present invention are methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hex Siloxy etc. are mentioned, One or more hydrogen atoms of the said alkyl can be substituted by the same substituent as the case of the C1-C20 alkyl group mentioned above.

The aryl group, which is a substituent used in the compound of the present invention, means a carbocyclic aromatic system having 6 to 30 carbon atoms including one or more rings, and the rings may be attached or fused together by a pendant method. The term aryl includes aromatic systems such as phenyl, naphthyl, tetrahydronaphthyl. In addition, at least one hydrogen atom of the aryl group may be substituted with the same substituent as in the case of the C 1 -C 20 alkyl group described above.

The arylalkyl group, which is a substituent used in the compound of the present invention, means that some of the hydrogen atoms in the aryl group as defined above are substituted with lower alkyl groups such as methyl, ethyl, propyl and the like. For example benzyl, phenylethyl, 4- (tertbutyl) benzyl, 3,5-di- (tertbutyl) benzyl, 3,5-di (isopropyl) benzyl and the like. At least one hydrogen atom of the arylalkyl group may be substituted with the same substituent as in the case of the above-described C1-C20 alkyl group.

The heteroaryl group, which is a substituent used in the compound of the present invention, contains 1, 2 or 3 heteroatoms selected from N, O, P or S, and the monovalent monocyclic having 2 to 30 ring atoms having the remaining ring atoms of C. Ring compounds or the rings may be attached or fused together in a pendant manner. Examples of the heteroaryl group include pyridyl, thienyl, furyl and the like.

The heteroarylalkyl group means that a part of the hydrogen atoms of the heteroaryl group is substituted with a lower alkyl group, and the definition of heteroaryl in the heteroarylalkyl group is as described above. At least one hydrogen atom of the heteroarylalkyl group may be substituted with the same substituent as in the case of the C 1 -C 20 alkyl group described above.

The cycloalkyl group means monovalent monocyclic having 4 to 30 carbon atoms. At least one hydrogen atom of the cycloalkyl group may be substituted with the same substituent as in the case of the C 1 -C 20 alkyl group described above.

The heterocycloalkyl group includes 1, 2 or 3 heteroatoms selected from N, O, P, or S, and means a monovalent monocyclic monocyclic monocyclic having 1 to 30 ring atoms, wherein the remaining ring atoms are C. The cycloalkyl group It means that a part of the hydrogen atom of is substituted with a lower alkyl group. At least one hydrogen atom of the cycloalkyl group may be substituted with the same substituent as in the case of the C 1 -C 20 alkyl group described above.

The compound represented by the formula (1) according to the present invention can be usefully applied to various image display devices as a dark blue light emitting material. In particular, it is possible as a host material or dopant in forming the red (R), green (G) and blue (B) light emitting layers of the organic EL device.

Hereinafter, an organic electroluminescent device employing the compound of Chemical Formula 1 and a method of manufacturing the same will be described.

Compound of Formula 1 can be used in the light emitting layer forming material when forming the organic electroluminescent device, the method of manufacturing an organic electroluminescent device (see FIG. 1) according to a preferred embodiment using the same will be described.

First, a patterned first electrode 12 is formed on the substrate 11 (not shown). The substrate 11 is a substrate used in a conventional organic electroluminescent device, preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof. And the thickness of the substrate 11 is preferably 0.3 to 0.7 mm.

The first electrode 12 may be formed of a conductive metal or an oxide thereof, which is easy to inject holes, and specific examples thereof may include indium tin oxide (ITO), indium zinc oxide (IZO), nickel (Ni), and platinum. (Pt), gold (Au), iridium (Ir) and the like are used.

After cleaning the substrate 11 on which the first electrode 12 is formed, UV / ozone treatment is performed. At this time, an organic solvent such as isopropanol (IPA) or acetone is used as the washing method.

A hole injection layer (HIL) 13 is selectively formed on the first electrode 12 of the cleaned substrate 11. When the hole injection layer 13 is formed in this manner, the contact resistance between the first electrode 12 and the hole transport layer 14 is reduced, and the hole transport capacity of the first electrode with respect to the light emitting layer is improved, thereby driving the device. It is possible to obtain the effect of improving overall and lifespan characteristics. The material for forming the hole injection layer 13 may be water-soluble material such as PEDOT {poly (3,4-ethylenedioxythiophene)} / PSS (polystyrene parasulfonate), a starburst amine material (e.g., IDE 406 (Idemitsu Kosan)), and the like. The same material is used, and spin-coating is performed on the first electrode 12 using the material, and then dried to form the hole injection layer 13.

When HIL is PEDOT which is a water-soluble substance, the drying temperature is preferably 100 to 250 ° C, more preferably about 200 ° C. In the case of other materials that can be vacuum deposited, the next layer is laminated without special measures.

A hole transport layer (HTL) 14 is formed on the hole injection layer 13.

The material for forming the hole transport layer 14 is not particularly limited, and N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine represented by Formula 26 {N, N'-di (naphthalene-1-yl) α-N, N '-diphenyl-benzidine: α -NPB} and the like are used, and the hole transport layer formation method is not particularly limited, but spin coating or vacuum deposition is used, and in the case of small molecules, vacuum deposition is used.

Subsequently, an emission layer (EML) 15 is formed on the hole transport layer 14. At this time, when the light emitting layer 15 is formed, it is possible to use the iridium compound of Formula 1 alone or in combination with a conventional host material using it as a dopant. As the host material, CBP (4,4'-Bis (carbazol-9-yl) -biphenyl represented by Chemical Formula 26 may be used.

The method of forming the light emitting layer 15 is not particularly limited, but a co-deposition method is used. When the compound of Formula 1 is used as a dopant, the content thereof is not particularly limited, and is preferably 5 to 40 parts by weight based on 100 parts by weight of the material for forming the light emitting layer 15. If the content of the dopant is out of the above range, the luminescence property of the EL element is lowered, which is not preferable.

It is preferable that the film thickness of the said light emitting layer 15 is 100-500 kPa. If the thickness of the light emitting layer 15 is less than 100 mW, the luminous efficiency is lowered.

A hole suppression layer (HBL) 16 is formed on the light emitting layer 15 to prevent excitons formed from the light emitting material from moving to the electron transport layer or to prevent holes from moving to the electron transport layer 17. . In this case, the material for forming the hole suppression layer 16 may be a phenanthrolines-based compound (eg, UDC, BCP), an imidazole-based compound, a triazoles-based compound, or an oxadiazoles-based compound. Compounds such as PBD, aluminum complex (UDC) and BAlq of the following structural formula are used. And its forming method is not particularly limited, and depending on the forming material, a deposition or spin coating method is used.

An electron transport layer (ETL) 17 is formed on the hole suppression layer 16. Examples of the material for forming the electron transport layer 17 include a compound of Formula 28, an oxazole compound, an isoxazole compound, a triazole compound, an isothiazole compound, an oxadiazole compound, and a thiadiazole compound. Compounds, perylene compounds, aluminum complexes such as Alq3 (tris (8-quinolinolato) -aluminum) BAlq, SAlq, Almq3, gallium complexes such as Gaq ' ₂ OPiv, Gaq' ₂ OAc, 2 (Gaq ' ₂ )) is used, and the electron transport layer 17 is formed by a vacuum deposition method or a spin coating method depending on the formation material.

 Perylene-Based Compound

     Alq3 BAlq

    SAlq Almq3

Gaq ' ₂ OPiv Gaq' ₂ OAc, 2 (Gaq'2)

An electron injection layer (EIL) 18 is stacked on the electron transport layer 17. As the forming material thereof, Alq3, LiF, NaCl, CsF and the like having the above-described structural formulas are used, and the forming method thereof is a vacuum deposition method or a spin coating method depending on the forming material. The thickness of the electron injection layer 18 is preferably in the range of 1 to 15 GPa.

A second electrode 19 is formed on the electron injection layer 18, and the resultant is sealed to complete the organic EL device.

The second electrode 19 is formed by depositing it using a metal having a small work function, that is, Li, Ca, LiF / Ca, LiF / Al, Al, Mg, or Mg alloy. The thickness of the second electrode 19 is preferably 800 to 3000 kPa.

The organic electroluminescent device of the present invention may have a lamination structure as shown in FIG. 1, and it is also possible to further form one or two intermediate layers as necessary. In addition, a hole suppression layer, an electron injection layer, etc. are a layer which can be selectively formed, and may not be formed in some cases.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the technical spirit of the present invention is not limited to the following examples.

Reagents Used

Calcium phosphate tribasic monohydrate, 1,4-dioxane, cupper iodide, (+,-)-trans-1,2-diaminocyclohexane are available from Acros Corporation. Product was used, iridium chloride hydrate, iridium chloride acetylacetonate, glycerol, 2-methoxyethanol, 2-ethoxyethanol, 1-pyrazole, 3-methyl-1-phenylpyrazole, 3-methyl-1- m-tolylpyrazole, 3,5-dimethyl-1-phenylpyrazole, 3-iodobenzonitrile, 4-iodobenzonitrile, acetylacetone and picolinic acid were used as products of Aldrich. . And methylene chloride, methanol, hexane, magnesium sulfate, magnesium carbonate used the product of Duksan Chemical.

Common way

All new compounds were identified by ¹ H-NMR, ¹³ C-NMR, UV and spectrofluorometers. ¹ H-NMR and ¹³ C-NMR were recorded using Bruker AM-300 spectrometer, UV was used for BECKMAN DU-650, and JASCO FP-7500 was used as spectrofluorometer. All chemical mobility was reported in ppm based on the solvent.

Synthesis Example 1 Preparation of 3-pyrazol-benzonitrile represented by Chemical Formula 3

Copper iodide (0.01 mmol), calcium phosphate tribasic monohydrate (2.1 mmol), 1-pyrazole (1.2 mmol) and 1,4-dioxane (10 mL) were added to a sealed tube, Nitrogen was injected and stirred for 30 minutes. Subsequently, 3-yodo benzonitrile, (+,-)-trans-1,2-diaminocyclohexane (0.1 mmol) was added to the reaction mixture, and the stopper was closed and heated at 110 ° C. for about 24 hours, followed by stirring.

After confirming the reaction state of the reaction mixture by Thin Layer Chromatography (TLC) to complete the reaction, the solvent was removed by high vacuum distillation. The resultant was then extracted with methylene chloride and then washed with saturated aqueous NaCl solution. The extracted methylene chloride solution was dried using MgSO ₄ and subjected to fresh column chromatography (eluent: methylene chloride and methanol) to obtain a solid material. The solid material thus obtained was dried under vacuum conditions for 3 hours to obtain a compound of formula 3. (Yield: 50%)

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 8.04 (d, J = 1.11.1H) 7.99 to 7.95 (m, 2H) 7.78 (d, J = 1.53,1H) 7.62 to 7.53 (m, 2H ) 6.54 (t, J = 2.11.1H)

Synthesis Example 2: Preparation of Compound (A)

Nitrogen was injected into 2-methoxyethanol (100 ml) at room temperature and stirred for 30 minutes, followed by addition of iridium chloride hydrochloride hydrate (4 mmol) and 3-pyrazole-benzonitrile (10 mmol), followed by nitrogen gas atmosphere. Under heating for 12 hours.

After the reaction was completed, the reaction mixture was distilled under high vacuum to remove the solvent, and then extracted with methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, and the extracted methylene chloride solution was removed using MgSO ₄ . Subsequently, the resultant was distilled under reduced pressure to leave a minimum amount of solvent, and then hexane was added to obtain a solid substance. The obtained solid material was filtered and then dried under vacuum for about 3 hours to obtain compound (A). (Yield 50%)

Synthesis Example 3: Compound Ir represented by Chemical Formula 4 (5-CNphenyl-pyrazol) ₂ manufacture of (acac)

After stirring for 30 minutes while injecting nitrogen into 2-ethoxyethanol (100 ml) at room temperature, Compound A (5 mmol) and acac salt (15 mmol) were added thereto, and 3N Na ₂ CO ₃ (2.5 ml) was added as a base. After stirring for 12 hours under a nitrogen gas atmosphere, the reaction was confirmed by TLC. The solvent was removed by high vacuum distillation and extracted with methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution. The extracted methylene chloride solution was removed with water using MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and then hexane was added to obtain a solid substance. The resulting product was filtered, and once again purified by column chromatography, dried under a vacuum pump for 3 hours to obtain a compound of formula 4 (yield: 50%).

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 8.82 (d, J = 2.874 Hz, 2H), 7.86 (d, J = 1.5 Hz, 2H), 7.81 (d, J = 2.157 Hz, 2H) , 6.97 to 6.52 (m, 4H), 6.41 (d, J = 7.773 Hz, 2H), 5.34 (s, 1H), 1.77 (s, 6H)

Synthesis Example 4 Compound Ir (5-CNphenyl-pyrazol) of Formula 5 ₂ (pic))

After stirring for 30 minutes while injecting nitrogen into 2-ethoxyethanol (100 ml) at room temperature, Compound (A) (5 mmol), picolinic acid (15 mmol) and 3N Na ₂ CO ₃ (2.5 ml) were added. After the reaction mixture was stirred for 12 hours under nitrogen atmosphere, the reaction progress was confirmed by TLC.

The reaction mixture was distilled under high vacuum to remove the solvent, and extracted with methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution. The extracted methylene chloride solution was removed with water with MgSO ₄ and the solvent was distilled off under reduced pressure, and hexane was added thereto to obtain a solid substance. This was filtered and once again purified by column chromatography and dried under vacuum pump for 3 hours to obtain a compound of formula 5 (yield: 50%).

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 8.38 (d, J = 7.626 Hz, 1H), 8.19 (d, J = 2.859 Hz, 1H), 8.165 (d, J = 2.87 Hz, 1H) , 8.017 (td, J = 1.45 Hz, 7.713 Hz, 1H), 7.467 (m, 3H), 7.029 (dd, J = 1.53 Hz, 7.78 Hz, 1H), 6.96 (dd, J = 1.428 Hz, 7.73 Hz, 1H), 6.8392 (d, J = 2.172 Hz, 1H), 6.7514 (t, J = 5.154 Hz, 1H), 6.5772 (t, J = 5.05 Hz, 1H), 6.5022 (d, J = 7.82 Hz, 1H) , 6.1772 (d, J = 7.797 Hz, 1H)

Synthesis Example 5 Preparation of Compound (4-pyrazol-bezonitrile) Represented by Chemical Formula 6

To the sealing tube was added copper iodide (0.01 mmol) and calcium phosphate tribasic monohydrate (2.1 mmol), 1-pyrazole (1.2 mmol), 1,4-dioxane (10 mL), which was then heated under nitrogen gas atmosphere. Stirred for a minute. Subsequently, 4-iodobenzonitrile, (+,-)-trans-1,2-diamino-cyclohexane (0.1 mmol) was added to the reaction mixture, and the stopper was closed. Then, the mixture was heated and stirred at 110 degrees for about 24 hours. .

After confirming completion of the reaction mixture by TLC, the solvent was removed by high vacuum distillation. The reaction mixture was then extracted with methylene chloride and then washed with saturated aqueous NaCl solution. The extracted methylene chloride solution was removed with MgSO _{4 and} then subjected to fresh column chromatography (eluent: methylene chloride and methanol) to obtain a solid material. The solid material thus obtained was dried for about 3 hours under a vacuum pump to obtain a compound represented by Chemical Formula 6. (Yield 75%)

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 8.00 (d, J = 2.86,1H) 7.84 to 7.81 (m, 2H) 7.77 to 7.71 (m, 3H) 6.53 (t, J = 2.06,1H )

Synthesis Example 6 Preparation of Compound (B)

After stirring for 30 minutes while injecting nitrogen into 2-methoxyethanol (100 ml) at room temperature, iridium chloride hydrochloride hydrate (4 mmol) and 4-pyrazole-benzonitrile (10 mmol) were added thereto, and the mixture was heated and stirred under a nitrogen gas atmosphere. It was.

After confirming the progress of the reaction by TLC, the reaction mixture was extracted with methylene chloride after removing the solvent by high vacuum distillation. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution. After removing the water of the extracted methylene chloride solution with MgSO ₄ and leaving a minimum amount of solvent by distillation under reduced pressure, hexane was added to obtain a solid material. After filtering the solid material thus obtained, it was dried for about 3 hours in a vacuum pump to give a compound (B) (yield: 75%).

Synthesis Example 7 Preparation of Compound represented by Formula 7 (Ir (4-CNphenyl-pyrazol) 2 (acac))

After stirring for 30 minutes while injecting nitrogen into 2-ethoxyethanol (100 ml) at room temperature, Compound (B) (5 mmol) and acac salt (15 mmol) were added thereto, and 3N Na 2 CO 3 (2.5 ml) was added as a base. The reaction mixture was stirred under heating with nitrogen gas for 12 hours.

After completion of the reaction by confirming the reaction state of the reaction mixture by TLC, the solvent was removed by distillation under high vacuum. The reaction mixture was extracted with methylene chloride, and the extracted methylene chloride layer was washed with saturated aqueous NaCl solution.

The extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and then hexane was added to obtain a solid substance. After filtration, the resultant was purified once more by column chromatography and dried under vacuum pump for 3 hours to obtain a compound represented by Chemical Formula 7. (Yield: 50%)

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 8.15 (d, J = 2.78 Hz, 2H), 7.66 (d, J = 1.74 Hz, 2H), 7.22 (d, J = 4.59 Hz, 4H) , 6.78 (t, J = 4.734 Hz, 2H), 6.4778 (s, 2H), 5.2902 (s, 1H), 1.8508 (s, 6H), 1.5848 (s, 5H)

Synthesis Example 8 Preparation of Compound (Ir (4-CNphenyl-pyrazol) 2 (pic)) Represented by Chemical Formula 8

Nitrogen was injected into 2-ethoxyethanol (100 ml) at room temperature and stirred for 30 minutes, followed by compound (B) (5 mmol), picolinic acid (15 mmol) and 3N Na ₂ CO ₃ (2.5 ml) as a base. Was added.

Under a nitrogen gas atmosphere, the reaction mixture was stirred with heating for 12 hours, and then TLC confirmed the completion state of the reaction. The reaction mixture was then vacuum dried under high vacuum to remove the solvent and extracted using methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, and the methylene chloride layer was removed with MgSO ₄ and then distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added to obtain a solid material. Subsequently, the solid material was filtered and then purified once more through a column chromatograph and dried for 3 hours under a vacuum pump to obtain a compound represented by Formula 8. (Yield: 50%)

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 8.37 (d, J = 7.79 Hz, 1H), 8.176 (t, J = 5.28 Hz, 2H), 8.0084 (td, 1H), 8.3834 (d, J = 2.364 Hz, 2H), 7.4492 (td, 14.29 Hz, 1H), 7.3456 (s, 2H), 7.2812 (m, 3H), 6.8580 (d, J = 2.18 Hz, 1H), 6.77422 (t, J = 5.187 Hz, 1H), 6.64209 (m, 2H), 6.45282 (s, 1H)

Synthesis Example 9 Compound represented by Chemical Formula 9 (fac Ir (5-methyl-phenylpyrazol) ₃ Manufacturing

In a nitrogen gas atmosphere, glycerol (100 mL) was stirred at room temperature for 30 minutes, and then Ir (acac) ₃ and 3-methyl-1-phenylpyrazole (6eq) were added thereto and heated at 180 to 200 ° C. for about 24 hours. Stirred.

After the reaction of the reaction mixture was terminated, water was added thereto to obtain a crude product with a glass filter, which was washed with hexane. The resultant was dissolved in methylene chloride, and then purified again by fresh chromatography, which was dried for about 3 hours under a vacuum pump to obtain a compound of formula 9. (Yield: 20%) The crystal structure of the compound of formula 9 obtained by dissolving 1 part by weight of methanol in methylene chloride and then diffusing hexane is shown in FIG. 12.

¹ H-NMR (CDCl ₃ , 300 MHz): 7.93 (d, J = 2.31, 3H) 7.18 (d, J = 13.44, 3H) 6.92 (t, J = 3.58, 3H) 6.74-6.62 (m, 6H) 6.14 (d, J = 2.55,3H) 1.708 (s, 9H)

                                Formula 10

Synthesis Example 10 Preparation of Compound (fac Ir (3,5-dimethyl-phenylpyrazol) 3) Represented by Chemical Formula 10

After stirring glycerol (100 mL) for 30 minutes at room temperature in a nitrogen gas atmosphere, Ir (acac) ₃ and 3,5-dimethyl-1-phenylpyrazole (6eq) were added thereto, and the mixture was stirred at 180 to 200 ° C for about 24 hours. Heated and stirred.

After the reaction of the reaction mixture was completed, water was added to the reaction mixture to obtain a crude product with a glass filter which was washed with hexane. The resultant was dissolved in methylene chloride, and then purified again through fresh chromatography, and dried for about 3 hours under a vacuum pump to obtain a compound represented by Formula 10. (Yield: 20%)

¹ H-NMR (CDCl ₃ , 300 MHz): 7.39 (d, J = 8.04, 3H) 6.90-6.84 (m, 3H) 6.70-6.61 (m, 6H) 5.86 (s, 3H) 2.75 (s, 9H) 1.62 (s, 9H)

Synthesis Example 11 Compound of Chemical Formula 11 (fac Ir (5-methylphenyl-4-methylpyrazol) ₃ Manufacturing

After stirring glycerol (100 mL) for 30 minutes at room temperature under a nitrogen gas atmosphere, Ir (acac) ₃ and 3-methyl-1-m-tolyl-pyrazole (6eq) were added thereto, and the mixture was stirred at 180 to 200 ° C for 24 hours. It was stirred while heating.

After the reaction of the reaction mixture was completed, water was added to obtain a crude product with a glass filter, which was washed with hexane. The resultant was dissolved in methylene chloride, and then purified again through fresh chromatography, and then dried under a vacuum pump for about 3 hours to obtain a compound of formula 11 (yield: 20%).

¹ H-NMR (CDCl ₃ , 300MHz): 8.36 (s, 3H) 7.20 (s, 3H) 6.81 (s, 3H) 6.48 ~ 6.41 (m, 6H) 2.17 (s, 9H) 2.02 (s, 9H)

                                   Formula 12

Synthesis Example 12 Preparation of Compound (Ir (5-methyl-pheynylpyrazol) 2 (oppz)) of Formula 12

After stirring 2-methoxyethanol for 30 minutes at room temperature under nitrogen gas atmosphere, iridium chloride hydrochloride hydrate (4 mmol) and 3-methyl-1-phenylpyrazole (10 mmol) were added thereto, and the mixture was heated under nitrogen for 12 hours and stirred. It was.

The progress of the reaction of the reaction mixture was confirmed by TLC, and after the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent. The resultant was extracted with methylene chloride, and the methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution. The extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. The solid material was filtered and dried for about 3 hours under a vacuum pump to obtain a dimer. (Yield 50%)

After stirring 2-ethoxyethanol (100 ml) for 30 minutes at room temperature under nitrogen gas atmosphere, the said dimer (5 mmol) and OHppz (15 mmol) were added, and 3N Na2CO3 (2.5 ml) was added as a base. The reaction mixture was stirred while heating for 12 hours under a nitrogen gas atmosphere, and then the progress of the reaction was confirmed by TLC. After the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent, which was extracted with methylene chloride. The methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. After filtering the solid material, it was once again purified by column chromatography and dried for 3 hours under a vacuum pump to obtain a compound of formula 12. (Yield 50%)

¹ H-NMR (CDCl ₃ , 300 MHz): 8.02 (d, J = 2.76,2H) 7.98 (d, J = 2.12,2H) 7.857 (d, J = 2.76,1H) 7.205 (d, J = 7.638,1H ) 7.134 ~ 7.082 (m, 2H) 6,955 ~ 6.86 (m, 3H) 6.749 ~ 6.636 (m, 4H) 6.539 ~ 6,48 (m, 2H) 6.34 ~ 6.28 (m, 3H) 6.099 (d, J = 2.73 , 1H)

Formula 13

Synthesis Example 13 Preparation of Compound (Ir (2- (4-phenyl-phenyl) -5-methylpyrazol) 2 (oppz)) Of Formula 13

After stirring for 30 minutes of 2-methoxyethanol at room temperature under a nitrogen gas atmosphere, it was added with iridium chloride hydrochloride hydrate (4 mmol) and 1-biphenyl-4-yl-3-methyl-1H-pyrazole ( 10 mmol) was added and stirred under heating in a nitrogen gas atmosphere for 12 hours.

After confirming the reaction by TLC, the solvent was removed by high vacuum distillation and extracted using methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with MgSO ₄ , and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. The solid material was filtered and dried for about 3 hours under a vacuum pump to obtain a dimer. (Yield 50%)

After stirring 2-ethoxyethanol (100 ml) for 30 minutes at room temperature under nitrogen gas atmosphere, the dimer (5 mmol) and OHppz (15 mmol) were added thereto, and 3N Na ₂ CO ₃ (2.5 ml) was added as a base. It was. The reaction mixture was stirred while heating for 12 hours under a nitrogen gas atmosphere, and then the progress of the reaction was confirmed by TLC. After the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent, which was extracted with methylene chloride. The methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. After filtering the solid material, it was once again purified by column chromatography and dried for 3 hours under a vacuum pump to obtain a compound of formula (13). (Yield 50%)

¹ H-NMR (CDCl ₃ , 300MHz): 8.57 (d, J = 2.79,1H) 8.37 (d, J = 2.65,2H) 7.55 (d, J = 8.17,1H) 7.44 ~ 7.09 (m, 14H)

6.87 ~ 6.80 (m, 2H) 6.72 (d, J = 1.94,1H) 6.56 ~ 6.40 (m, 5H) 6.32 (d, J = 2,75,1H)

                               Formula 14

Synthesis Example 14 Preparation of Compound (Ir (2- (4-phenyl-phenyl) -5-methylpyrazol) 2 (pic)) of Formula 14

After stirring 2-methoxyethanol for 30 minutes at room temperature under nitrogen gas atmosphere, it was added with iridium chloride hydrochloride hydrate (4 mmol) and 1-biphenyl-4-yl-3-methyl-1H-pyrazole (10 mmol). ) Was added and stirred under heating in a nitrogen gas atmosphere for 12 hours.

After confirming the reaction by TLC, the solvent was removed by high vacuum distillation and extracted using methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with MgSO ₄ , and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. The solid material was filtered and dried for about 3 hours under a vacuum pump to obtain a dimer. (Yield 50%)

After stirring 2-ethoxyethanol (100 ml) for 30 minutes at room temperature under a nitrogen gas atmosphere, the dimer (5 mmol) and picolinic acid (15 mmol) were added thereto, and 3N Na ₂ CO ₃ (2.5 ml) was used as a base. Was added. The reaction mixture was stirred while heating for 12 hours under a nitrogen gas atmosphere, and then the progress of the reaction was confirmed by TLC. After the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent, which was extracted with methylene chloride. The methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. After filtering the solid material, it was once again purified by column chromatography and dried under vacuum pump for 3 hours to obtain a compound of formula (14). (Yield 50%)

¹ H-NMR (CDCl ₃ , 300 MHz): 8.37 (s, 1H) 8.00 ~ 7.96 (m, 4H) 7.39 ~ 7.19 (m, 17H) 6.44 ~ 6.40 (m, 2H) 2.51 (s, 3H) 1.65 (s , 3H)

                                  Formula 15

Synthesis Example 15 Compound of Formula 15 (Ir (2- (5-phenyl-phenyl) -5-methylpyrazol) ₂ (pic))

After stirring 2-methoxyethanol for 30 minutes at room temperature under a nitrogen gas atmosphere, iridium chloride hydrochloride hydrate (4 mmol) and 1-biphenyl-3-yl-3-methyl-1H-pyrazole (10 mmol) were added thereto. ) Was added and stirred under heating in a nitrogen gas atmosphere for 12 hours.

After confirming the reaction by TLC, the solvent was removed by high vacuum distillation and extracted using methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with MgSO ₄ , and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. The solid material was filtered and dried for about 3 hours under a vacuum pump to obtain a dimer. (Yield 50%)

After stirring 2-ethoxyethanol (100 ml) for 30 minutes at room temperature under a nitrogen gas atmosphere, the dimer (5 mmol) and picolinic acid (15 mmol) were added thereto, and 3N Na ₂ CO ₃ (2.5 ml) was used as a base. Was added. The reaction mixture was stirred while heating for 12 hours under a nitrogen gas atmosphere, and then the progress of the reaction was confirmed by TLC. After the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent, which was extracted with methylene chloride. The methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. After filtering the solid material, it was once again purified by column chromatography and dried for 3 hours under a vacuum pump to obtain a compound of formula 15. (Yield 50%)

¹ H-NMR (CDCl ₃ , 300MHz): 9.01 (t, J = 3.58,2H) 8.11 (s, 2H) 7.98 (d, J = 1.70,1H) 7.94 ~ 7.90 (m, 2H) 7.70 ~ 7.62 (m , 6H) 7.44 ~ 7.38 (m, 4H) 7.31 ~ 7.29 (m, 2H) 7.09 ~ 7.06 (m, 2H) 7.01 (d, J = 7.41,1H)

6.81 (t.J = 2.49,1H) 6.76 (t, J = 2.54,1H) 6.35 (d, J = 7.80,1H) 6.23 (d, J = 7.80,1H)

                                                              Formula 16

Synthesis Example 16 Preparation of Compound (fac Ir (ppz) 2 (oppz)) of Formula 16

2-methoxyethanol was stirred for 30 minutes at room temperature under a nitrogen gas atmosphere, and then, lithium hydride hydrochloride hydrate (4 mmol) and ppz (10 mmol) were added thereto, followed by stirring under heating in a nitrogen gas atmosphere for 12 hours.

After confirming the reaction by TLC, the solvent was removed by high vacuum distillation and extracted using methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with MgSO ₄ , and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. The solid material was filtered and dried for about 3 hours under a vacuum pump to obtain a dimer. (Yield 50%)

After stirring 2-ethoxyethanol (100 ml) for 30 minutes at room temperature under nitrogen gas atmosphere, the dimer (5 mmol) and OHppz (15 mmol) were added thereto, and 3N Na ₂ CO ₃ (2.5 ml) was added as a base. It was. The reaction mixture was stirred while heating for 12 hours under a nitrogen gas atmosphere, and then the progress of the reaction was confirmed by TLC. After the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent, which was extracted with methylene chloride. The methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. After filtering the solid material, it was once again purified by column chromatography and dried under vacuum pump for 3 hours to obtain a compound of formula (16). (Yield 50%)

¹ H-NMR (CDCl ₃ , 300MHz): 8.02 (d, J = 2.76,1H) 7.96 ~ 7.92 (m, 2H) 7.32 (d, J = 1.89,1H) 7.17 ~ 7.02 (m, 7H) 6.89 ~ 6.82 (m, 2H) 6.74 ~ 6.66 (m, 2H) 6.62 ~ 6.54 (m, 1H) 6.50 ~ 6.36 (m, 4H) 6.23 (d, J = 7.35,1H)

                                                                Formula 17

Synthesis Example 17 Preparation of Compound (Ir (2- (5-phenyl) -phenylpyrazol) 2 (oppz)) of Formula 17

After stirring 2-methoxyethanol for 30 minutes at room temperature under a nitrogen gas atmosphere, iridium chloride hydrochloride hydrate (4 mmol) and 1-biphenyl-3-yl-1H-pyrazole (10 mmol) were added thereto. Stirring while heating under nitrogen gas atmosphere for 12 hours.

After confirming the reaction by TLC, the solvent was removed by high vacuum distillation and extracted using methylene chloride. The extracted methylene chloride layer was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with MgSO ₄ , and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. The solid material was filtered and dried for about 3 hours under a vacuum pump to obtain a dimer. (Yield 50%)

After stirring 2-ethoxyethanol (100 ml) for 30 minutes at room temperature under nitrogen gas atmosphere, the dimer (5 mmol) and OHppz (15 mmol) were added thereto, and 3N Na ₂ CO ₃ (2.5 ml) was added as a base. It was. The reaction mixture was stirred while heating for 12 hours under a nitrogen gas atmosphere, and then the progress of the reaction was confirmed by TLC. After the reaction was completed, the reaction mixture was distilled under high vacuum under reduced pressure to remove the solvent, which was extracted with methylene chloride. The methylene chloride layer obtained by extraction was washed with saturated aqueous NaCl solution, the extracted methylene chloride solution was removed with water with MgSO ₄ and distilled under reduced pressure to leave a minimum amount of solvent, and hexane was added thereto to obtain a solid material. After filtering the solid material, it was purified again through column chromatography and dried under vacuum pump for 3 hours to obtain a compound of formula 17. (Yield: 50%) The NMR spectrum of the compound of Formula 17 in the CHCl ₃ solution state is as shown in FIG. 6.

The PL (Photoluminescence) characteristics of the iridium compounds represented by Chemical Formulas 4, 5, 7, and 8 prepared according to the synthesis example in the CH ₂ Cl ₂ solution state were examined, and the resulting PL spectrum is as shown in FIG. 2. .

Referring to FIG. 2, the iridium compounds of the cyano group-substituted phenylpyrazole ligands showed PL characteristics in a very dark blue region of 435 to 450 nm.

Investigating PL characteristics at low temperature of 77K, not at room temperature, shows the location of luminescence peaks such as metal to ligand charge transfer (MLCT) or ligand centered (LCCT) of iridium compounds. PL characteristics at were investigated, and the results are shown in FIGS. 3 and 4.

3 and 4, it can be seen that the main emission peak of the cyri group-substituted iridium compound exhibits luminescence properties in the dark blue region of 454 and 448 nm similar to those at room temperature.

Since the PMMA polymer does not emit light, it is possible to observe the light emission characteristics of the thin film state of the compound when the compound is doped, so that 6 parts by weight of the iridium compound of Formula 8 is doped into 94 parts by weight of polymethyl methacrylate The solid PL properties of the resulting films were examined and the results are shown in FIG. 5.

Referring to FIG. 5, even in the thin film state, Compound 6 showed a main emission peak in the blue region of 452 nm, indicating that red-shift due to self aggregation was not a problem.

In the iridium compounds of the formulas (9), (10), (11) and Ir (ppz) 3 prepared according to the synthesis example, PL characteristics in a CH ₂ Cl ₂ solution state were investigated, and the results are shown in FIG. 7.

Referring to FIG. 7, the compounds 9, 10, and 11 emit light in the dark blue region near 440 nm, and the emission efficiency was greater than that of Ir (ppz) 3.

In the iridium compound of Chemical Formula 11, PL characteristics at room temperature and 77 K in a CH ₂ Cl ₂ solution were investigated, and the results are shown in FIG. 8.

Referring to FIG. 8, it can be seen that Chemical Formula 11 emits light in a dark blue region near 435 nm at both room temperature and 77K.

PL properties in the CH ₂ Cl ₂ solution of Formulas 12, 13, 16, and 17 prepared according to the synthesis example were investigated, and the results are shown in FIG. 9.

Referring to FIG. 9, Formulas 12, 13, 16, and 17 emit blue light at around 440 nm at 430, and the emission intensity taken at the same concentration shows that Formula 13 is the largest.

PL properties of the iridium compound of Formula 15 prepared according to the synthesis example in the CH ₂ Cl ₂ solution state and PL properties under 77 K of the iridium compound of Formula 17 were investigated, and the results are shown in FIGS. 10 and 11. .

Referring to FIGS. 10 and 11, it was found that Formula 15 had a main emission peak of 432 nm blue region and Formula 17 had a main emission peak of 463 nm blue region.

Example 1

Corning's 10 Ω / cm 2 ITO substrate was used as an anode, and an IDE406 was vacuum deposited on the substrate to form a hole injection layer having a thickness of 600 μs. Subsequently, the TPD on the hole injection layer The compound was vacuum deposited to a thickness of 300 GPa to form a hole transport layer. Compound CBP of Chemical Formula 4 was spin coated on the hole transport layer to form a light emitting layer having a thickness of 200 μm.

Thereafter, BCP was vacuum-deposited on the emission layer to form an HBL layer having a thickness of 50 μs. Thereafter, Alq3 was vacuum deposited on the emission layer to form an electron transport layer having a thickness of 200 kHz. An organic electroluminescent device was completed by forming a LiF / Al electrode by sequentially vacuum depositing LiF 10kV and Al 3000kV on the electron transport layer.

In the organic EL device manufactured according to Example 1, luminance, color coordinates, and efficiency characteristics were measured.

As a result of the measurement, it can be seen that it is driven at high efficiency and low voltage, and it was confirmed that the color coordinate also has suitable characteristics as a blue light emitting material.

As described above, the iridium compound of Chemical Formula 1 according to the present invention is a blue phosphorescent material, which can emit deep blue light than conventional blue materials. Do.

1 is a cross-sectional view showing the structure of a general organic electroluminescent device,

FIG. 2 is a diagram showing a PL (photoluminescence) spectrum of the iridium compound represented by Chemical Formulas 4, 5, 7, 8 of the present invention in a CH ₂ Cl ₂ solution;

3 is a diagram showing a PL spectrum at 77K for the compound of Formula 7 of the present invention,

4 is a diagram showing a PL spectrum at 77K for the compound of Formula 8 of the present invention.

5 is a view showing the solid PL characteristics of a film prepared by doping 6 parts by weight of the compound of Formula 8 of the present invention with 94 parts by weight of PMMA polymer,

6 is a view showing an NMR spectrum of the iridium compound represented by the formula (17) of the present invention in the CHCl ₃ solution state,

7 is a diagram showing a photoluminescence (PL) spectrum in the state of the CH ₂ Cl ₂ solution of Ir (ppz) 3 and the iridium compound represented by Chemical Formulas 9, 10, and 11 of the present invention;

8 is a diagram showing a PL spectrum at room temperature and 77 K in a CH ₂ Cl ₂ solution state of an iridium compound represented by Chemical Formula 11 of the present invention,

9 is chemical formula 12, 13, 16 and 17 of the present invention In CH ₂ Cl ₂ solution of the iridium compound represented by a diagram showing a PL (photoluminescence) spectrum,

10 is a diagram showing a photoluminescence (PL) spectrum in the CH ₂ Cl ₂ solution state of the iridium compound represented by Chemical Formula 15 of the present invention,

11 is a diagram showing a PL spectrum obtained from 77K of the iridium compound represented by Formula 17 of the present invention,

12 is a view showing a crystal structure of an iridium compound represented by the formula ( 9) of the present invention.

<Brief description of the major symbols in the drawings>

11 substrate 12 first electrode

13 ... hole injection layer 14 ... hole transport layer

15 ... light emitting layer 16 ... hole barrier layer

17 ... electron transport layer 18 ... electron injection layer

19 ... Second electrode

Claims (9)

Iridium compound represented by the following formula (1): [Formula 1] Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are each independently a hydrogen atom, a cyano group, a hydroxyl group, a thiol group, a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C6-C30 Arylalkyl group, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C2-C30 heteroarylalkyl group, substituted or unsubstituted C2- C30 heteroaryloxy group, substituted or unsubstituted C5-C20 cycloalkyl group, substituted or unsubstituted C2-C20 heterocycloalkyl group, C1-C20 alkylthio group or -Si (R ') (R ") (R ''') (wherein R' and R '' is hydrogen or an alkyl group of C1-C20 irrespective of each other) , -N (R ') (R'') (wherein R' and R '' Is independently of each other hydrogen or C1-C20 Alkyl group), At least two selected from R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, and R ₇ may be connected to each other, X is a monoanionic, bidentate ligand, a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 3. Provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are all hydrogen, a is 3 and b is 0, and R ₁ , R ₂ , R ₃ , R ₄ and R All ₇ are hydrogen, R ₅ and R ₆ are all fluorine, X is picolinate (pic), a is 2 and b is 1 except where. The iridium compound according to claim 1, wherein when a is 3, b is 0, or when a is 2, b is 1. The method of claim 1, wherein X is acetylacetonate (acac), hexafluoroacetylacetonate (hexafluoroacetylacetonate), salicylidene (sal), picolinate (picolinate: pic), 8- Hydroxyquinolinate (8-hydroxyquinolinate), α-amino acid L-proline (L-pro), benzoylacetonate (benzoylacetonate (bza), dibenzoylmethane (dbm), tetramethylheptanedione (tetrametylheptandione: tmd) , (1- (2-hydroxyphenyl) pyrazolate) (1- (2-hydoxyphenyl) pyrazolate: oppz). The method according to claim 1, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are independently of each other methyl, ethyl, propyl, n-butyl, isopropyl, tert-butyl, sec -Butyl, tert-amyl, trifluoromethyl, pentafluoroethyl, perfluoroalkyl, benzyl, 4- (tertbutyl) benzyl, 3,5-di- (tertbutyl) benzyl, 3,5-di- (Isopropyl) benzyl, naphthyl, phenyl, furyl, thienyl, pyridyl, cyano, methoxy, ethoxy, an iridium compound characterized in that it is selected from the group consisting of halogen atoms. According to claim 1, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are independently selected from the group consisting of halogen atoms, methyl, ethyl, propyl, phenyl, cyano groups Iridium compound, characterized in that. The method of claim 1, wherein R ₁ , R ₂ , R ₃ are methyl or ethyl irrespective of each other, and R ₄ , R ₅ , R ₆ , R ₇ are halogen atoms, methyl, ethyl, phenyl, Iridium compound, characterized in that selected from the group consisting of cyano groups. The iridium compound according to claim 1, which is one of the compounds represented by the following Chemical Formulas 4-5 and 7 to 24. [Formula 4] [Formula 5] [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] In an organic electroluminescent element having an organic film between a pair of electrodes, The organic electroluminescent device according to claim 1, wherein the organic film comprises the iridium compound of any one of claims 1 to 7. The organic electroluminescent device according to claim 8, wherein the organic film is a light emitting layer.